GASIFICATION OF BIOMASS IN SUPERCRITICAL WATER

Promotion committee: Prof.dr. W.H.M. Zijm Prof.dr.ir. A. Bliek Prof.dr.ir. W.P.M. van Swaaij Dr.ir. W. Prins Dr. S.R.A.Kersten Dr.ir. L. van de Beld Prof.dr.ir. J.A.M. Kuipers Prof.dr.ir. M. Wessling Prof.dr. E. Dinjus Chairman University of Twente Secretary University of Twente Promoter University of Twente Assistant-promoter University of Twente/BTG BV Assistant-promoter University of Twente BTG B.V. University of Twente University of Twente Forschungszentrum Karlsruhe

The research reported in this thesis was executed under: 1. A grant of the Netherlands Organization for Scientific Research Chemical Sciences (NWO-CW) in the framework of the research program Towards Sustainable Technologies, subproject BIOCON with the financial contributions from Shell Global Solutions International B.V. and the Dutch Ministries of Economic Affairs (EZ/SenterNovem) and Environmental Affairs (VROM). 2. A grant of the European Commission in the framework of the Super Hydrogen program EC-contract: ENK5-CT2001-00555. 3. A grant of the New Energy and Industrial Technology Development Organization (NEDO) from Japan in the framework of the research program Technical Feasibility of Biomass Gasification in a Fluidized Bed with Supercritical Water.

Cover designer: Vesna Smiljani Publisher: Whrmann Print Service, Zutphen, The Netherlands Biljana Potic, Enschede, The Netherlands, 2006

No part of this work may be reproduced by print, photocopy or any other means without the permission in writing from the author. ISBN 90-365-2367-2

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GASIFICATION OF BIOMASS IN SUPERCRITICAL WATER

Proefschrift

ter verkrijging van de graad van doctor aan de Universiteit Twente, op gezag van de rector magnificus, prof. dr. W.H.M. Zijm, volgens besluit van het College voor Promoties in het openbaar te verdedigen op vrijdag 12 mei 2006 om 13.15 uur

door Biljana Potic geboren op 20 september 1970 te Novi Sad, Servi en Montenegro

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Dit proefschrift is goedgekeurd door de promotor: Prof.dr.ir. W.P.M. van Swaaij en de assistent-promotoren: Dr.ir. W. Prins Dr. S.R.A. Kersten

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Luna, Mila and Goran, you are my life and my orientation. I love you!

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Contents

Summary Samenvatting Chapter 1 Chapter 2 Introduction A High-throughput Screening Technique for Conversion in Hot Compressed Water Chapter 3 Gasification of Model Compounds and Wood in Hot Compressed Water Chapter 4 Chapter 5 Chapter 6 Chapter 7 Pilot Plant SCWG Experiments in a Micro Continuous Flow Reactor Fluidization with Supercritical Water in Microreactors Reactor Design Considerations for Biomass Gasification in Hot Compressed Water Acknowledgements List of Publications Curriculum Vitae

1 5 11 37

53

79 97 111 131

141 145 147

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viii

Summary
Application of biomass and waste, as a renewable and possibly sustainable energy source, has gained an important role in the worlds future energy policy. The Dutch government, for instance, has set a target for 2020, which states that 5% of the total primary energy production must be based on biomass and waste input. For the year 2040 this could rise to 30%. The European Committee has put similar directives forward. An important fraction of the available biomass and waste streams has a high moisture content (say more than 70 wt % water). Wet streams cannot be converted economically by thermal conversion techniques like combustion, pyrolysis and gasification because of the large amount of energy required for evaporation of water. Partial conversion of wet biomass by anaerobic biological processes, producing convenient energy carriers like methane or ethanol, is possible and practiced for suitable feedstock materials. Over the last decades research activities worldwide have been devoted towards the development of new thermochemical processes, which can convert wet biomass efficiently and economically. One of the novel technologies for conversion of wet biomass and waste streams is gasification in supercritical water (SCWG: T > 3750C, P > 221 bar). Hydrogen and/or methane can be produced by SCWG with selectivities that can be controlled by the process conditions and catalysis. The research described in this thesis is dealing with the SCWG process. Due to the severe process conditions (typically: T = 600C, P = 300 bar and a corrosive environment), experimental investigation on SCWG is expensive and time consuming. Despite these challenges, experiments were conducted by different groups in the world revealing the influence of process conditions (temperature, pressure, residence time, concentration of the organics, catalysis) on the yields and the selectivity of the desirable gas products. All laboratory scale experiments reported in the past were conducted in metal reactors. This was demonstrated to cause a difficult to quantify catalytic effect of the reactor wall that makes interpretation and comparison of the available data uncertain. Therefore, part of the present work is focusing on gasification experiments not influenced by catalytic effects. For this non-catalytic gasification, a high throughput technique for mapping of the reaction space has been developed. In this technique, quartz capillaries of 1 mm inside diameter are used as batch reactors. SCWG experiments could then be performed in a safe, cheap, and quick manner; one capillary measurement takes about 5 min. compared to several hours for earlier batch and continuous methods. Via validation measurements with formic acid and glucose solutions it has been

demonstrated that the technique is sufficiently reliable for screening purposes including trend detection. The quartz capillary batch reactor technique has been subsequently used to study the non-catalytic gasification of glycerol, glucose and pinewood in supercritical water. Mapping of the reaction space has been done by performing over 700 experiments in which T, P, the heating time, the reaction time and the concentration of the feedstock were varied. The most important observations were that the pressure turned out to have no effect on the conversion rate to gas-phase products and product yields, and that, without catalytic effects, complete conversion to the gas-phase is only possible for very diluted feedstock solutions (<2 wt %). Compared with previous work in metal reactors, conversion rates and final conversion to gas phase products was lower while the product gas composition was also different. By adding Ruthenium on a TiO2 carrier to the capillaries, the potential of heterogeneous catalysis has been demonstrated. When adding this catalyst to the capillaries, glucose solutions in the range of 1 to 17 wt % could be gasified completely already at 600oC. A first generation pilot plant (intake 30 l feed/h) for the supercritical water gasification process, designed to gain operating experience and to identify problems related to the overall process from feed preparation to product gas analysis, is described and operated. Non-charring feedstocks such as glycerol and methanol solutions could be successfully gasified with this plant. However, charring feedstocks like starch caused fouling and blockage in the reactor and heat-exchanger demonstrating that already during heating up problems occur. Results have been compared with those of the micro reactor systems used in this work. The observed differences have been explained by the presence and extend of the catalytic activity of metal reactor walls, or absence of such activity. As the operation of this large plant was expensive and cumbersome, a new micro continuous reactor system was set-up. Unfortunately the use of quartz in this system led to too frequent failure of the reactor and connections. Therefore, the reactors used in the system were tubular reactors of 1 mm internal diameter made of different metals namely Inconel 625 and stainless steel (SS-316). In this system, the influence of the process conditions and reactor construction materials on feedstock conversion to different gas phase products has been examined. In a second series of experiments, the empty tube reactor is placed in series with a packed bed of catalyst particles to study its influence on conversion and selectivity. Catalysts used are 3 wt % Ru on TiO2 and charcoal of beech wood. After the gasification, burn-off of carbonaceous deposits was performed and the CO2 production was measured. The tested Ru catalyst increased strongly the carbon conversion to gas phase products, probably by converting intermediates products that without catalyst would slip trough the reactor and end-up as liquid dissolved products. Glucose produced carbonaceous by-products in the form of deposits in the SCWG reactor. In a few tests, these deposits were combusted with air under controlled
2

process conditions. This burn-of or regeneration may be an important aspect of an industrial SCWG reactor system, where the catalyst will most likely be in a fluidized state. As ultimately this convenient continuous reactor set-up would be used for catalytic SCWG with a highly active catalyst compared to the moderate catalytic influence of the reactor wall, the catalytic activity of the wall was accepted. To pave the way for introducing a fluidized catalyst bed in a SCWG reactor and especially in a continuous micro plant, a new micro-fluid bed technique for investigation of supercritical water fluidization was designed and operated. A cylindrical quartz reactor of only 1 mm internal diameter with a quartz ball as distributor was used for process conditions up to 5000C and 244 bar. Properties of the fluid bed like: minimum fluidization velocity (Umf), minimum bubbling velocity (Umb), bed expansion, and the identification of the fluidization regime were investigated by visual observation. Dedicated 2D and 3D Discrete Particle Models (DPM) models were used to simulate the micro-fluid beds for gas-solid fluidization (fluid density range from 16 to 230 kg/m3). It has been found that the results for Umb from the simulations are in accordance with experimental data and somewhat higher than predictions from existing empirical relations. Experiments in three different scale cylindrical reactors namely: 26 mm, 12 mm and 1 mm inside diameter, showed that to mimic large-scale homogeneous fluidized bed systems in the 1 mm reactor only small particles (d < 100 micron) can be used. Finally, based on the present work and literature results, the different requirements for a SCWG system are listed and discussed. A preliminary conceptual design is proposed including fluidized/circulating bed systems, heat-exchangers and a regeneration section. Such a system could possibly cope with the operational problems expected for a pilot plant or commercial SCWG system processing real biomass, but much more research and development work is required before it can be realized.

Samenvatting
Het gebruik van biomassa en afval als een hernieuwbare, en mogelijk duurzame energiebron, wordt wereldwijd een steeds belangrijker onderdeel van het energie beleid. De Nederlandse regering bijvoorbeeld, heeft in haar doelstelling voor 2020 bepaald dat 5% van de totale primaire energieproductie gebaseerd moet zijn op biomassa en afval als grondstof. De Europese Commissie heeft vergelijkbare richtlijnen voorgesteld. Een belangrijk deel van de beschikbare biomassa- en afvalstromen heeft echter een hoog vochtgehalte (meer dan 70 gewichtsprocent water). En zulke natte stromen kunnen niet op economisch verantwoorde wijze worden omgezet met de traditionele thermische conversietechnieken (verbranding, pyrolyse en vergassing) vanwege de grote hoeveelheid energie die er nodig is voor de verdamping van water. Gedeeltelijke omzetting van natte biomassa met behulp van biologische processen waarbij nuttige energiedragers zoals methaan of ethanol worden gevormd, is mogelijk en wordt in de praktijk veelvuldig toegepast voor bepaalde typen biomassa. De afgelopen twintig jaar is er op een aantal plaatsen in de wereld ook onderzoek verricht m.b.t. de ontwikkeling van nieuwe thermochemische processen om natte biomassa efficint en economisch verantwoord om te zetten in nuttige producten. En van de nieuwe technologien voor de verwerking van natte biomassa en afval is de vergassing in superkritiek water, in het Engels aangeduid met de afkorting SCWG (Super Critical Water Gasification). Bij temperaturen boven 375oC en drukken boven 221 bar (het superkritieke punt van water) kan er waterstof en/of methaan gemaakt worden. De productselectiviteit wordt geregeld met de keuze van procescondities en de toepassing van katalysatoren. Het onderzoek dat in dit proefschrift is beschreven gaat over het SCWG-proces. Gewoonlijk zijn de experimenten tijdrovend en kostbaar vanwege de strenge procescondities (reactie in een corrosief medium, typisch bij T = 600oC en P = 300 bar). Ondanks deze bezwaren zijn er door verschillende onderzoeksgroepen in de wereld experimenten uitgevoerd waarbij duidelijk is geworden wat de invloed is van de procescondities (temperatuur, druk, verblijftijd, biomassaconcentratie en katalyse) op de opbrengst en de verdeling van de gewenste producten. Alle laboratoriumexperimenten waarover in het verleden is gerapporteerd zijn uitgevoerd in reactoren van metaal. Inmiddels is ook aangetoond dat dit de interpretatie en vergelijking van resultaten bemoeilijkt omdat de metaalwand een onbekend
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katalytisch effect veroorzaakt. Daarom was een deel van het onderzoek voor dit proefschrift gericht op vergassingsproeven waarbij zulke ongewenste katalytische effecten zijn uitgesloten. Er is een techniek ontwikkeld om snel, en veel experimenten te doen (high-throughput screening) ten einde de mogelijke reactiecondities in kaart te brengen. Hierbij zijn kwartsglazen capillairen van 1 mm inwendige diameter gebruikt als batch reactor. De SCWG experimenten konden op deze wijze veilig, goedkoop en snel worden uitgevoerd; een experiment met zon capillair duurt maar vijf minuten terwijl in het verleden een experiment vele uren in beslag nam. De techniek is eerst gevalideerd, door de omzetting van mierenzuur en glucose te bestuderen, en bleek voldoende betrouwbaar voor snelle verkennende proeven en het vastleggen van trends. Vervolgens is de capillaire techniek gebruikt om de niet-katalytische vergassing van glycerol, glucose en dennenhout in superkritiek water te onderzoeken. Het operatiegebied voor de vergassingsreactie is in kaart gebracht door 700 experimenten uit te voeren waarbij de temperatuur, de druk, de opwarmsnelheid, en de concentratie van de organische stof in het water zijn gevarieerd. De belangrijkste waarnemingen waren: a) dat de druk geen invloed bleek te hebben op de snelheid van de omzetting naar gasfase producten en de productopbrengsten, en b) dat een volledige omzetting naar gasfase producten zonder toepassing van katalyse alleen maar mogelijk is voor verdunde oplossingen (minder dan 2 gewichtsprocent organische stof in water). In vergelijking met het eerdere werk uitgevoerd in metalen reactoren, bleek de omzettingssnelheid en de uiteindelijke omzetting naar gasfase producten lager te zijn terwijl ook de productsamenstelling afweek van eerder gepubliceerde resultaten. Door ruthenium op een TiO2-drager als katalysator toe te voegen aan de capillairen, kunnen glucoseoplossingen met een concentratie varirend van 1 tot 17 gew. % al bij 600oC volledig vergast worden, waarmee de potentie van katalyse voor SCWG is aangetoond. In dit proefschrift wordt ook het ontwerp, de bouw en het testen van een volledige pilot-plant installatie beschreven. Deze SCWG pilot-plant heeft een capaciteit van 30 liter vloeistof per uur, en is bedoeld om procesgerelateerde problemen van allerlei aard te identificeren en op te lossen, en ervaring te krijgen met continue operatie. Voedingen die geen coke vormen, zoals glucose en methanol, konden in deze pilot-plant goed worden vergast. Maar de vergassing van zetmeel, leidde tot vervuiling en tenslotte tot verstopping van de warmtewisselaar en de reactor, waaruit valt af te leiden dat er al problemen ontstaan tijdens de opwarming van de voeding naar de gewenste reactietemperatuur. De resultaten van succesvolle pilot-plant zijn vergeleken met die van de kleinschalige laboratoriumproeven en de waargenomen verschillen zijn verklaard met de katalytische activiteit van de metalen wand van de pilot-plant reactor.

Het bedrijven van de pilot-plant is duur en lastig gebleken. Daarom is er een veel kleinere opstelling gebouwd voor continue SCWG-vergassingsproeven. Helaas bleek het niet goed mogelijk om in deze micro-opstelling een kwartsglazen reactor te gebruiken. Met name de verbinding met staal leidde vaak tot breuk tijdens het op druk en temperatuur brengen van de reactor. Er is tenslotte besloten om met een metalen buisreactor te werken van 1 mm inwendige diameter, gemaakt van Inconel 625 of roestvrij staal (SS-316). De opstelling is gebruikt om de invloed van de procescondities, en het type metaal van de reactorwand, op de conversie van de voeding naar de verschillend productgassen te onderzoeken. En in een tweede serie experimenten is er een gepakt bed van katalysatorpoeder in serie geplaatst met een lege buisreactor om de invloed van de katalysator op de conversie en selectiviteit te bestuderen. De beproefde katalysatormaterialen zijn 3 gew.% ruthenium op TiO2 en kool van beukenhout. Na de vergassing werd de geaccumuleerde kool in de reactoren afgebrand met lucht, en de hoeveelheid ervan bepaald door de CO2 productie te meten. Er bleek dat de ruthenium katalysator de koolstofconversie naar gasfaseproducten sterk verbetert, waarschijnlijk doordat intermediare producten, die zonder de aanwezigheid van een katalysator door de reactor slippen en als opgeloste componenten in de waterfase terechtkomen, in dit geval wel worden omgezet. Het gebruik van glucose als voeding veroorzaakte koolachtige bijproducten in de vorm van waarneembare afzettingen in de reactor. In enkele proeven zijn deze koolafzettingen verbrand met lucht onder gecontroleerde omstandigheden. Het afbranden, c.q. uitbranden van koolafzettingen zal voor een grootschalig SCWGproces erg belangrijk zijn om het systeem te reinigen en de katalysator (mogelijk in een fluid bed reactor) te regenereren. De kleine continue opstelling is gemakkelijk te bedrijven en zal in de toekomst verder worden gebruikt voor het testen van katalysatoren voor SCWG. In dat verband is een beperkte katalytische activiteit van de wand acceptabel omdat deze wegvalt tegen de veel grotere activiteit van de toegepaste katalysatordeeltjes. Om de introductie van een fluid bed als katalytische reactor in SCWG voor te bereiden, en met name ook voor toepassing van fludisatie in kleine laboratoriumopstellingen, (microreactor), is er een nieuwe microtechniek ontwikkeld en toegepast om de fludisatie van katalysatordeeltjes in superkritiek water te onderzoeken. Een cilindrische kwartsbuis van slechts 1 mm inwendige diameter, met een kwartskogeltje onderin om het fludisatie medium te verdelen, is gebruikt voor proeven bij temperaturen tot 500oC en drukken tot 244 bar. Eigenschappen van het gefludiseerde bed, zoals de minimum fludisatiesnelheid (Umf), de minimale belsnelheid (Umb), de bedexpansie, en het fludisatieregiem, zijn onderzocht aan de hand van visuele waarnemingen. Bovendien zijn er geavanceerde twee- en driedimensionale modellen toegepast (DPM: discrete particle models) om gasvast fludisatie te simuleren voor zulke micro fluid bedden met dichtheden varirend van 16 tot 230 kg/m3. De uitkomsten van de simulaties zijn vergelijkbaar met de experimentele resultaten, maar zijn
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iets hoger dan wat de gangbare empirische correlaties voorspellen. Experimenten waarbij de reactordiameter is gevarieerd (26, 12, en 1 mm inwendige diameter) hebben laten zien dat het gedrag van grootschalige homogeen gefludiseerde bedden goed kan worden nagebootst, mits er in de 1mm reactordeeltjes worden gebruikt die kleiner zijn dan 100 m. Tenslotte is er, op basis van dit onderzoek en de literatuur, een overzicht gemaakt van de verschillende eisen die aan een SCWG-systeem gesteld moeten worden. Er is een voorlopig ontwerp gepresenteerd waarin gefludiseerde bedden en vaste stof circulatie zijn opgenomen, om warmtewisseling tussen voeding en reactor effluent alsmede katalysatorregeneratie, mogelijk te maken. Zon systeem zou mogelijk de operationele problemen die te verwachten zijn van een pilot-plant of een commercile SCWG installatie voor echte biomassa, kunnen ondervangen. Maar er is meer onderzoek en ontwikkelingswerk nodig om dit allemaal te realiseren.

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Chapter 1
Introduction
Biomass as sustainable energy source
During the last three decades, concerns on the use of fossil sources have increased enormously. Care about the environment and uncertainties about the security of energy supply are the main reasons for these concerns. It is a well-established fact that the concentration of carbon dioxide in the atmosphere has increased notably over the past 150 years (United Nations Environment Programme, 2005). There is also considerable evidence that the increase of the carbon dioxide concentration in the atmosphere since the industrial revolution is primarily caused by human activity (United Nations Environment Programme, 2005). How the combustion of fossil fuels and the resulting unbalanced global CO2 flows will affect life on earth on the long term is strictly speaking not known. The fact that the consequences are unknown should however be enough to start considering sustainable energy systems. Our measures to counteract the increasing CO2 level should be guided by the precaution principle. It is by far the safest strategy to assume that mankinds increasing fossil CO2 emissions turns out to do irreversible harm to the well-being and prosperity of generations to come. At present, we are able to develop the required technologies for the conversion of sustainable sources into heat, power, fuels, and chemicals. The most important hurdles for rapid development of such technologies are economic and mainly related to the still low price of crude oil, natural gas, and coal. Besides these concerns on global warming, the worlds current political situation also gives rise for reconsideration of energy strategies. The majority of the crude oil reservoirs and reserves (90%, (World Energy Council, 2004)) are located in potentially political unstable countries in the Middle East, which makes availability principally unsure. This motivates several countries to invest in the development of alternatives from locally available fossil resources such coal, shale and natural gas, but also increasingly from renewable sources like hydro, solar, wind, and biomass (e.g. State of the Union

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Speech of US president Bush, January 2006), (Bush, 2006, The National Renewable Energy Laboratory's, 2006). Moreover, it is projected by most scenarios that the worlds oil and gas reserves are limited to ca. 60 years (e.g. BP statistical review (BP, 2005)). Obviously, this will have far reaching consequences for the security of supply in a fossil dominated energy system. For the distant future it is evident that we have to rely on sustainable sources, no matter if the fossil reserves turn out to sufficient for 200, 500 or 1000 years. Because biomass is built-up from carbon extracted from the atmosphere in the form of CO2, which, in a short cycle, is returned again to the atmosphere after decay or combustion, the utilization of biomass does not overall influence the atmospheric CO2 concentration. While considering alternatives for fossil feedstocks, it becomes clear that biomass is the only sustainable source containing carbon and thus allows direct matching with existing fossil derivatives like transportation fuels and chemicals. Integrating and partnering with the existing fossil-based industries and logistic facilities is of utmost importance in the transition towards a completely sustainable society, because it lowers the capital investments and offers guaranteed markets for the products (Van Swaaij et al., 2004). Without this initial partnering with the fossil industry it is to be doubted if the very large capital investments required for achieving the directives on sustainable energy of the Dutch government and the European Union will ever be brought up. Moreover, the total amount of biomass in the form of forestry, agricultural and plantation residues is huge (say the equivalent of half the worlds crude oil production, (Groeneveld, 2000). Moreover, even possible to grow biomass especially for energy production (e.g. seeds for bio-diesel, and corn or sugar cane for bio-ethanol), also as part of agricultural policies. When combining biomass-based processes with CO2 sequestration, the CO2 concentration in the atmosphere can even be reduced. Biomass as a renewable source should of course be used in a sustainable fashion. Several factors should be considered like competition with the food chain, energy for production and transportation of biomass, ecological aspects, bio-diversity soil exhaustion, etc. As an example it should be realized that biomass always contains minerals, which should be carefully considered in relation to a sustainable and ecological responsible use of biomass.

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Biomass conversion
For the conversion of biomass to energy or energy carriers, the moisture content of the biomass is of crucial importance in view of the net lower heating value and the flame temperature (see Figure 1.1). The net lower heating value is defined here as: LHVnet = (1 Xmoisture) x LHV Xmoistue x Hvap in which Xmoisture is the mass fraction of moisture in the biomass, LHV is the lower heating value of the dry fraction and Hvap the enthalpy of vaporization of water. This definition of the net lower heating value thus includes the energy required for vaporization of the moist. Biomass with a moisture content of more than 60% on dry weight basis cannot be combusted efficiently. Drying of the biomass is expensive and will consume rapidly a large fraction of the energy available in the wet biomass unless special measures are taken. Water can be removed by methods like sun drying, mechanical pressing, utilization of hot flue gas, multiple effect evaporation, vapor recompression, and superheated steam drying. Sun drying in the open air is the cheapest but not always possible. Other drying techniques are costly and generally not yet optimized for bulky biomass. That is why conversion technologies for wet biomass streams, which do not request the initial evaporation of the water associated with the biomass, can be very attractive. Examples of wet biomass streams are by-products from food processing and certain streams in future biorefineries.
25

Flame temperature [ C/100]

20

15

10

LHVnet [MJ/kg]

0 0.0

0.2

0.4

0.6

0.8

1.0

moisture content [kg/lg]

Figure 1.1

Influence of the moisture content on the net heating value of the feedstock and the

adiabatic flame temperature in air. In this introduction we will consider briefly the technologies that utilize dry or dried biomass, after which the conversion technologies for wet biomass will be discussed.
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Dry biomass conversion

Examples of dry biomass are: rice husk, wood chips, straw, saw dust, cotton stalk, nut shell, etc. Dry biomass can be used as a solid fuel in direct combustion or be converted thermochemically for the production of various secondary energy carriers. Figure 1.2 gives an overview. Apart from the classical combustion in household stoves, grate boilers etc., also more advanced boilers like fluidized bed and circulating fluidized bed boilers are used now to generate energy from e.g. wood and straw (Quaak et al., 1999). A recent development is large-scale combustion of biomass in coalbased power stations, by co-firing up to a level of 10 wt % (IEA, 1998). This is indeed a quick and efficient way to reduce fossil carbon-based CO2 emissions and produce green electricity, for which reason it is stimulated in some countries by fiscal measures and subsidies. The combustion with energy generation of organic fractions in waste incineration is also counted sometimes as a contribution to the reduction of CO2 emissions. Here, of course, only organic fractions from non-fossil sources should be counted, e.g. thus excluding most plastics.

Dry Biomass
direct combustion flash pyrolysis oil pressing

gasification

ash

ash

ash
oil

organic liquid fuel gas or (+ water) synthesis gas

liquid fuels hydrocarbons methanol etc.

Figure 1.2 A simplified overview of the conversions of dry biomass into secondary energy carriers. Flash pyrolysis (Bridgwater et al., 1999; Wang et al., 2005) is a process in which dry biomass is heated rapidly to produce vapors that can be condensed to a liquid product that is usually indicated as bio-oil. If carried out properly, about 70 - 80% of the product can be converted into bio-oil. Some char and incondensable gas is produced, which can be used to generate heat and power for the process itself, or for the local market. Conversion to bio-oil increases the bulk density of the material from applied directly in engines, furnaces, turbines etc. After gasification in existing oil gasifiers (from 20014

300 kg/m3 to 1300 kg/m3 allowing for long distance transport and easy storage. The oil can be SHELL, LURGI or TEXACO), the produced bio-oil syngas can be used for the production of chemicals, Fischer Tropsch diesel, or as a fuel-cell feedstock. Biomass can also be pyrolyzed slowly, that is in a more traditional way, to produce e.g. charcoal from wood as a secondary solid fuel. But that will not be discussed here. Dry biomass can be gasified (Beenackers and Maniatis, 1997; Kersten, 2002; Kersten et al., 2003) by partial oxidation with air or oxygen/steam mixtures, to transfer the combustion value of the biomass to fuel gas or syngas respectively. A wide range of processes to achieve this gasification has been developed. Over the last decades, the research group in Twente has analyzed the performance and made experimentally verified reactor models of various gasifier types, such as the co-current moving bed (Groeneveld, 1980), fluidized bed (Van den Aarsen, 1985), and circulating fluid bed (Kersten, 2002). For large-scale operation entrained flow gasifiers are attractive (Higman and Van der Burgt, 2003). Product gas can be fired in boilers, turbines and engines or shifted to hydrogen for application in fuel cells. It can be converted to liquid fuels like methanol or hydrocarbons via the Fischer-Tropsch synthesis. If biomass consists of oilseeds, oil can also be extracted and converted to green diesel but this will not be discussed here (Boerrigter et al., 2003).

Wet biomass conversion

Examples of wet biomass streams are vegetable, fruit and garden waste, waste streams from agricultural, food and beverage industries, manure, sewage sludge, and some household wastes. Seaweed and micro-algae are examples of cultivated wet biomass crops. According to estimates of ECN (Hemmes, 2004), between 5.3 and 12 million ton (dry matter) of wet streams are annually available in The Netherlands. Besides, these streams that are already available it is expected that within a future biorefinery also diluted side streams (by-products) are present. A bio-refinery is an integrated concept aiming at full utilization of biomass, in which different fractions of biomass are converted in large-scale plants (economy of scale) or in standardized small-scale units (economy of numbers) in an economically optimal product slate. This thesis deals with the conversion of wet biomass streams. An overview of these processes is given in Figure 1.3. By biological processes methane can be produced which will easily separate from the bioreactor fluid, leaving a non-fermentable organic fraction (Hill and Bolte, 2000).

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Wet Biomass HTU

Pressure cooker

SCWG
Pressure cooker

P=150 bar, T=300oC

P=300 bar, T=600oC

Phase separation

Phase separation

Phase separation

Water + Ash

Methane, alcohols etc.

Water + Ash Hydrophobic oil

Water + Ash

Gaseous fuel (H2)

Figure 1.3: Simplified overview of conversion processes for wet biomass. Bio-ethanol can be produced also from various feedstock materials, especially from starch and sugars. It can also be recovered from the bioreactor by refined distillation or extraction processes (Reith et al., 2002). Biological processes with their special feedstock and operation conditions differ considerably from the thermochemical processes and will not be further discussed here. Biological and thermochemical conversion process will both be needed to develop a biorefinery that utilizes the whole lignocellulosic feedstock. In this refinery a multitude of conversion steps will be present; byproducts from biological conversions will be used as feedstock for thermochemical conversions and vise versa. Two other conversion processes indicated in Figure 1.3 are thermochemical, viz. HTU and supercritical water gasification (SCWG). These processes are operated at elevated temperatures, and under high pressure to avoid the evaporation step of water. They both require extensive heat exchange between the feed inlet and product outlet streams in counter current operation to become energy efficient. HTU or HydroThermal Upgrading is a thermochemical process in subcritical water in which biomass is converted to liquid bio-crude with a reduced oxygen content (Goudriaan and Peferoen, 1990). In some hydrothermal processes by application of a catalyst the production of methane is aimed for (Elliott et al., 2004). Gasification of biomass in supercritical water for the production of hydrogen or methane rich gas is the topic of this thesis.
16

Gasification of wet biomass feedstocks in supercritical water

As stated above, the high moisture content of so-called wet biomass streams makes conventional thermochemical technologies inefficient due to the high-energy requirement for water evaporation (2.4 MJ/kg at atmospheric conditions). Although wet biomass (moisture > 60 wt %) has a very low overall heating value, products with a high heating value can still be extracted from it by applying advanced conversion processes. Biomass gasification in hot compressed water (SCWG, 600C, 300 bar) is considered as a promising technique to convert such wet streams into a gas that is rich in either hydrogen or methane depending on the operating conditions and applied catalysis. In hot compressed water (P > 200 bar), the heat effect associated with water evaporation is marginal compared to that at ambient conditions (Hvap becomes zero at Pc). Therefore, by practicing counter-current heat exchange between the feed stream and the reactor effluent, high thermal efficiencies can be reached despite the low dry matter content of the feedstock. In Figure 1.4 a conceptual flow sheet of the SCWG process is given.

Figure 1.4 Conceptual flow sheet of the SCWG process. It is therefore crucial for the process that the sensible heat content of the reactor effluent is utilized as far as possible to pre-heat the feedstock stream (mainly water) to reaction conditions (see Figure 1.4). The efficiency of the heat exchange in relation to the applied pressure can be calculated from the heat balance for a counter-current shell and tube heat-exchanger. The result is presented in Figure 1.5, in which the heat-exchanger efficiency is plotted as a function of the operating pressure and the available
17

area per unit throughput in kilogram per second. In case of an infinitely long heat-exchanger, the steep asymptotic approach to 100% efficiency above 200 bar is a result of the sharp decrease of Hvap to zero beyond that pressure. For heat-exchangers with finite surface area, the effect of the operating pressure is less pronounced. In practice, a hundred percent transfer of the available heat in the reactor effluent to the feedstock stream is impossible. In fact, efficiencies of ca. 75% are typical for liquidliquid shell and tube heat-exchangers (Kersten et al., 2004). For such efficiency the operating pressure should be ca. 200 bar in case of 50 m2 per kg/s throughput or 300 bar in case of 25 m2 per kg/s throughput (see Figure 1.5).

1.0 0.9 0.8

100 50 25

efficiency (HE) [-]

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0 50

AHE = 10

HE =

Hcold,out -Hcold,in Hhot,in -Hcold,in

100 150 200

Supercritical Pressure

250

300

350

pressure [bar]
Figure 1.5 Calculated efficiencies of a water-water counter-current heat-exchanger plotted versus the operating pressure for different surface areas, AHE = area (m2) per unit throughput (kg/s). The flow rates (kg/s) on both sides were assumed to be equal. U = 1000 W/(m2.K), Inlet conditions: Thot,in = 600oC, Tcold,in = 25oC. Promises of biomass gasification in supercritical water are that: The technology is suitable for efficient processing of wet feedstock (> 70 wt % moisture); evaporation of water is avoided and feedstock/product heat exchange is quite well possible. Contrary to anaerobic digestion and fermentation processes, the technology allows in principle for complete feedstock conversion. The product gas is made available at high pressure (> 250 bar) and, for its application, expensive gas compression can be avoided.
18

The product gas is clean; minerals, metals, and the undesired gases like CO2, H2S and NH3 (which have a high solubility in compressed water) remain in the water phase and can thus be recovered.

The product gas is not diluted with inert gas. The selectivity towards either methane or hydrogen can be controlled with temperature, pressure and the application of catalysts. Sequestration of (pure) CO2 seems convenient.

These promises however go together with a series of problems that need to be solved in the process development. Pumping of biomass slurries to pressures of up to 300 bar is a challenge. The high temperatures and pressures involved put serious demands on the construction materials to be used, especially because corrosion problems are expected. Heat exchange between the reactor feed and effluent is required to make the process efficient, but heating of a biomass slurry is likely to cause fouling and plugging in the heat-exchanger as the biomass starts to decompose already around 250oC. Ash deposits may cause similar problems, and an effective ash removal system must therefore be part of the reactor/process. Although carbon formation can be suppressed by applying high temperatures or using a catalyst, the process should include an option to burn this carbon off the catalyst (when applied) and the reactor walls. When the future process development is successful in solving the problems of heat exchange, corrosion, and fouling, interesting applications are foreseen. Compressed methane can be used for blending with synthetic natural gas and compressed natural gas for motorcars. In The Netherlands CH4/H2 mixtures could be fed to the natural gas pipelines. Compressed hydrogen is an attractive feedstock for upgrading processes within the bio refinery concept and for storage of hydrogen for mobile and stationary fuel cells. CO2 sequestration is especially interesting because it would, together with the use of biomass as a feedstock material, create the opportunity to reduce the amount of CO2 in the atmosphere (carbon sink).

19

Relevant properties of supercritical water The vapor pressure curve in the P-T diagram of water, which indicates the co-existence of liquid and vapor, ends in the critical point at Tc = 373.95 and Pc = 220.64 bar.

Figure 1.6 Phase diagram of water. At the critical point, the distinction between vapor and liquid disappears. The right upper quadrant enclosed by the critical isotherm Tc and the critical isobar P = Pc is the area where the fluid is supercritical. The properties of supercritical water are quite different from those of the normal liquid or steam at atmospheric pressure. For instance, at the critical point the density is around 0.3 g/cm3 (versus 1 g/cm3 for liquid water at ambient conditions), the dielectric constant e is 5 (versus 80 for liquid water at ambient conditions) and the ion product Kw = [H+][OH-] is 10-11 (versus 10-14 for liquid water at ambient conditions). The most striking feature of supercritical water is the possibility to manipulate and control its properties around the critical point by tuning the temperature and pressure. For instance, by raising the pressure from 10 to 50 MPa at a temperature of 400oC, the dielectric constant is increased from 2 to 14, the ion product from 10-28 about to 10-12 , and the density from less than 0.1 to about 0.5 g/cm3. As an important consequence of the change in the dielectric constant, supercritical water behaves like a non-polar solvent and exhibits a high solubility towards non-polar organic compounds like benzene. Also gases like oxygen, nitrogen, carbon dioxide and methane are completely miscible in supercritical water. Contrary, the solubility of inorganic salts like NaCl is decreased to very low values. All relevant properties of (supercritical) water are known accurately (see e.g. NIST).
20

Chemistry and thermodynamics

Biomass gasification in supercritical water is the result of thermal decomposition reactions (catalyzed or not), followed by a multitude of reactions between intermediates and end-products (Kruse et al., 2002; Kruse and Gawlik, 2003). In the vicinity of the critical point where the ion product is high (1011), the H+ concentration is about 30 times higher than at ambient conditions offering increased opportunities for acid catalyzed reactions (Buhler et al., 2002; Kabyemela et al., 1997; Kabyemela et al., 1997; Kabyemela et al., 1998; Kabyemela et al., 1999). Presumably, at the higher temperatures where hydrolysis as a result of the very low ion product Kw is impossible, radical reactions (pyrolysis and cracking) will control the chemistry (Antal et al., 1993; Antal et al., 1999; Antal et al., 2000; Hao et al. 2003; Lee et al., 2002; Potic et al., 2002; Potic et al., 2004; Potic et al., 2005; Schmieder, 1999). Steam reforming and methanization of the biomass cover the extremes of possible stoichiometric equations: C6H10O5 + 7H2O 6CO2 + 12H2 C6H10O5 + 1H2O 3CO2 + 3CH4 (1) (2)

Thermal decomposition of biomass and the subsequent reforming of intermediate fragment molecules at higher temperatures could profit from the supercritical conditions, because of the good miscibility of organic compounds and gases in supercritical water. It offers an opportunity to conduct chemistry in a single phase that otherwise would have to occur in a multiphase system. As a consequence, there are no interphase mass transfer limitations reducing the reaction rates, and higher concentrations of reactants and intermediate products can be maintained. There is an extensive literature (Kabyemela et al., 1997; Kabyemela et al., 1997; Kabyemela et al., 1997; Kabyemela et al., 1998; Kabyemela et al., 1999; Kruse et al., 2002; Kruse and Gawlik, 2003; Kruse et al., 2003; Minowa et al., 1998; Mok and Antal, 1992; Saka and Ueno, 1999; Sinag et al., 2003; Sinag et al., 2004; Stein et al., 1983) available on the elucidation of the chemical pathways of biomass conversion in hot compressed water. Although there seems to agreement on certain elements of the whole degradation chain, an overall model suitable for reactor design is not present yet. As there is no mechanistic reaction path model available, equilibrium calculations could be used to produce indicative results for comparison with experimental results. The thermodynamic calculations for supercritical gasification of C6H10O5 (cellulose), of which the results are presented in Figure 1.7, are obtained with Gibbs free energy minimization model (Kyle, 1999) using the predictive Soave Redlich Kwong equation of state to calculate the required fugacity
21

coefficients (Bertucco et al., 1995; Soave, 1972; Soave et al., 1993). Such calculations have a limited quantitative value in case the reactions involved are too slow to reach equilibrium, but they may be useful in predicting trends and the results desired upon application of an appropriate catalyst. In Figure 1.7 yields are plotted that are defined as the moles produced of a certain component out of one mole of C6H10O5. If water is consumed in the reaction the corresponding water yield is negative. Complete gasification of wet feedstock is thermodynamically possible. Actually, at 600C and 250 bar dry matter concentrations of up to 50 wt % do not have thermodynamic or stoichiometric limitations (see Figure 1.7a) regarding the full conversion the gas-phase. At a lower temperature of 350C, complete conversion is only possible for feedstocks with less than 30 wt % organics (see Figure 1.7a). In the thermodynamic calculations the non gasified part feedstock remains as solid carbon. Thermodynamics predict that high temperature gasification would produce a hydrogen-rich gas (at least for dry matter contents of less than 10 wt %) while at low temperature a methane-rich gas is produced (see Figures 1.7b, 1.7c and 1.7d). Complete reforming of the feed (Eq. 1) to hydrogen is thermodynamically possible at temperatures above 600C and concentrations of organics lower than 1 wt %. Below 400C while using feedstocks with more than 15 wt % organics, complete conversion of the feed to methane (Eq 2) is favored by the Second Law. Between 350C and 600C there is a large difference in composition of the produced gas (compare Figures 1.7b and 1.7c), while increasing the temperature from 600C to 700C results in only minor changes (compare Figures 1.7c and 1.7d). It is also interesting to note that according to thermodynamics water is net consumed in the decomposition reactions under all relevant conditions (see Figures 1.7b, 1.7c, 1.7d, 1.7e and 1.7f). For low temperature gasification, the content of dry matter in the feed does not influence the product distribution to a large extent; the yields are almost unaffected (see Figure 1.7b). On the contrary, at higher temperature there is a continuous varying product distribution ranging from nearly pure hydrogen for very low weight percentages of dry matter, to a mixture hydrogen methane for high organic fractions in the feed (see Figures 1.7c and 1.7d). Below 200 bar, the pressure has a profound influence on the product distribution (see Figure 1.7e). Once above 200 bar, the operating pressure does not influence the product distribution to a large extent (see Figure 1.7e). It is worthwhile to note that, from a thermodynamic point of view, high temperature gasification should be carried out at the lowest possible pressure to achieve maximal hydrogen yields (see Figure 1.7e). Figure 1.7f shows predictions for typical SCWG conditions, viz. 250 bar and a feed stream that contains 10 wt % organics. For these conditions, according to thermodynamics, there is strong shift from methane towards hydrogen and carbon monoxide upon increasing the temperature. Methane-rich gas can be produced up to temperatures of approx. 500oC, higher temperatures favor the production of hydrogen.

22

1.0

600 C & 250 bar

Yields, mole produced/mole C6H10O5

12 9 6 3 0 -3 -6

fraction carbon gasified

0.8

350 C & 250 bar

CO CO2 CH4 H2 H2O

0.6

350 C & 250 bar

0.4

0.2

0.0 0 20 40 60 80 100

10

15

20

25

30

wt.% organics in feed

wt.% organics in feed

(a)
Yields, mole produced/mole C6H10O5

(b)
CO CO2 CH4 H2 H2O

Yields, mole produced/mole C6H10O5

12

12 9 6 3 0 -3 -6 0 5 10

600 C & 250 bar

9 6 3 0 -3 -6 0 5 10 15 20 25

700 C & 250 bar

CO CO2 CH4 H2 H2O

30

15

20

25

30

wt.% organics in feed

wt.% organics in feed

(c)
Yields, mole produced/mole C6H10O5
Yields, mole produced/mole C6H10O5
12 9 6 3 0 -3 -6 0 100 200 300 400

(d)
12 9 6 3 0 -3 -6 300 400 500
o

o 10 wt% organics in feed, 600 C

CO CO2 CH4 H2 H2O

10 wt% organics in feed, 250 bar

CO CO2 CH4 H2 H2O

600

700

800

Pressure, bar

T, C

(e) water.

(f)

Figure 1.7 Results of equilibrium calculations of cellulose (C6H10O5) gasification in hot compressed

23

Literature review
Here a short literature review is presented dealing with those reported results that are relevant for process development. For a more complete and detailed review the reader is referred to a joint paper of the SCWG community (Matsumura et al., 2005), which was co-authored by the author of this thesis. The reported experimental results concerning the effects of the operating conditions and applied catalysis are analyzed from a reactor engineering point of view. There is also significant information available concerning the chemical pathways of model compounds near the critical point (see e.g. Buhler et al., 2002; Kabyemela et al., 1998; Kruse and Gawlik, 2003; Savage, 1999). These results are however less relevant for the severe conditions of SCWG. Listing and discussing this information is therefore beyond the scope of this work.

Historical background
In the mid seventies of the last century, researchers at MIT (Amin, 1975; Woerner, 1976) discovered that biomass could be liquefied without producing char by processing it in supercritical water. In 1985, Modell (Modell, 1985) reported these experiments. It concerned experiments in which glucose, cellulose, hexanoic acid, polyethylene and maple wood sawdust samples were quickly immersed in sub- en supercritical water. Most experiments were performed with glucose or maple wood sawdust, of which 10 and 2 g were injected respectively in ca. 300 g of water. Char was collected as reaction product when operating below the critical point of water, while just above the critical point char was not observed. Other interesting observations were that polyethylene produced char under sub- and supercritical conditions and that using 30 g of glucose instead of 10 g resulted in significant char formation. Also in 1985, Elliot and Sealock (Elliott and Sealock, 1985) presented work that showed that the combined advantage of a high-pressure water environment and a metal catalyst (nickel) could compensate in the slow reaction kinetics typical for gasification at lower temperature. In supercritical water of 450C, 80% of the carbon present in the feedstock (10 wt % wood flour in water) could be converted to gases. In hindsight, the results presented in these papers should be regarded as the pioneering work that set off the research on gasification of biomass in hot compressed water. It is interesting to note that the motivation for this early research was not to develop a process for the effective conversion of wet biomass streams, but to minimize char production and to optimize steam reforming of biomass. At that time, the carbonaceous by-product of gasification and liquefaction processes was considered a serious problem. It was reasoned that char decreased the yield of the fluid products and could cause technical processing difficulties. Already in 1978 biomass was proposed as a potential feedstock for hydrogen production via steam reforming (Antal, 1978) and studies were reported of the reaction kinetics of cellulose pyrolysis in steam. It was found that biomass did not react directly with steam at atmospheric pressure to produce the desired products. Significant amounts of tar
24

and char were formed, and the gas contained higher hydrocarbons in addition to the desired light gases (Antal, 1985; Antal et al., 1987; Antal and Mok, 1988; Mozaffarian et al., 2004; Stein et al., 1983). Since the mid eighties, roughly speaking, two approaches to gasification in hot compressed water have been investigated in terms of reaction temperature ranges. In low-temperature catalytic gasification at 350 to 500oC, the feedstock is gasified with the help of a catalyst into a methane-rich gas. High temperature supercritical gasification is carried out in the range of 500 to 750oC, with or without catalysis, and aims at producing primarily hydrogen. The carbon efficiency is often used in literature to characterize the gasification process; it is defined as fraction of carbon in the feedstock that has been converted to permanent gases.

Low temperature gasification

Looking at the reported results, the catalytic low-temperature process (350 - 500C) must be regarded as very promising. It provides the opportunity to produce a pressurized methane-rich gas at relatively low temperatures. Even for feedstocks with a dry matter concentration of up to 10 wt %, carbon efficiencies of 90% and up were achieved in batch and continuous bench-scale facilities, while without catalyst the carbon efficiency is limited to ca. 20% (Elliott et al., 1993; Elliott et al., 1994; Elliott et al., 2004). However, near 100 percent carbon efficiency was never reached yet; typically the carbon efficiency was in the range of 94 to 98% when using the optimal catalyst at 400C. The comparison of several feedstocks using Ru and Ni catalyst showed the highest reactivity with manure, lignocellulosic feedstocks showed lower activity as a group. The observed effect of temperature was obvious (higher carbon efficiency at higher temperature), but there was no dramatic effect noticeable passing the supercritical point of water (374oC). Only a limited range of catalytic metals and supports can be used in the process because of the oxidation and degradation problems in the hot-water environment (Matsumura et al., 2005). New catalyst formulations for low-temperature gasification include combinations of metals stable under the applied conditions, such as ruthenium or nickel bimetallics and stable supports, such as certain titania, zirconia, or carbon. For example, the ruthenium on rutile titania extrudate is particularly effective in this process (Matsumura et al., 2005).

High temperature gasification

All reported laboratory results on high temperature gasification (500 - 750 C) were obtained in metal reactors. Stainless steel, Inconel, Hastelloy and corroded Hastelloy were used as construction materials. Both empty tubular reactors and stirred cells were used in the laboratory work that was carried out so far. Results obtained by processing model compounds and various wet biomass species in tubular reactors were reported mainly by Antal and co-workers (Antal et al., 1993; Antal et al., 2000). Hao et al. (Hao et al., 2003) and Lee et al. (Lee et al., 2002) reported experiments in tubular
25

reactors with glucose solutions as feedstock while varying the operating conditions. The diameter of the tubular reactors was in the range of 1.44 mm to 6.22 mm with a corresponding specific possible catalytic wall area of 2778 m2 to 643 m2 per unit volume reactor. Sinag et al. (Sinag et al., 2004) conducted SCWG experiments in a 190 mL metal autoclave equipped with a stirrer. In their experiments a cold feed stream was continuously injected into the hot autoclave. Literature data indicate that the reactor material has a significant effect on the gasification process. Yu et al. (Yu et al., 1993), for instance, reported results of gasification of glucose in the same experimental set-up under identical conditions, but using other metals for the reactor. They found large differences between experiments carried out in Inconel, Hastelloy and corroded Hastelloy reactors. For a test series using 0.6 M acetic acid they observed 14% carbon efficiency in the Inconel reactor whereas in the corroded Hastelloy reactor the carbon efficiency was as high as 53%. In a nutshell the results reported for non-catalytic (not taking into account the catalytic effect of the reactor wall) SCWG in the range of 500 - 750C can be summarized as follows: The metal reactor wall itself and deposits on it are catalytically active influencing both the carbon efficiency and the product distribution. Due to this catalytic effect of the wall, which may also be influenced by corrosion, published data are difficult to compare and interpret. Besides, the catalytic activity of small laboratory equipment cannot be translated to large-scale reactors, which have a much smaller wall area over volume ratio. Temperature is the most important process parameter; at 500C without catalyst hardly any gas is produced, while at 600C using a low concentrated feedstock complete gasification can be achieved. It is important to note here that results reported by Antal and co-workers before report the temperature in the last section of the tubular reactor while it turned out later that in the entrance (mixing) region peak temperatures were present that were more than 100C higher. Complete conversion of the feedstock to the gas-phase is achieved only for very diluted solutions of glucose and glycerol (< 5 wt %). Higher concentrations (> 5 wt %) of model compounds and more complicated feedstocks (e.g. wood, lignin, starch) cannot be gasified completely. The carbon conversion is typically between 75 and 90% for solutions with more than 5 wt % organics in it. The overall reaction is reasonably fast reaching the maximum conversion at 600C within one minute. Processing complicated feedstocks such as wood and starches that contain more than 10 wt % organics cause severe plugging problems in the reactor due to deposits of carbonaceous and mineral material.

26

The catalytic activity of the reactor wall suggested that heterogeneous catalysis might be employed to increase the extent of gasification for concentrated feeds. Antal and co-workers employed carbonaceous catalysts to investigate this possibility (Antal et al., 2000; Xu et al., 1996; Xu and Antal, 1998) and concluded that the available surface area of the carbon does not significantly influence the results. Of the tested carbons, coconut shell activated carbon was the most active one. They obtained complete gasification of a 22 wt % glucose solution at 600C (peak temperature not given). Besides glucose also other model compounds (e.g. ethylene glycol, phenol) and various realistic biomass feedstocks such as sewage sludge, wood sawdust, and starches were tested. Although complete gasification was not always possible, carbonaceous catalysts were found effective for all the compounds tested. To achieve reasonable carbon efficiencies (> 85%) for feedstocks such as potato starch catalyst bed temperatures of up to 750C had to be applied.

High temperature gasification pilot plants

SCWG is in an early stage of development. Due to its promises with respect to possible conversion of waste materials to a valuable gas, the laboratory research is developing rapidly. However, large-scale commercial installations do not yet exist. The gap between small-scale testing in laboratories to practical demonstration of a new process is bridged by experimentation with pilot plants. At present there are two pilot plants being operated in the world. The largest plant, in operation since the beginning of 2003, is the one of Forschungszentrum Karlsruhe (FzK) in Germany (Boukis et al., 2002). It has a design capacity of 100 l/h, and was built to demonstrate supercritical gasification of wet residues from wine production. EU subsidies plus a grant awarded by the Japanese NEDO enabled the construction of a well-equipped process development unit (PDU) in Enschede, The Netherlands, with a maximum throughput capacity of 30 l/h (Potic et al., 2002, Potic et al., 2004, Van de Beld et al., 2003). BTG Biomass Technology Group B.V. has been responsible for the technical realization and start-up of this small pilot plant.

27

Outline of this thesis

The further development of the SCWG process requires input from various disciplines. On the feedstock side, pre-treatment and pumping problems have to be tackled. Due to the severe operating conditions, studying of the long-term performance of selected construction materials is of utmost importance. Detailed chemical studies that provide more insight in the reaction pathways and kinetics at the severe SCWG conditions would help to select the optimal process conditions. This thesis focuses on the reactor engineering aspects of SCWG. Four main research lines (goals) will be addressed: Development of high-throughput experimental techniques. Mapping of the operating window under catalytically inert conditions. Investigating the potential of heterogeneous catalysis. Development of elements of a SCWG that can deal with heterogeneous catalysis under fouling conditions. Below the relevance of these research lines will be elucidated. 1. Development of high-throughput experimental techniques. Due to the severe operating conditions of SCWG, conventional laboratory equipment (e.g. autoclaves with significant volumes) requires extensive safety measures, and is costly and time intensive. In such systems, typically, 1 to 2 experiments can be performed per day, while 10 to 20 would be desirable to speedup the pace of the research. In this thesis, a high-throughput batch screening technique using quartz capillaries of only 1 mm internal diameter (Chapter 2) has been developed. With this method 20 cheap and safe tests per day have been performed. For catalyst screening and to study possible ways to recover or to avoid carbonaceous deposits when processing realistic feedstock materials, a continuous flow micro system (1 mm i.d.) is designed and applied (Chapter 5). In the same system, fluidization with sub- and supercritical water has been studied (Chapter 6). 2. Mapping of the operating window under catalytically inert conditions. It is know that metal reactor walls are catalytically active and influence the gasification process. Due to this catalytic effect of the wall published data are difficult to compare and interpret. Besides, the catalytic activity of small laboratory equipment cannot be translated to large-scale reactors, which have a much smaller wall area over volume ratio. In the present work, catalytically inert quartz capillaries have been used for the investigation of gasification in hot compressed water (Chapters 2 and 3). These results are supposed to represent the plain performance of the process and can provide reliable information on the chemistry and kinetics of biomass and waste gasification in high temperature and high-pressure water.
28

3.

Investigating the potential of heterogeneous catalysis. Results of previous research already made it clear that with catalysis only very diluted feed streams (say < 5 wt % organics) can be gasified completely. When processing feedstock with higher concentrations, carbonaceous deposits (not always e.g. not for glycerol) and water soluble organics are produced next to gases. Carbonaceous deposits cause fouling and blocking problems within the process. The organics containing effluent water requires an additional waste water treatment system, which obviously affects the economics of the process negatively. In this thesis, a catalyst developed for subcritical conversion has been tested under SCWG conditions in the microreactors (Chapters 3 and 5). Both the gasification performance and the burn-off characteristics of this catalyst have been investigated. The latter aspect is of importance for the development of the SCWG process.

4.

Development of elements of a SCWG process that can deal with heterogeneous catalysis under fouling conditions. Like mentioned above, catalysis is needed when dealing with concentrated feedstocks. Besides, when processing charring feedstock fouling will occur. These two items define the severe boundary conditions for process development; viz. the SCWG should be able to deal with catalysis under fouling conditions. In Chapter 7, based on results gathered in Chapters 2 to 6, an integrated heat-exchanger/reactor system based on fluid beds and circulating solids is proposed.

Notation AHE H Hvap Kw LHV LHVnet Pc Tc Thot,in Tcold,in U Xmoisture HE Area per unit throughput, m2/(kg/s) Enthalpy, J/kg Enthalpy of vaporization of water, MJ/kg Ion product Lower heating value of the dry fraction, MJ/kg Net lower heating value, MJ/kg Critical pressure, bar Critical temperature, oC Inlet temperature of the hot stream, oC Inlet temperature of the cold stream, oC Overall heat transfer coefficient, W/(m2.K) Mass fraction of moisture in the biomass Heat-exchanger efficiency

29

References

Amin, S.I., MSc Thesis, MIT, 1975. Antal, M.J., Energy from Biomass and Waste. In Class, D.L.; Chicago, 1978. Antal, M.J., Mathematical Modelling of Biomass Pyrolysis Phenomena. Fuel 1985, 64 1483. Antal, M.J.; Brittain, A.; DeAlmeida, C.; Ramayya, S.; Roy, J.C., Heterolysis and Homolysis in Supercritical Water. In Supercritical Fluids: Chemical and Engineering Principles and Applications, Squires, T.G.; Paulaitis, M.E., Eds.; American Chemical Society, Washington, DC, 1987. Antal, M.J.; Mok, W.S., A Study of the Acid Catalyzed Dehydratation of Fructose in Near-Critical Water. In Research in Thermochemical Biomass Conversion, Bridgwater, A.V.; Kuester, L.J., Eds.; Elsevier, New York, 1988. Antal, M.J.; Manarungson, S.; Mok, W.S., Hydrogen Production by Steam Reforming Glucose in Supercritical Water. In Advances in Thermochemical Biomass Conversion; Bridgwater, A.V., Ed.; Blackie Academic and Professional: London, 1993, 1367. Antal, M.J.; Allen, S.; Lichwa, J.; Schulman, D.; Xu, X., Hydrogen Production from High-Moisture Content Biomass in Supercritical Water. In U.S. DOE Hydrogen Program Review, 1999. Antal, M.J.; Allen, S.G.; Schulman, D.; Xu, X.; Divilio, R.J., Biomass Gasification in Supercritical Water. Ind. Eng. Chem. Res. 2000, 39, 4040. Beenackers, A.A.C.M.; Maniatis, K., Gasification Technologies for Heat and Power from Biomass. In Biomass Gasification and Pyrolysis: State of Art and Future Prospects; Kaltschmitt, M.; Bridgwater, A.V., Eds.;CLP Press, UK, 1997. Bertucco, A.; Barolo, M.; Soave, G., Estimation of Chemical Equilibria in High-Pressure Gaseous Systems by a Modified Redlich-Kwong-Soave Equation of State. Ind. Eng. Chem. Res. 1995, 34, 3159. Boerrigter, H.; Uil, H.D.; Calis, H.P., Green Diesel from Biomass by Fischer-Tropsch Synthesis: New Insights in Gas Cleaning and Process Design. ECN-RX--03-047; ECN: Petten, The Netherlands, 2003. Boukis, N.; Diem, V.; Dinjus E.; Galla U.; Kruse A., Advances with the Process of Biomass Gasification in Supercritical Water. Presented at the 4th International Symposium on High Pressure Technology and Chemical Engineering, Venice: Italy, 2002. BP Statistical Review of World Energy 2005, 2005. http://www.bp.com/genericsection.do?categoryId=92&contentId=7005893 Bridgwater, A.V.; Meuer, D.; Radlein, D., An Overview of Fast Pyrolysis of Biomass. Org. Geochem. 1999, 30, 1479. Buhler, W.; Dinjus, E.; Ederer, H.J.; Kruse, A.; Mas, C., Ionic Reactions and Pyrolysis of Glycerol as Competing Reaction Pathways in Near- and Supercritical Water. J. Supercrit. Fluids 2002, 22, 37.
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Bush, J.W., State of the Union Speech; 2006. http://www.whitehouse.gov/stateoftheunion/2006/index.html Elliott, D.C.; Sealock, L.J., Low Temperature Gasification of Biomass Under Pressure. In Fundamentals of Thermochemical Biomass Conversion, Overend, R.P.; Milne, T.A.; Mudge, L.K., Eds.; Elsevier Applied Science Publishers: London, 1985. Elliott, D.C.; Sealock, L.J.; Baker, E.G., Chemical Processing in High-Pressure Aqueous Environment: 2. Development of Catalyst for Gasification. Ind. Eng. Chem. Res. 1993, 32, 1542. Elliott, D.C.; Sealock, L.J., Jr.; Baker, E.G., Chemical Processing in High-Pressure Aqueous Environment. 3. Batch Reactor Process Development Experiments for Organics Destruction. Ind. Eng. Chem. Res. 1994, 33, 558. Elliott, D.C.; Neuenschwander, G.G.; Hart, T.R.; Butner, R.S., Low-Temperature Catalytic Gasification of Wet Biomass Residues. In Proceedings of the 2nd World Biomass Conference, Biomass for Energy, Industry, and Climate Protection; van Swaaij, W. P. M.; Fjallstrom, T.; Helm, P.; Grassi, A., Eds.; ETA-Florence and WIP-Munich: Rome, Italy, 2004, p. 746. Goudriaan, F.; Peferoen, D.G.R., Liquid Fuels from Biomass via a Hydrothermal Process. Chem. Eng. Sci. 1990, 45, 2729. Groeneveld, M.J., Personal communication, 2000. Groeneveld, M.J., The co-current moving bed gasifier. Technical High School of Twente, Enschede, 1980. Hao, X.H.; Guo, L.J.; Mao, X.; Zhang, X.M.; Chen, X.J., Hydrogen Production from Glucose used as a Model Compound of Biomass Gasified in Supercritical Water. Hydrogen Energy 2003, 28, 55. Hemmes, K. Vergassing van natte biomassa/reststromen in superkritiek water (SG), voor de productie van groen gas (SNG), SNG/H2-mengsels, basis chemicalin en puur H2. ECN: 2004. Higman, C.; van der Burgt, M., Gasification. Elsevier 2003. Hill, D.T.; Bolte, J.P., Methane Production from Low Solid Concentration Liquid Swine Waste Using Conventional Anaerobic Fermentation. Bioresource Technology 2000, 74, 241. IEA World Energy Outlook 1998; IEA/OECD; IEA: Paris, France, 1998. Kabyemela, B.M.; Adschiri, T.; Malaluan, R.; Arai, K., Degradation Kinetics of Dihydroxyacetone and Glyceraldehyde in Subcritical and Supercritical Water. Ind. Eng. Chem. Res. 1997, 36, 2025. Kabyemela, B.M.; Adschiri, T.; Malaluan, R.M.; Arai, K., Kinetics of Glucose Epimerization and Decomposition in Subcritical and Supercritical Water. Ind. Eng. Chem. Res. 1997, 36, 1552. Kabyemela, B.M.; Adschiri, T.; Malaluan, R.M.; Arai, K.; Ohzeki, H., Rapid and Selective Conversion of Glucose to Erythrose in Supercritical Water. Ind. Eng. Chem. Res. 1997, 36, 5063. Kabyemela, B.M.; Takigawa, M.; Adschiri, T.; Malaluan, R.M.; Arai, K., Mechanism and Kinetics of Cellobiose Decomposition in Sub- and Supercritical Water. Ind. Eng. Chem. Res. 1998, 37, 357.

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Kabyemela, B.M.; Adschiri, T.; Malaluan, R.M.; Arai, K. Glucose and Fructose Decomposition in Subcritical and Supercritical Water: Detailed Reaction Pathway, Mechanisms, and Kinetics. Ind. Eng. Chem. Res. 1999, 38, 2888. Kersten, S.R.A., Biomass Gasification in Circulating Fluidized Beds. University of Twente: Enschede, 2002. Kersten, S.R.A.; Prins, W.; van der Drift, B.; van Swaaij, W.P.M., Principles of a Novel Multistage Circulating Fluidized Bed Reactor for Biomass Gasification. Chem. Eng. Sci. 2003, 58, 725. Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M., Reactor Design Considerations for Biomass Gasification in Hot Compressed Water. In Proceedings of the 2nd World Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection; van Swaaij, W.P.M.; Fjallstrom, T.; Helm, P.; Grassi, A., Eds.; ETA-Florence and WIP-Munich: Rome, Italy, 2004; p. 777. Kruse, A.; Gawlik, A.; Henningsen, T., Biomass Liquefaction and Gasification in Near- and Supercritical Water: Key Compounds as a Tool to Understand Chemistry. Presented at the 4th International Symposium on High-Pressure Technology and Chemical Engineering, Venice: Italy, 2002. Kruse, A.; Gawlik, A., Biomass Conversion in Water at 330 - 410oC and 30 - 50 MPa. Identification of Key Compounds for Indicating Different Chemical Reaction Pathways. Ind. Eng. Chem. Res. 2003, 42, 267. Kruse, A.; Henningsen, T.; Sinag, A.; Pfeiffer, J., Biomass Gasification in Supercritical Water: Influence of the Dry Matter Content and the formation of Phenols. Ind. Eng. Chem. Res. 2003, 42, 3711. Kyle, B.G., Chemical and Process Thermodynamics. Prentice Hall PTR, New Jersey, 1999. Lee, I.; Kim, M.-S.; Ihm, S.-K., Gasification of Glucose in Supercritical Water. Ind. Eng. Chem. Res. 2002, 41, 1182. Matsumura, Y.; Minowa, T.; Potic, B.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M.; van de Beld, L.; Elliott, D.C.; Neuenschwander, G.G.; Kruse, A.; Antal, M.J., Biomass Gasification in Near- and Supercritical Water: Status and Prospects. Biomass Bioenergy 2005, 29, 269. Minowa, T.; Zhen, F.; Ogi, T., Cellulose Decomposition in Hot-Compressed Water with Alkali or Nickel Catalyst. J. Supercrit. Fluids 1998, 13, 253. Modell, M., Gasification and Liquefaction of Forest Products in Supercritical Water. In Fundamentals of Thermochemical Biomass, Overend, R.P.; Milne, T.A.; Mudge, L.K., Elsevier Applied Science Publishers Ltd.: London, 1985, p. 95. Mok, W.S.L.; Antal, M.J., Uncatalyzed Solvolysis of Whole Biomass Hemicellulose by Hot Compressed Liquid Water. Ind. Eng. Chem. Res. 1992, 31, 1157. Mozaffarian, M.; Deurwaarder, E.P.; Kersten, S.R.A., Green Gas (SNG) Production by Supercritical Gasification of Biomass; ECN-C-03-066; ECN: Petten, The Netherlands, 2004. National Institute of Standards and Technology, (NIST), Gaithersburg, MD.

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Potic, B.; van de Beld, L.; Assink, D.; Prins, W.; van Swaaij, W.P.M., Gasification of Biomass in Supercritical Water. In Proceedings of the 2nd European Conference and Exhibition on Biomass for Energy, Industry and Climate Protection, Palz, W.; Spitzer, J.; Maniatis, K.; Kwant, K.; Helm, P.; Grassi, A., Eds.; ETA Florence, WIP Munich: Amsterdam, 2002, p. 777. Potic, B.; Kersten, S.R.A.; Prins, W.; Assink, D.; van de Beld, L.; van Swaaij, W.P.M., Gasification of Biomass in Supercritical Water: Results of Micro and Pilot Scale Experiments. In Proceedings of the 2nd World Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection; van Swaaij, W. P. M.; Fjallstrom, T.; Helm, P.; Grassi, A., Eds.; ETA-Florence and WIPMunich: Rome, Italy, 2004, p. 742. Potic, B.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M. Gasification of Model Compounds and Wood in Hot Compressed Water. Submitted to Ind. Eng. Chem. Res. 2005. Quaak, P.; Knoef, H.; Stassen, H.M., Energy from Biomass: A Review of Combustion and Gasification Technologies. World Bank Publications, 1999. Reith, J.H.; Uil, H. de; Veen, H. van; Laat, W.T.A.M. de.; Niessen, J.J.; Jong, E. de.; Elbersen, H.W.; Weusthuis, R.; Dijken, J.P. van; Raamsdonk, L., Co-production of Bio-ethanol, Electricity and Heat from Biomass Residues. ECN-RX-02-030; Petten: The Netherlands, 2002. Saka, S.; Ueno, T., Chemical Conversion of Various Celluloses to Glucose and its Derivates in Supercritical Water. Cellulose 1999, 6, 177. Savage, P. E., Organic Chemical Reactions in Supercritical water. Chem. Rev. 1999, 99, 603. Schmieder, H.A.J.; Boukis, N.; Dinjus, E.; Kruse, A.; Kluth, M.; Petrich, G.; Sadri, E.; Schacht, M., Hydrothermal Gasification of Biomass and Organic Wastes. Proceedings of the 5th Conference on Supercritical Fluids and their Applications: Garda, Italy, 1999, p. 347. Sinag, A.; Kruse, A.; Schwarzkopf, V., Key Compounds of the Hydropyrolysis of Glucose in Supercritical Water in the Presence of K2CO3 . Ind. Eng. Chem. Res. 2003, 42, 3516. Sinag, A.; Kruse, A.; Rathert, J., Influence of the Heating Rate and the Type of Catalyst on the Formation of Key Intermediates and on the Generation of Gases During Hydropyrolysis of Glucose in Supercritical Water in a Batch Reactor. Ind. Eng. Chem. Res. 2004, 43, 502. Soave, G., Equilibrium Constants from a Modified Redlich-Kwong Equation of State. Chem. Eng. Sci. 1972, 27, 1197. Soave, G.; Barolo, M.; Bertucco, A., Estimation of High-Pressure Fugacity Coefficient of Pure Gaseous Fluids by Modified SRK Equation of State. Fluid Phase Equilib. 1993, 91, 87. Stein, Y.S.; Antal, M.J.; Jones, M., A Study of the Gas-Phase Pyrolysis of Glycerol. J. Anal. Applied Pyrolysis 1983, 4, 283-296. The National Renewable Energy Laboratory's, Energy Efficiency and Renewable Energy Technology Development in China; 2006. United Nations Environment Programme, Introduction to Climate Change; 2005.

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Van de Beld, L.; Wagenaar, B.M.; Assink, D.; Potic, B.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M.; Penninger, J.M.L., Biomass and Waste Conversion in Supercritical Water for the Production of Renewable Hydrogen. Presented at the 1st European Hydrogen Energy Conference, Grenoble: France, 2003. Van den Aarsen, F.G., Fluidised Bed Wood Gasifier Performance and Modelling. Technical High School of Twente, Enschede, The Netherlands, 1985. Van Swaaij, W.P.M.; Prins, W.; Kersten, S.R.A., Strategies for the Future of Biomass for Energy, Industry and Climate Protection. In Proceedings of the 2nd World Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection; van Swaaij, W.P.M.; Fjallstrom, T.; Helm, P.; Grassi, A., Eds.; ETA-Florence and WIP-Munich: Rome, Italy, 2004. Wang, X.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M., Experimental Validation of Model Results. Ind. Eng. Chem. Res. 2005, 8767. Woerner, G. A., MS Thesis, MIT, 1976. World Energy Council, Survey of Energy Resources 2004. Elsevier, 2004. Xu, X.; Matsumura, Y.; Stenberg, J.; Antal, M.J., Carbon-Catalyzed Gasification of Organic Feedstocks in Supercritical Water. Ind. Eng. Chem. Res. 1996, 35, 2522. Xu, X.; Antal, M.J., Jr., Gasification of Sewage Sludge and Other Biomass for Hydrogen Production in Supercritical Water. Enviromental Progress 1998, 17, 215. Yu, D.; Aihara, M.; Antal, M.J., Hydrogen Production by Steam Reforming Glucose in Supercritical Water. Energy Fuels 1993, 7, 574.

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35

36

Chapter 2
A High-Throughput Screening Technique for Conversion in Hot Compressed Water
Abstract

Conversion in hot compressed water (e.g. 600oC and 300 bar) is considered to be a promising technique to treat very wet biomass or waste streams. In this chapter, a new experimental method is described that can be used to screen the operating window in a safe, cheap, and quick manner (one measurement takes about 5 min). Small sealed quartz capillaries (i.d. = 1 mm) filled with biomass or model compounds in water are heated rapidly in a fluidized bed to the desired reaction temperature. The reaction pressure can be controlled accurately by the initial amount of solution in the capillary. After a certain contact time, the capillaries are lifted out of the fluidized bed, rapidly quenched, and destroyed to collect the produced gases for GC analysis. Results of measurements for formic acid and glucose solutions have shown that the technique is reliable enough for screening purposes including trend detection. For conversions above 30%, three identical measurements are sufficient to produce reasonably accurate average values with a confidence level of 95%.

This chapter has been published in Ind. Eng. Chem. Res, 43 (2004), p. 4580

37

Introduction
Process intensification is a novel design approach in which reduction of equipment size leads to less energy consumption, improved safety, lower capital costs, and less pollution (Burns and Ramshaw, 1999; Dummann et al., 2003; Rebrov et al., 2003). In this chapter, the intensification principle has been applied to a screening technique for the conversion of biomass in hot compressed water, in particular gasification of biomass/waste in supercritical water (SCWG). Very wet biomass (moisture content > 70 wt %) cannot be converted economically by traditional techniques such as combustion and gasification due to the energy required for water evaporation (2.4 MJ/kg). In SCWG, water evaporation is avoided and intensive countercurrent heat exchange is practiced. Therefore, SCWG is considered as a promising technique to convert wet streams into a hydrogen-rich gas (Antal et al., 1993; Holgate et al., 1995; Modell, 1985). Biomass is converted in the presence of water, e.g. via: C6H12O6 + 6H2O 6CO2 + 12H2

The above stoichiometric equation is highly idealized; in practice, also CO, CH4, C2-3-components, liquids (including H2O), and polymers are formed next to CO2 and H2 (Schmieder et al., 2000). The product distribution appears to be a strong function of the reactor temperature and the weight percentage of organic material in the feedstock (Kruse et al., 1999). Antal and co-workers (Yu et al., 1993) found that the wall material (Hastelloy, Inconel) of their bench-scale continuous flow reactor had a large effect on the obtained results. This finding points to an important role of catalysis in SCWG. Consequently, data obtained in small-scale metal reactors are obscured by undefined catalytic effects, and therefore difficult to interpret and extrapolate. The novel method uses quartz capillaries of 1 mm i.d., 2 mm o.d., and 150 mm length as batch reactors, which have no catalytic activity. Unfortunately, the number of experimental SCWG data published is small, while at the same time the range of conditions explored is narrow. This is partly due to the severe operating conditions (300 bar and 600oC), which make laboratory testing at bench-scale (1 - 100 g/h, 10 mL < Vreactor < 1 L) problematic, expensive, and time-consuming. The proposed technique will allow mapping of the complete operating area and trend detection of the process at moderate costs in just a short period of time. Because of the small diameter and the properties of quartz, these microreactors can withstand conditions up to 900oC and 600 bar. Apart from SCWG of biomass, this technique can be used also to study other thermochemical conversion processes of wet feedstock, such as hydrothermal liquefaction, oxidation in supercritical water (SCWO), and possibly many other high pressure processes. Hereafter, the novel technique will be explained and validated in detail.

38

Experimental
Methodology The method uses quartz capillaries of 1 mm i.d., 2 mm o.d., and 150 mm length as batch reactors (see Figure 2.1). An experiment is started by charging a capillary with a known amount of aqueous solution (biomass or a model compound dissolved in water). Hereafter the capillary is sealed and rapidly heated in a high-temperature fluidized bed to the desired reaction temperature. In the heating trajectory, the pressure increases as a result of the evaporating water. By varying the amount of solution in the capillary, the final pressure is known and can be adjusted quite accurately, as the water vapor pressure predominantly determines the total pressure. If a more precise estimate of the pressure is required, thermodynamic calculations can be applied on the basis of the initial amount of water and the measured amount of product gases. After a certain contact time at a specific reaction temperature and pressure, the capillary is quenched to ambient conditions, which ensures that all reactions are stopped. Finally, the gas phase inside the capillary is analyzed with respect to the absolute amount and the composition.

Figure 2.1 Photograph of the capillaries together with 1 euro coin. Advantages and Restrictions This new experimental method has several advantages: conducting an experiment is fast, cheap, and safe (the reactor volume is 0.12 mL), the quartz capillaries are strong enough to withstand extremely high pressures (600 bar) and high temperatures (900oC), quartz has no or hardly any catalytic activity, quartz is resistant to corrosion, catalysts can be easily added , and only very small amounts are required, the reactor content can be inspected visually (char, water-soluble organic compounds, and tars can be identified in case of SCWG of biomass) and, the quartz reactors can be heated and cooled rapidly, leading to more precise results.

39

A disadvantage of the technique is that analysis of the liquid phase is extremely difficult, due to very small sample volume, and has not been practiced up to now. Hence, when products are present in the liquid phase, complete mass balance closure cannot yet be obtained. Depending on the development/availability of liquid analysis methods with respect to the minimum required sample volume, this disadvantage can be overcome. Small (diameter) reactors are required in order to hold the large pressure built up and to ensure fast heat transfer. Fast heat transfer will guarantee accurate knowledge concerning the reaction temperature, which is necessary for correct data interpretation. It is common knowledge that in fluidized beds high heat transfer coefficients can be achieved, especially when the bed particles and the immersed objects are small (Parmar and Hayhurst, 2002; Prins et al., 1986; Prins et al., 1989). This has been checked by submerging a silver cylinder with the same dimensions as the used capillaries in a fluidized bed (dp = 250 m, u/umf = 2). The external heat transfer coefficient derived from the heating curve appeared to be ca. 1000 W/(m2.K), which is in good agreement with predictions from literature correlations (Parmar and Hayhurst, 2002, Prins et al., 1989). Inside the quartz wall of the capillaries, no important temperature gradients will be present because of the small dimensions (Dwall = 0.5 x 10-3 m) and the relatively high thermal conductivity ( = 1.8 W/(m.K)). The heating time of the used capillaries in the FB was determined experimentally to be approximately 5 s at a reactor temperature of 600oC. For this measurement, a thermocouple was welded into a water-filled capillary. The measured heating time (5 s) is in good agreement with the calculated one (4.5 s), which is based upon the measured external heat transfer coefficient, the known properties of the quartz wall, and minimum heat transfer conditions from the wall to the solution inside. The pressure-temperature and density trajectories of the feed material during heating to the reaction conditions differ from those of continuous reactors. Continuous reactors are operated essentially isobaric, whereas the capillaries, because of the fixed volume and initial mass, are isochoric reactors. This could, in principle, be a cause for deviations in results between continuous reactors and the batch capillaries. However, from a few special SCWG tests in which the heating trajectory of the capillaries was varied, it appeared that the product composition is determined almost entirely by the final process pressure and temperature.

Experimental Setup As mentioned before, the capillaries were heated in a fluidized bed (sand particles of dp = 250 m, u/umf = 2), which was placed in a temperature-controlled oven. For each measurement two capillaries were placed on a holder especially designed to allow quick and safe manual operation. The temperature inside the FB was measured with thermocouples. After a certain contact time at the desired reaction temperature and pressure, the capillaries were quenched in a water bath to ambient
40

conditions, to ensure that no further reactions proceeded. The produced gases were analyzed by the following method: a quenched capillary was put into a stainless steel chamber of 50 mL, then this chamber was flushed with helium to remove traces of product gas from a previous run, hereafter, the chamber was closed (with valves) and the capillary was crushed completely with a hammer mechanism, finally, a gas sample was taken from the chamber and led to a gas chromatograph. It is essential to crush the capillaries completely. Otherwise gas gaps, containing products, could be captured between liquid phases, and excluded from the gas analysis. Gaseous products were analyzed with a gas chromatograph using TCD cells (Varian Micro GC CP2003). Two columns were used: a Molsieve 5A, operated at 90C and 155 mbar, and a Porapak Q operated at 75C and 155 mbar. Helium was used as a carrier gas. The chromatograms were obtained and interpreted with Varian CP-Matre Elite software. Figure 2.2 is a schematic representation of the setup.

41

6
PI

TI

7 He
TI

Analytical section
PI

1 in

in 8

4 1 7 out

GC

out

TC 10

N2

Figure 2.2

Schematic representation of the capillary reactor technique: (1, capillary; 2, nitrogen

supply for the fluidized bed; 3, oven; 4, fluidized bed; 5, thermocouples; 6, capillary holder; 7, sampling chamber; 8, pressure indicator; 9, gas chromatograph; 10, temperature controller for the oven).

Data Interpretation and Possible Errors The degree of conversion of carbon in biomass to permanent gases (carbon efficiency, Xc) is chosen here as the main process parameter for SCWG, because it indicates the distribution of carbon over the desired products (permanent gases) and the undesired product (liquids and polymers). In practice, the product composition can be modified catalytically, viz., by water-gas shift to produce CO2 and H2, or by methanation to produce CH4. Xc is defined by:

Xc =

N c , permanent gas N c , solution

PV ( RT ) =

( msolution f ) nc

chamber

CO

+ CO2 + CH 4 + 2C2 H 4 + ...

42

Like every other experimental technique, also the newly developed capillary reactor method contains certain error margins in the experimental parameters (see Table 2.1). Table 2.1 Possible maximum experimental errors estimated for an experiment with a 17 wt % glucose solution in water. Quantity
chamber

(PV RT )

Value (x) 3 x 10-3 9 x 10-5 Varies

Error (x) 3 x 10-5 3.6 x 10-6 Varies

Units Mol Mol -

x/x (%) 1 4 2 1 8

( msolution f ) nc

TFB Maximal possible error

As the main output of the method is the carbon efficiency, the error analysis will be focused on this parameter. The number of moles present in the sampling chamber is known accurately by precise measurement of T (within 1oC), P (within 500 Pa), and V (within 0.1 mL). The reaction solution was prepared in batches of 50 g using high-precision balances (accuracy 0.001 g). For the mass of solution actually put into the capillary, the error is the highest (ca 4%). This error is introduced mainly because the capillaries are sealed rapidly and carefully in a hydrogen flame, but, nevertheless, some water will be evaporated. Furthermore, it has been found that small variations in the fluid bed temperature may cause differences in carbon efficiency ( 1% every 3oC for a 17 wt % glucose solution at Xc < 50%; see Figure 2.4). In the low conversion regime this error is significant, whereas near the maximum conversion, obviously, the effect of the exact process conditions disappears. Overall, the maximal possible experimental error in the carbon efficiency was estimated to be approximately 8% in a typical case (see Table 2.1), which is accurate enough for trend detection.

43

Results and Discussion

Visualization As mentioned before, some products, such as tars and solid carbon (char), for SCWG, are clearly visible after the reaction has been carried out in the quartz capillaries. In practice, char formation in the heat-exchanger (the feed-site exit temperature is typically 450oC) will be one of the major bottlenecks of the SCWG process (Potic et al., 2002). Figure 2.3 shows capillaries with high and low levels of char/tar formation, indicating that possible problems can indeed be identified visually.

(a)

(b) Figure 2.3 Capillaries with a different level of char/tar formation after SCWG (a) 17 wt % glucose in water at 600oC, (b) 10 wt % glucose in water at 720oC.

Effects of the Heating Trajectory To understand the effect of the heating trajectory of the capillaries on the carbon efficiency, special tests have been performed. The following results were compared: capillaries with a short residence time in the FB (columns 1-3 of Table 2.2), capillaries which were quenched after a short residence time (the same as in columns 1-3 of Table 2.2) and then reheated up to a 1 min total residence time in the FB (column 4 of Table 2.2), capillaries with a 60 s residence time without interruption (column 5 of Table 2.2).

44

Table 2.2

Carbon efficiency, Xc (%), measured for a 10 wt % glucose solution in water. The final

conditions are 600oC and 300 bar. Illustration of the effect of heating interruption after 1, 2, or 3 s.

Heating time and sequence 1s Xc Xc Xc Xc 0.08 0.08 0.1 0.15 2s 3s 60 s residence time after the interruption 0.69 0.76 0.69 0.71 60 s residence time without any interruption 0.69 0.72 0.73 0.73

From Table 2.2 it can be concluded that the heating trajectory has no notable effect on the final carbon efficiency. Continuation of interrupted experiments results approximately in the same final carbon-togas conversion degrees as those of noninterrupted experiments. The differences between the figures in the last two columns of Table 2.2 are all well below the experimental error. It should be realized that the results of Table 2.2 have been derived for isochoric conditions. Whether or not the corresponding conclusion is also valid for continuous tubular reactors should be proven in subsequent experimental work.

Validation of the Technique Mass balance closure was investigated by experiments with components which, according to the literature (Yu and Savage, 1998), should be converted completely to gas-phase components at temperatures above 700oC and low feed concentrations. Additional measurements were carried out under conditions that should give a much lower carbon conversion. They were used to evaluate the reproducibility of the method for SCWG in case a significant amount of carbon remains in the liquid or solid phase. Formic acid and glucose were selected as model compounds. On basis of this analysis, the number of identical experiments could be defined whose average should represent a good estimate of the mean value. As mentioned before, the carbon efficiency was selected as an identifier for the process. Table 2.3 shows series of measurements for which the average carbon efficiency and related experimental error were calculated.

45

Table 2.3 Results of SCWG measurement series illustrating the reproducibility and accuracy of the experimental technique (P > Pc).

Model Compd Formic Acid Glucose Glucose Glucose

Concn. wt % 1.2 0.8 18 17

T(oC)

Nr 4 3 4 8

<Xc> 1.005 1.003 0.535 0.203

/<Xc> (%) 4.1 4.1 8.1 16.2

Nr required for 95% CI 5% error 3 3 10 41 10% error 1 1 3 10

700 700 550 460

0.041 0.041 0.043 0.033

The first two series (100% carbon efficiency, see Table 2.3) show that all produced gases can be recovered with the novel method despite the very small volumes used. For all the series, the experimental error found is acceptable and not in disagreement with the estimated one, except for the low conversion range (< 25%). The reaction system is here possibly very sensitive to auto-catalytic effects. On the basis of the estimations of Table 2.1, in combination with statistical analysis (Devore, 2000) of the first three series of Table 2.3, it was decided that three identical experiments is sufficient to guarantee, for a confidence level of 95%, a mean value with an error width of 0.1 < Xc > (see Table 2.3, last column). Clearly, the experimental technique described in this chapter can be used very well to estimate reaction kinetics, determine trends, and explore the operating window for SCWG. An example of a measured trend is presented in Figure 2.4.

46

100

80

60

Xc [%]

40

20

0 400

500

600

700

800

o T [ C]

Figure 2.4 Measured carbon efficiency of a 17 wt % glucose solution versus the reactor temperature. = 60 s. The plotted line represents a trend line. It has been found that, for a 17 wt % glucose solution in water above Pc with a contact time of 1 min, the carbon efficiency increases asymptotically from 20% to 80% within a temperature range of 460 700oC.

47

Conclusion
A novel high-throughput screening technique has been developed which allows quick and safe experimentation with thermochemical conversion reactions of wet feedstock at severe operating conditions in a noncatalytic environment. This technique gives sufficient accuracy for all the measuring conditions and is certainly satisfactory for the overall mapping of the experimental area and trend detection. Advantages of the technique are the possibility of applying high temperatures and pressures, the absence of undesired catalytic effects of the reactor wall, the absence of corrosion, rapid heating and cooling, and easy visual inspection. Future developments may open the possibility of liquid analysis, which has not been practiced up to now. The reactor system is isochoric, and the heating trajectories of the reactants differ from those of a continuous isobaric system, but this does not seem to affect the results in an important way. For this work, formic acid and glucose were used as model compounds. Future experiments will include real biomass samples such as wood and agricultural waste.

Notation dp F ID M msolution nc Nc,permanent gas Nr Nsolution o.d. P Pc R T TFB U umf V Vreactor Particle diameter in the fluidized bed oven, m Fraction of biomass in the solution, g/g Inside diameter, mm Molar mass, g/mol Mass of the solution, g Number of carbon atoms in one molecule of biomass Number of carbon moles in the permanent gas Number of samples Number of carbon moles in the solution Outside diameter, mm Pressure, Pa Critical pressure, Pa Gas constant, J mol-1 K-1 Temperature, K Temperature of the fluidized bed, K Velocity of the air in the fluidized bed oven, m/s Minimum fluidization velocity, m/s Volume, mL Volume of the reactor, mL
48

Xc Greek Symbols Subcripts

c

Carbon efficiency, %

Standard deviation Reaction time, s Mole fraction

Carbon

Operators <> Mean

References

Antal, M.J.; Manarungson, S.; Mok, W.S., Hydrogen Production by Steam Reforming Glucose in Supercritical Water. In Advances in Thermochemical Biomass Conversion; Bridgwater, A.V., Ed.; Blackie Academic and Professional: London, 1993, 1367. Burns, J.R.; Ramshaw, C., Development of a Microreactor for Chemical Production. Trans. Inst. Chem. Eng. 1999, 77, 206. Devore, J.L., Probability and Statistics for Engineering and the Sciences; Duxbury: Pacific Grove, CA, 2000. Dummann, G.; Quittmann, U.; Groschel, L.; Agar, D.W.; Worz, O.; Morgenschweis, K., The Capillary-Microreactor: a New Reactor Concept for the Intensification of Heat and Mass Transfer in Liquid-Liquid Reactions. Catal. Today, 2003, 79-80, 433. Holgate, H.R.; Meyer, J.C.; Tester, W.J., Glucose Hydrolysis and Oxidation in Supercritical Water, AIChE J. 1995, 41, 637. Kruse, A.; Abeln, J.; Dinjus, E.; Kluth, M.; Petrich, G.; Schacht, M.; Sadri, H.; Schmieder, H., Gasification of Biomass and Model Compounds in Hot Compressed Water. Presented at the International Meeting of the GVC-Fachausschu "Hochdruckverfahrenstechnik", Karlsruhe, Germany, 1999; paper no. 107. Modell, M., Gasification and Liquefaction of Forest Products in Supercritical Water. In Fundamentals of Thermochemical Biomass, Overend, R.P.; Milne, T.A.; Mudge, L.K., Eds.; Elsevier Applied Science Publishers Ltd.: London, 1985, p. 95. Parmar, M.S.; Hayhurst, A.N., The Heat Transfer Coefficient for a Freely Moving Sphere in a Bubbling Fluidised Bed. Chem. Eng. Sci. 2002, 57, 3485.

49

Potic, B.; van de Beld, L.; Assink, D.; Prins, W.; van Swaaij, W.P.M., Gasification of Biomass in Supercritical Water. In Proceedings of the 12th European Conference and Exhibition on Biomass for Energy, Industry and Climate Protection; Palz, W.; Spitzer, J.; Maniatis, K.; Kwant, K.; Helm, P.; Grassi, A., Eds.; ETA Florence, WIP Munich: Amsterdam, 2002; p. 777. Prins, W.; Draijer, W.; van Swaaij, W.P.M., Heat Transfer to Immersed Spheres Fixed or Freely Moving in a Gas-Fluidized Bed. In Heat and Mass Transfer in Fixed and Fluidized Beds. Van Swaaij, W.P.M.; Afgan, N.H., Eds.; Hemisphere Publishing Corp.: Washington, DC, 1986. Prins, W.; Harmsen, G.J.; De Jong, P.; van Swaaij, W.P.M., Heat Transfer from an Immersed Fixed Silver Sphere to a Gas Fluidized Bed of Very Small Particles. In Fluidization VI; Grace, J.R.; Shemilt, L.W.; Bergougnou, M.A., Eds.; Engineering Foundation: New York, 1989. Rebrov, E.V.; Duinkerke, S.A.; de Croon, H.M.J.M.; Schouten, J.C., Optimization of Heat Transfer Characteristic, Flow Distribution and Reaction Processing for a Microstructured Reactor/Heatexchanger for Optimal Performance in Platinum Catalyzed Ammonia Oxidation. Chem. Eng. J. 2003, 93, 201. Schmieder, H.; Abeln, J.; Boukis, N.; Kruse, A.; Kluth, M.; Petrich, G.; Sadri, E.; Schacht, E., Hydrothermal Gasification of Biomass and Organic Wastes. J. of Supercrit. Fluids 2000, 17, 145. Yu, D.; Aihara, M.; Antal, M.J., Hydrogen Production by Steam Reforming Glucose in Supercritical Water. Energy Fuels 1993, 7, 574. Yu, J.; Savage, P.E., Decomposition of Formic Acid under Hydrothermal Conditions. Ind. Eng. Chem. Res. 1998, 37, 2.

50

51

52

Chapter 3
Gasification of Model Compounds and Wood in Hot Compressed Water
Abstract
In this chapter, an experimental investigation is presented that concerns the gasification of glycerol, glucose, and pinewood in supercritical water. The batch experiments were performed in quartz capillary reactors with an internal diameter of only 1 mm. Because these quartz reactors are catalytically inert, the process could be studied in absence of the interfering catalytic influence of a metal reactor wall, as used in all previous studies. The reaction space has been mapped by performing over 700 experiments in which the temperature, pressure, reaction time, and concentration of the feedstock were varied. The most important observations were that the pressure turned out to have no effect on the conversion and product yields, and that, noncatalytically, complete conversion to the gas phase is only possible for very diluted feedstock solutions (< 2 wt %). By adding ruthenium on a TiO2 carrier (Ru/TiO2) to the capillaries the potential of heterogeneous catalysis has been demonstrated. When adding this catalyst to the capillaries, glucose solutions in the range of 1 - 17 wt % could be gasified completely.

53

Introduction
Application of biomass and waste, as a renewable energy source, has gained an important role in the worlds future energy policy. The Dutch government, for instance, has set a target for 2020, which states that 5% of the total primary energy production must be based on biomass and waste input (MEZ, 1995, 1997). Similar directives have been put forward by the European Committee in their White Paper (European Commission, 2000). Biomass and waste streams can be classified by their moisture content. Wet feedstock is defined here as containing > 70 wt % moisture. Examples of wet waste streams include the following: vegetable, fruit and garden waste; waste streams from agricultural, food and beverage industries; manure; sewage sludge; and some household wastes. Seaweed and micro-algae are examples of cultivated wet biomass crops. According to estimates of the Energy Research Centre of The Netherlands (ECN), (Hemmes, 2004), 5.3 - 12 million tons (dry matter) of wet streams are annually available in The Netherlands. This corresponds to 70 - 160 PJ of energy (assuming 65% efficiency), which represents 2.3 - 5.3% of the current Dutch annual energy consumption. This chapter examines the conversion of wet streams into H2 and/or CH4 by means of gasification in hot compressed water. Wet biomass cannot be converted economically by traditional techniques such as pyrolysis, gasification, and combustion, because of the large amount of energy required for the evaporation of water. Partial conversion by anaerobic digestion is possible and already practiced for suitable feedstock materials (Sarada and Joseph, 1996). Gasification in supercritical water (SCWG) is a novel technology for the conversion of wet biomass and waste streams to hydrogen or methane-rich gas (Antal et al., 2000; Hao et al., 2003; Holgate et al., 1995; Lee et al., 2002; Manarungson et al., 1993; Matsumura, 2002; Matsumura et al., 2005; Modell, 1985; Yu et al., 1993). Regarding the useful products of SCWG, hydrogen, and/or methane, it is interesting that the selectivity can be controlled by the process conditions and catalysis. Biomass-derived hydrogen could be applied in the future as a renewable feedstock for fuel cells. Methane from biomass may be attractive as a renewable substitute of natural gas (SNG). The product gases could be available at high pressure, which is required for storage and transportation and in many end applications. The CO2 byproduct is almost pure and suitable for sequestration or fertilization in greenhouses. For proper process development of SCWG, data concerning the influence of the process conditions (temperature (T), pressure (P), reaction time (t), concentration (c)) on the gas yields and byproduct formation (char, liquid intermediates) are needed. Laboratory-scale results of SCWG experiments have been reported by several research groups (Antal et al., 1993; Hao et al., 2003; Holgate et al., 1995; Kabyemela et al., 1999; Kruse et al., 1999; Kruse et al., 2000; Kruse et al., 2002; Kruse and Gawlik, 2003; Kruse et al., 2003; Modell, 1985; Potic et al., 2002; Schmieder, 1999; Sinag et al., 2004; Xu et al., 1996; Xu and Antal, 1997; Yu et al., 1993). However, previously reported data are
54

obtained in small metal (e.g., Inconel, Hastelloy, stainless steel) reactors, which, to a variable extent, exhibit catalytic activity (Diem et al., 2003; Sinag et al., 2004; Yu et al., 1993). Because of this illdefined catalytic activity, the reported data on SCWG are difficult to compare and interpret. In this work, it is shown that Inconel indeed does have catalytic influence on SCWG reactions. Results of noncatalytic SCWG experiments are presented. These results have been obtained by experimentation with inert quartz microreactors (Potic et al., 2004) and are supposed to represent the plain (noncatalytic) performance of the process. Results of model compounds and pinewood are presented. The potential of heterogeneous catalysis for SCWG is discussed on the basis of experiments in which Ru/TiO2 catalyst was added to the quartz reactors.

55

Experimental
The investigation presented here is based on more than 700 experiments that have been conducted in the batch capillary reactors. In a previous paper (Potic et al., 2004), this measurement technique is described in detail, including an error analysis. The technique uses quartz capillaries with an inner diameter (ID) of 1 mm, an outer diameter (OD) of 2 mm, and a length of 150 mm as batch reactors. An experiment starts by charging a capillary with a known amount of aqueous solution (biomass or a model compound suspended or dissolved in water). Hereafter, the capillary is sealed and rapidly heated in a high-temperature fluidized bed to the desired reaction temperature. The heating time of the capillary in the fluid bed is 5 s. In the heating trajectory, the pressure increases as a result of the evaporating water. By varying the amount of solution in the capillary, the final pressure is known and can be adjusted quite accurately, because the water vapor pressure predominantly determines the total pressure. The reaction time is defined as the time that the capillary has been immersed in the fluid bed, minus the heating time (5 s). In a standard experiment, a reaction time of 60 s has been applied, because this reaction time turned out to be sufficient to reach the maximum conversion at the lowest typical SCWG temperature under noncatalytic conditions (600oC; see the section, Effects of Reaction Time). After a certain fixed time at a specific reaction temperature and pressure, the capillary is quenched to ambient conditions, which ensures that all reactions are stopped. Gas products are released in a metal sampling chamber (50 mL) by smashing the capillary with a hammer mechanism. Finally, the gas phase inside the capillary is analyzed to determine the absolute amount and the composition. On the basis of the readings of a gas chromatograph, the total number of moles present in the sampling chamber, and the amount of feedstock, the mass balance (yields and conversion) is calculated. The aim of the present investigation is mapping of the operating window of noncatalytic SCWG. The following parameters were varied: temperature (400 - 800oC), pressure (50 - 450 bar) and the concentration of organics in the feedstock (1 - 20 wt %). Different model compounds were used as feedstock (viz., glucose, glycerol, and cellulose). Besides these model compounds, pinewood also was used. Hereafter, every experimental data point presented in the figures shown is an average value that is based on at least six experimental data points (average standard deviation on the carbon conversion is 6%). The investigation is divided into two areas: noncatalytic gasification and catalytic gasification. For the catalytic investigation, ruthenium on TiO2 (Ru/TiO2) has been applied. Moreover, Inconel 625 powder has been used as an additive for identification and quantification of the catalytic influence of the metal wall of the reactors that have been reported in open literature. The carbon conversion, the product yields, and the cold-gas efficiency are chosen here as the main output parameters of the process.
56

The carbon conversion is defined as degree of conversion of carbon from biomass to permanent gases:

Xc =

N c,i x100

N c , feed

The product yield is defined as:

Yi =

Ni N feed

In case of wood, the elemental composition has been normalized to C6HyOz (glucose C-basis). The cold-gas efficiency (LHV) is defined as:

LHV =

Y LHV
i i

LHV feed

x100

As described previously, the capillary is charged in air, resulting in a certain amount of oxygen (air) being inevitably present in the capillary after the sealing. The amount of hydrogen lost due to oxidation by slipped-in oxygen can be estimated from the experimental results of low-concentration glucose solutions (1 wt %) processed at high temperature (800C). Typical product gas yields per mol of glucose of SCWG at 800oC were as follows: 5.5 for CO2, 0.5 for CH4, 0 for CO, 0 for C2- and C3components, and 6 for H2 (see Figure 3.4 which will be discussed later in this work). From a carbon balance under these conditions, it follows that carbon gasification is complete for this experiment: 5.5C (CO2) + 0.5C (CH4) = 6C (in glucose). If the reaction would proceed via the pathway C6H12O6 + 5H2O 2 + 5.5CO2 + 0.5CH4 the value of would be 10. However, for these low-concentration solutions, has been measured to be 6. This would mean that 4 mol of H2 per mol of glucose were oxidized by slipped-in O2. In absolute numbers, this comes down to ca. 1 x 10-6 mol of H2. The maximum amount of O2 from air present in the capillaries is 9 x 10-7 mol. If we may assume that the O2 inclusion is the same in absolute value, the effect of slipped-in oxygen can be neglected for all other conditions investigated in this work.
57

Results and discussion

Catalytic Effects of Metal Reactors As mentioned earlier, all previously reported results on gasification in hot compressed water were obtained in metal reactors. Stainless steel, Inconel, Hastelloy, and corroded Hastelloy were used as construction materials. Both empty tubular reactors and stirred cells were used in the laboratory work that has been performed thus far. Results obtained in tubular reactors were reported mainly by Antal and co-workers (Antal et al., 2000; Xu et al., 1996; Yu et al., 1993). The diameter of the tubular reactors was in the range of 1.44 mm to 6.22 mm with a corresponding specific possible catalytic wall area of 2778 m2 per unit volume reactor to 643 m2 per unit volume reactor. Reynolds numbers were mostly in the range for laminar flow. Nevertheless, the flow in these reactors presumably approached plug flow. Because of the small reactor diameter, radial mixing by molecular diffusion was fast enough to compensate for mixing effects caused by the laminar flow velocity profile (the Peclet number always exceeded 50). Sinag et al. (Sinag et al., 2003) conducted SCWG experiments in a 190 mL metal autoclave that was equipped with a stirrer. In their experiments, a cold feed stream was continuously injected into the hot autoclave. Literature data already indicate that the reactor material has a significant effect on the gasification process. Yu et al. (Yu et al., 1993), for instance, reported results of gasification of glucose in the same experimental setup under identical conditions, but using other metals for the reactor. They found large differences between experiments that were conducted in Inconel, Hastelloy, and corroded Hastelloy reactors. For a test series using 0.6 M acetic acid, they observed 14% carbon conversion in the Inconel reactor, whereas in the corroded Hastelloy reactor, the carbon conversion was as high as 53%. In the present work, catalytically inert quartz capillaries have been used for the investigation of gasification in hot compressed water. These results are supposed to represent the plain performance of the process. Table 3.1 shows a comparison between glucose gasification tests in the quartz capillaries and in metal reactors (data from literature) for almost identical conditions. Clearly, the results obtained in the noncatalytic quartz tubes deviate from those obtained in metal reactors (see Table 3.1) in cases where the feedstock contains only a low amount (1.8 wt %) of glucose. Compared to Inconel reactors, the conversion of carbon from the feed to the gas phase is less in the quartz capillaries. Apparently, nickel in the Inconel reactor wall (there is ca. 60 wt % nickel in Inconel 625) catalyzes the glucose decomposition into gaseous components. Results that have been obtained in the stainless steel reactor are similar to those obtained in quartz capillaries, with respect to carbon conversion; however, the hydrogen production, as a result of the water-gas shift reaction, is significantly higher. Al data obtained in the quartz capillaries were compared with (almost) identical
58

tests that have been reported in the literature. Based on this analysis, it can be concluded that the carbon conversion in the quartz capillaries is lower than that in Inconel and Hastelloy reactors. The difference in carbon conversion is high, up to 20%, for low-concentration feeds (for example, 3 wt %) and reduces to zero for solutions that contain > 10 wt % of organics. Metal reactors always show more water-gas shift activity than the quartz capillaries, irrespective of the feedstock concentration. Table 3.1 Comparison between SCWG results obtained in inert quartz capillaries and metal reactors (data from literature) glucose, low concentration 1.8 wt % (Hao et al., 2003) SS 316 tubular 600 250 61 31.2 41.7 21.8 4.0 1.3 1.8 wt % (Yu et al., 1993) Inconel tubular 600 345 90 61.6 29 2 7.2 not available 1.8 wt % this work Quartz batch 600 300 70 13.3 20 53 6 7.4 glucose, high concentration 10 wt % (Lee et al., 2002) Hastelloy tubular 600 280 67.3 43.1 28.2 9.7 11.6 7.4 10 wt % this work Quartz batch 600 300 69 11.7 8.9 60.5 12.9 6.0

feed reference reactor T [oC] P [bar] Xc [-] H2 CO2 CO CH4 C2+

gas composition [mol %]

Generally, it can be concluded that, in metal reactors, carbon monoxide formation is low and H2 formation is high, compared to the quartz capillaries (see Table 3.1). This indicates that small-scale metal reactors have a tendency to promote the water-gas shift reaction. To show the catalytic effect of Inconel, Inconel powder (dp = 100 - 200 m) was added to the inert quartz capillaries. Tests were conducted at 600C with a 5 wt % glycerol solution. The results are presented in Figure 3.1.

59

1.4

100

yield [mole gas/ mole glycerol]

1.2 80 1.0 0.8 0.6 0.4 20 0.2 0.0 0 2 4 6 0 H2 CO CO2 CH4 60

carbon efficiency [%]

C2H4 C2H6 carbon efficiency [%]

40

inconel powder [g Inconel/g solution]

Figure 3.1 Effect of Inconel 625 on the carbon efficiency and product-gas yields. Inconel was added to the capillaries in powder form. A 5 wt % glycerol solution in water was used as feedstock. T = 600
o

C, P = 300 bar, = 60 s.

Although the mixing of the powder in the capillary was not ideal, resulting in some scatter in the results, the general trend of the carbon conversion and gas distribution can be observed. The carbon conversion and the yields of CO, CO2, CH4, and H2 increase due to the addition of Inconel powder to the capillary reactor (see Figure 3.1). Although it is impossible to relate the amount of Inconel added to the capillaries to the catalytic activity of a metal reactor wall, it is obvious that Inconel has a profound influence on the results of glucose gasification. It is clear from the data presented above that the metal laboratory reactors used in previous investigations exhibited a catalytic effect. Metal walls seem to catalyze the carbon conversion (total gas production) and the water-gas shift equilibrium. Because of this catalytic effect of the wall, which may also be influenced by corrosion, published data are difficult to compare and interpret. Besides, the catalytic activity of small laboratory equipment cannot be translated to large-scale reactors, which have a much smaller ratio of wall area to volume. As a consequence, reliable information on the chemistry and kinetics of biomass and waste gasification in high-temperature and high-pressure water is missing. The difficulties regarding the interpretation of laboratory-scale data become already clear when comparing the available laboratory data with the few pilot-plant experiments that have been conducted so far. In pilot-plant runs with the UT/BTG facility (Potic et al., 2004; Van de Beld et al., 2003), less H2 and more CO production was observed, compared to the tests conducted in laboratory reactors made from the same material and under similar conditions (T, P, c, ). This can be ascribed to the lower ratio of (catalytic) wall-area to volume of the pilot facilities. The tubular reactor in the pilot facility of BTG/UT has a specific wall area of 286 m2 per m3 reactor, being ca. a factor of 7 lower than for the majority of the laboratory reactors (see above).
60

Noncatalytic Gasification in Hot Compressed Water It has been demonstrated that tests in small laboratory reactors are obscured by undefined catalytic effects. In this section, results of gasification experiments in catalytically inert quartz capillaries that are supposed to represent the plain performance of SCWG will be presented.

Effects of temperature and concentration Decomposition in hot compressed water starts already at temperatures as low as 200oC, producing mainly tarry products and char. Figure 3.2 shows a photograph of a capillary reactor after reaction. The reaction medium of 10 wt % glucose solution was exposed to 400oC and 250 bar for a reaction time of 60 s. The photograph shows that, at such low temperatures, liquid and solid products are formed. Currently, the exact nature of these reaction products cannot be identified with the applied capillary technique.

Figure 3.2 Photograph of the content of a capillary reactor after low-temperature gasification. A 10 wt % glucose solution in water was used as feedstock. (T = 400oC, P = 300 bar, t = 60 s). Figure 3.3 shows the effect of the reactor temperature and the concentration of organics in the feed on the carbon conversion. For the model compounds (glucose and glycerol), the conversion reaches a constant level beyond 650C. Further increasing the temperature up to 800oC does not change the carbon conversion. Hence, the carbon conversion reaches a maximum value. This maximum conversion is dependent on the concentration of organic material in the feed: 1 wt % glucose in water can be converted completely, whereas the maximum carbon conversion of 17 wt % glucose is only 83%. This dependency of the conversion on the concentration was also found by Antal and co-workers (Yu et al., 1993). Pinewood has a much lower maximum conversion (ca. 40%) than the model compounds used. Below 650C, the carbon conversion is a strong function of the temperature. For glucose and glycerol, the difference between 600C and 650C is, more or less, equivalent to 20% conversion. This result points toward the need for precise control and measurement of the reactor temperature to obtain well-defined experimental results. In that respect, the temperature gradients and peak temperatures, sometimes reported to be present in the reactors used to study SCWG (Antal et al., 2000), may have influenced earlier results significantly. This has also been discussed by Antal et al. (Antal et al., 2000).
61

100

80

Xc [%]

60

40

20

0 400

glycerol 19 wt % wood 15 wt% glucose 1 wt% glucose 10 wt% glucose 17 wt%

500 600 700 800

T [oC]

(a)
100

80

gas composition [%]

60

glycerol 19 wt% H2 CO2 CO CH4 glucose 17 wt% H2 CO2 CO CH4

40

20

550

600

650

700

T [oC]

(b) Figure 3.3 (a) Influence of the temperature and the concentration on the carbon efficiency for SCWG of glycerol, glucose, and pine wood. (b) Influence of the temperature on the gas production for SCWG of high-concentration solutions of glucose and glycerol (C2 and C3 components are not shown. P = 300 bar. = 60 s.). Glucose and glycerol show identical gasification behavior, with respect to the carbon conversion (see Figure 3.3a). This is rather surprising, given the fact that they are different chemical species: glucose is a sugar and glycerol is an alcohol. It may indicate that the main reactions of gasification in hot compressed water are thermal cracking reactions, just like in dry gasification. Also, in dry gasification, it has been found that the exact nature of the feedstock hardly influences the process performance (Van der Drift et al. 2001). However, looking at the H2/CO ratio for high concentrations of glycerol and glucose at temperatures of 550, 600, 650, and 700oC (see Figure 3.3b), a significant difference is observed. The production of hydrogen, mainly as a result of the water-gas shift reaction, is at least 2 times higher in the case of glycerol. Apart from H2, CO, CO2, and CH4, some C2 (C2H4, C2H6) and C3 (C3H6, C3H8) components are produced (~10%), with ethane being a major component.
62

The carbon conversion of wood is very low, compared to that of glucose and glycerol, which can be ascribed by the presence of lignin in wood. Lignin itself is difficult to gasify and it has been observed that lignin blocks the conversion of woods other constituents: cellulose and hemi-cellulose (Yoshida and Matsumura, 2001; Yoshida et al., 2004). The effect of the reactor temperature on the product distribution is discussed based on the results of glucose solutions processed at 300 bar and a reaction time of 60 s, with a low (1 wt %), medium (10 wt %), and high (17 wt %) concentration of glucose (see Figure 3.4). The main gas products of the reaction are carbon monoxide, carbon dioxide, hydrogen, methane, ethane, and propane. Along with the carbon conversion, the yield of CO2, H2, and CH4 increase as the temperature increases. Also, the CO yield initially increases, but above 700C, CO rapidly decreases at constant carbon conversion (see Figure 3.4c), indicating that, above this temperature, the water-gas shift reaction starts to proceed. C3 components are not present in the product gas at temperatures of > 700C and the yield of C2 components strongly decreases at > 700C. This could point to enhanced reforming of C2 components at > 700oC.

hydrogen
10

1wt%

theoretical value

6 5 4 3 2 1 0 400

carbon dioxide
1wt%

yield [mole gas/ mole glucose]

yield [mole gas/ mole glucose]

10 wt%
8

10 wt% 17 wt%

17 wt%

0 400

500

600

700

800

o T [ C]

500

o T [ C]

600

700

800

(a)
carbon monoxide
3.0

(b)
1.5

methane
1wt%

1wt%
yield [mole gas/ mole glucose]

yield [mole gas/ mole glucose]

10 wt%
2.5 2.0 1.5 1.0 0.5 0.0 400

17 wt%

10 wt%
1.0

17 wt%

0.5

500

600

700

800

o T [ C]

0.0 400

500

600

700

800

o T [ C]

(c)
63

(d)

0.4

C2
1wt%

0.20

C3
1wt%

yield [mole gas/ mole glucose]

0.3

10 wt% 17 wt%

yield [mole gas/ mole glucose]

10 wt%
0.15

17 wt%

0.2

0.10

0.1

0.05

0.0 400

500

600

700

800

0.00 400

500

600

700

800

T [ C]

T [ C]

(e)

(f)

Figure 3.4. Influence of the temperature and the concentration of the glucose on the gas yields of (a) hydrogen, (b) carbon dioxide, (c) carbon monoxide, (d) methane, (e) C2 components, and (f) C3 components. (P = 300 bar, t = 60 s). The effect of the concentration on the yields can be summarized as follows. H2 and CO2 increase with decreasing concentration while CO, CH4, and C2 decrease. Figure 3.5 shows that, over the entire temperature range, the measured yields do not resemble the yields predicted by chemical equilibrium. At < 700oC, the deviation is very large. At 800oC and 1wt %, the experimentally found yields slowly start to approach chemical equilibrium mainly due to an enhanced water-gas shift reaction (see Figure 3.5) The equilibrium calculations were performed according to the Gibbs minimization method (Kyle, 1999). Fugacity coefficients were calculated with the modified Soave-Redlich-Kwong equation of state (Soave et al., 1993). The parameters for the modified Soave-Redlich-Kwong equation of state were obtained from Bertucco and Soave (Bertucco et al., 1995, Soave, 1972). Thermodynamic properties were taken from a NIST-JANAF source (NIST).

64

gas yield [mole gas/ mole glucose]

7 6 5 4 3 2 1

Capillary results H2 CO2 CO CH4

H2

CO2

CH4 CO
500 600 700 800

0 400

T [oC]

(a)
gas yield [mole gas/ mole glucose]
12 10 8 6 4 2 0 400
Capillary results H2 CO2 CO CH4

H2

CO2

CH4 CO
500 600 700 800

T [ C]

(b) Figure 3.5 Comparison between the measured and predicted chemical equilibrium product

distribution: (a) 17 wt % glucose and (b) 1 wt % glucose. (P = 300 bar, t = 60 s). In Figure 3.6, the cold-gas efficiency, and the individual contribution of the components to it, are plotted. In the same figure, the LHV of the product gas also is presented. Clearly at low temperature (low carbon conversion), only a small amount of energy stored in the feed can be transferred to the gas. For all three glucose solutions (1, 10, and 17 wt %) the maximum coldgas efficiency is attained near the temperature at which the carbon conversion is maximal (compare Figure 3.3 and 3.6). Up to 700 oC, the product gas can be characterized as fuel gas: it consists of CO, H2, CH4, and C2, all of which contribute significantly to the heating value. Above 700oC, the product

65

1.2

glucose 1 wt%
1.0

H2 CO CH4 C2,3 LHVgas

20

LHV gas/ LHV glucose

15

0.6

10

0.4 5 0.2

0.0

400

500

600

T [oC]

700

800

900

(a)
1.2 1.0

glucose 10 wt%

20

LHV gas/ LHV glucose

15 LHV gas [MJ/m ] 0.8 0.6 0.4 5 0.2 0.0 400 0 900 10
3

500

600

T [oC]

700

800

(b)
1.2

glucose 17 wt%

20

LHV gas/ LHV glucose

15 0.8 0.6 0.4 5 0.2 0.0 400 0 900 10

500

600

700

800

o T [ C]

(c) Figure 3.6. Cold gas efficiency, the individual contribution of the components to it, and the LHV of the produced gas versus the temperature: (a) 1 wt %, (b) 10 wt %, (c) 17 wt %. (P = 300 bar, t = 60 s).
66

LHV gas, MJ/m

1.0

LHV gas, MJ/m

0.8

gas is more pure: for the 1 wt % solution, the majority of the energy in the feed is transformed to hydrogen; a 10 wt % glucose solution produces a H2/CH4 mixture with some CO and C2, and in the case of 17 wt % glucose solution, methane represents most of the gas energy content. When the gas mixture becomes less complex at higher temperatures, the cold-gas efficiency slightly decreases. This effect can be ascribed to pre-reforming reactions of C2 components to methane, and to hydrogen production via the water-gas shift reaction, which both are exothermic. The volumetric heating value of the product gas goes through a maximum in the range of 600 - 700oC. Hence, above 700oC, the produced gas is more pure, but the heating value of the gas is significantly lower.

Effect of reaction time Figure 3.7 shows that already after 5 s of reaction time at 600oC, some gaseous products are produced from glucose SCWG. After 40 s of reaction time at 600oC, the carbon conversion and product distribution reach their asymptotic value. Increasing the reaction time does not increase the carbon conversion, nor does it change the product distribution. The concentration of the glucose does not significantly influence the relative conversion rate, which suggests a possible first-order overall reaction.

67

100

80

glucose

60

Xc [%]

40

20

1.8 wt.% 20 wt.%

0 0 20 40 60 80 100

time [s]

(a)
3

yield [mole gas/ mole glucose]

1.8 wt.% H2 2 CO2 CO CH4 20 wt.% H2 CO2 CO CH4 0 0 20 40 60 80 100

time [s]

(b) Figure 3.7. Influence of the reaction time on (a) the carbon conversion and (b) the gas yield for 1.8 wt % and 20 wt % glucose solution. (T = 600oC, P = 300 bar). Another important finding regarding the reaction time is that the heating trajectory has no considerable effect on the final carbon conversion. This result was obtained by comparing the carbon efficiency from interrupted and noninterrupted experiments (Potic et al. 2004). In a practical SCWG process, the reaction zone is spread out over the heat-exchanger and the reactor. Although laboratory-scale tests showed that the heating trajectory has no effect on the final conversion, it remains important that all products formed in the heat-exchanger (gas, liquid, and solids) end up in the reactor and are not deposed on the heat-exchanger wall. In that way, the final carbon efficiency will be the result of the process conditions as prevailing in the reactor. This may be achieved by using a particle loaded scouring heat-exchanger (Kersten et al., 2004).
68

Effect of the pressure Although it has been suggested that supercritical water properties would be beneficial for the gasification reaction, experimental results from capillary reactors showed that pressure has no influence on the carbon efficiency (see Figure 3.8a) and product gas yield (see Figure 3.8b). It is crucial for the SCWG process that the heat content of the reactor effluent be utilized as much as possible to preheat the feedstock stream (mainly water) to reaction conditions. However, heat exchange between these streams is not practical at low pressure, because of the high heat of evaporation under almost isothermal and isobaric conditions. Heating of the feedstock stream to the desired gasification temperatures in a heat-exchanger without evaporation requires operation at high pressures. This is the true incentive of the high pressures involved in wet gasification.
100

80

60

Xc [%]

40 glucose 10 wt.% glycerol 10 wt. % cellulose 10 wt.%

20

0 0 100 200 300 400 500

P [bar]

(a)
4

glucose 650 C, 10 wt.% yield [mole gas/ mole glucose]

3 138 bar 162 bar 197 bar 255 bar 297 bar 418 bar

H2

CO2 CO CH4 C2H4 C2H6 C3H6 C3H8

(b) Figure 3.8 Effect of pressure on (a) the carbon efficiency for glucose, glycerol, and cellulose, and (b) the gas yield for the 10 wt % glucose solution. (T = 650oC, t = 60 s).

69

Catalytic SCWG Addition of potassium and sodium cations Many researchers (Kruse et al., 2000; Schmieder et al., 2000; Sinag et al., 2003; Sinag et al., 2004; Van de Beld et al., 2003) have investigated the influence of K+ and Na+ cations on the SCWG process. Kruse et al., for example, found that these alkali metals promote the water-gas shift reaction slightly, but not the carbon conversion. We performed a few experiments with these alkali metals, which confirmed their conclusions. The influence of NaOH on the gas distribution is presented in Table 3.2. Table 3.2. Influence of the addition of NaOH to a 17 wt % glucose feed solution. parameter temperature, T [oC] pressure, P [bar] Reaction time, t [s] carbon conversion, Xc H2 CO2 CO CH4 C2 C3 no additives 600 300 60 60 9.9 8.2 62.2 12.9 4.5 2.3 0.5 wt % NaOH 600 300 60 55 gas composition 21 47 7 19 4 2 17 45 12 20 4.2 1.8 17 47 9 21 4.2 1.8 1 wt % NaOH 600 300 60 52 3 wt % NaOH 600 300 60 60

Use of 3 wt % ruthenium on TiO2 A compound comprised of 3 wt % ruthenium on TiO2 (Ru/TiO2) was kindly provided to us by Pacific Northwest National Laboratory. This catalyst was used by Pacific Northwest National Laboratory for the conversion of waste streams, in subcritical water (200 bar, 350C), to methane (Elliott et al., 1993). To test the catalyst, a 17 wt % glucose solution that cannot be converted completely without a catalyst was used. Figure 3.9 shows the results of identical experiments with and without a catalyst.

70

100

80

Xc[%]

60

40

20

0 400

glucose 17 wt.% + Ru catalyst glucose 17 wt.%

500 600 700 800

T [oC]

Figure. 3.9 Influence of the temperature on the carbon efficiency of the 17 wt % glucose solution for noncatalytic and catalytic processes. (T = 600oC, t = 60 s). The ruthenium catalyst is able to increase the conversion from 70% to 100% at the commonly used process temperature of 600oC (see Figure 3.9). This is an interesting and surprising result, because this catalyst was not designed for SCWG conditions. The measured product distribution, as a function of the temperature, is given in Figure 3.10. With a catalyst, the product distribution is clearly different than without a catalyst (compare Figure 3.5 to Figure 3.10). In fact, except for hydrogen, the gas at 600oC resembles the equilibrium gas for those conditions rather well (compare Figure 3.5 and 3.10).
3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 400 C o 500 C o 600 C
o

Glucose 17 wt.%

yield [mole gas/ mole glucose]

H2

CO2

CO

CH4

Figure 3.10

Effect of temperature on the gas production for the 17 wt % glucose solution with

ruthenium catalyst (P = 300 bar, t = 60 s). Contrary to noncatalytic SCWG, in case of the Ru/TiO2 catalyst, the conversion is not a function of the concentration of organics in the feed. For solutions of 1, 5, 12, and 17 wt % glucose in water, complete
71

conversion of carbon to the gas phase is achieved. However, the product distribution remains a function of the concentration (see Figure 3.11). Ru/TiO2 is designed as a methanation catalyst. If applied for SCWG, the methane production is strongly dependent on the concentration of the organics in the feed (see Figure 3.11). The product gas for a 1 wt % glucose solution consists of only hydrogen and carbon dioxide. With increasing concentration, the product-gas distribution shifts from hydrogen to the methane-rich gas. With these results, the potential of heterogeneous catalysis is clearly demonstrated. However, this catalyst may not be suitable for the actual process, because it was developed for T < 400oC and lifetime at 600oC is never examined. Besides, the support (TiO2) of the ruthenium catalyst may not be stable under the applied process conditions (Wang et al., 2004).

yield [mole gas/ mole glucose]

glucose 1 wt.% + Ru glucose 5 wt% + Ru glucose 12 wt.% + Ru glucose 17 wt.% + Ru

H2

CO2

CO

CH4

Figure 3.11 Effect of the glucose concentration on the gas production for the catalytic gasification of glucose. (T = 600oC, P = 300 bar, t = 60 s).

72

Conclusions
The conclusions of this work can be summarized as follows. It has been demonstrated in the present work that results obtained in small-scale (1 mm < d < 7 mm) metal reactors are obscured by undefined catalytic effects of the reactor wall, improving the carbon conversion (except for the stainless steel reactor) and/or gas shift activity. The noncatalytic gasification in supercritical water (SCWG) has been studied in inert quartz capillaries. From these tests, the following can be concluded: Below 650oC, the carbon conversion is a strong function of the temperature. Increasing the temperature from 650oC to 800oC hardly affects the carbon conversion. The maximum conversion is a function of the concentration. Complete conversion of the feedstock to the gas phase is achieved only for very diluted solutions of glucose and glycerol (1 wt %). Higher concentrations ( 5 wt %) cannot be gasified completely. The carbon conversion is typically in the range of 75% - 90% for solutions that contain > 5 wt % organics. A high temperature of 800oC is needed for enhanced water-gas shift activity to produce hydrogen, but equilibrium still is not reached. For glucose solutions with a concentration of 1 - 20 wt %, a reaction time of 40 s is sufficient to reach the maximum conversion at 600oC. The relative conversion rates are hardly dependent on the concentration of the feedstock solution, indicating an overall first-order reaction. Under identical conversion conditions, pinewood has a considerably lower maximal conversion than glucose and glycerol (e.g., 45% vs 83% at 700oC). Pressures in the range of 50 - 500 bar have no influence on the carbon conversion and the product distribution is not affected in the range of 50 - 450 bar. Up to 700oC, the product gas can be characterized as fuel gas that consists of CO, H2, CH4, and C2+ components. Above 700oC, the product gas becomes less complex: at low glucose concentration, an excess of H2 is produced; a medium concentration results in a mixture of H2 and CH4, and a high concentration produces mainly CH4. The addition of K+ or Na+ cations to the reaction mixtures promotes the water-gas shift reaction, which leads to more H2 and less CO but does not increase the carbon conversion. By adding a 3 wt % ruthenium on TiO2 (Ru/TiO2) catalyst, complete conversion of solutions with 1 to 17 wt % glucose is achieved. These experiments show the potential of heterogeneous catalysis. However, a catalyst for the process is still missing and the development of commercial catalysts should be considered as a necessary and essential step in the process development.

73

Notation

LHV feed LHV product gas ,i

N c ,i N c , feed N product gas ,i N feed
P T T Xc

Lower heating value of feed dry and ash free, MJ/m3, MJ/mol Lower heating value of product gas component i, MJ/m3, MJ/mol Number of moles carbon in product gas component I produced, mol Number of moles carbon in the feed, mol Number of moles of product gas component i Number of moles of feed Reaction pressure, bar Reaction time, s Reaction temperature, oC Carbon conversion, dimensionless, or % Gas yield, mol/mol Cold gas efficiency, %

Yi

LHV

References

Antal, M.J.; Manarungson, S.; Mok, W.S., Hydrogen Production by Steam Reforming Glucose in Supercritical Water. In Advances in Thermochemical Biomass Conversion; Bridgwater, A.V., Ed.; Blackie Academic and Professional: London, 1993, 1367. Antal, M.J.; Allen, S.G.; Schulman, D.; Xu, X.; Divilio, R.J., Biomass Gasification in Supercritical Water. Ind. Eng. Chem. Res. 2000, 39, 4040. Bertucco, A.; Barolo, M.; Soave, G., Estimation of Chemical Equilibria in High-Pressure Gaseous Systems by a Modified Redlich-Kwong-Soave Equation of State. Ind. Eng. Chem. Res. 1995, 34, 3159. Derde Energienota; Ministerie van Economische Zaken (MEZ): Den Haag, The Netherlands, 1995. Diem, V.; Boukis, N.; Habicht, W.; Hauer, E.; Dinjus, E., Reforming of Methanol in Supercritical Water - Catalysis by the Reactor Material. Presented at the Sixth Italian Conference on Chemical and Process Engineering, Pierucci, S., Pisa, Italy, 2003. Duurzame Energie in Opmars, Actieprogramma 1997-2000; Ministerie van Economische Zaken (MEZ): Den Haag, The Netherlands, 1997. Elliott, D.C.; Sealock, L.J.; Baker, E.G., Chemical Processing in High-Pressure Aqueous Environment: 2. Development of Catalyst for Gasification. Ind. Eng. Chem. Res. 1993, 32, 1542.

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Hao, X.H.; Guo, L.J.; Mao, X.; Zhang, X.M.; Chen, X.J., Hydrogen Production from Glucose Used as a Model Compound of Biomass Gasified in Supercritical Water. Hydrogen Energy 2003, 28, 55. Hemmes, K., Vergassing van natte biomassa/reststromen in superkritiek water (SG), voor de productie van groen gas (SNG), SNG/H2-mengsels, basis chemicalin en puur H2. Energy research Centre of The Netherlands (ECN): Petten, The Netherlands, 2004. Holgate, H.R.; Meyer, J.C.; Tester, W.J., Glucose Hydrolysis and Oxidation in Supercritical Water. AIChE J. 1995, 41, 637. Kabyemela, B.M.; Adschiri, T.; Malaluan, R.M.; Arai, K., Glucose and Fructose Decomposition in Subcritical and Supercritical Water: Detailed Reaction Pathway, Mechanisms, and Kinetics. Ind. Eng. Chem. Res. 1999, 38, 2888. Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M., Reactor Design Considerations for Biomass Gasification in Hot Compressed Water. In Proceedings of the 2nd World Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection; van Swaaij, W.P.M.; Fjallstrom, T.; Helm, P.; Grassi, A., Eds.; ETA-Florence and WIP-Munich: Rome, Italy, 2004; p. 1062. Kruse, A.; Abeln, J.; Dinjus, E.; Kluth, M.; Petrich, G.; Schacht, M.; Sadri, H.; Schmieder, H., Gasification of Biomass and Model Compounds in Hot Compressed Water. Presented at the International Meeting of the GVC-Fachausschu "Hochdruckverfahrenstechnik", Karlsruhe, Germany, 1999; paper No. 107. Kruse, A.; Meier, D.; Rimbrecht, P.; Schacht, E., Gasification of Pyrocatechol in Supercritical Water in the Presence of Potassium Hydroxide. Ind. Eng. Chem. Res. 2000, 39, 4842. Kruse, A.; Gawlik, A.; Henningsen, T., Biomass Liquefaction and Gasification in Near- and Supercritical Water: Key Compounds as a Tool to Understand Chemistry. Presented at the 4th International Symposium on High Pressure Technology and Chemical Engineering, Venice: Italy, 2002. Kruse, A.; Gawlik, A., Biomass Conversion in Water at 330 - 410oC and 30 - 50 MPa. Identification of Key Compounds for Indicating Different Chemical Reaction Pathways. Ind. Eng. Chem. Res. 2003, 42, 267. Kruse, A.; Henningsen, T.; Sinag, A.; Pfeiffer, J., Biomass Gasification in Supercritical Water: Influence of the Dry Matter Content and the Formation of Phenols. Ind. Eng. Chem. Res. 2003, 42, 3711. Kyle, B.G., Chemical and Process Thermodynamics; Prentice Hall PTR: Englewood Cliffs, N.J., 1999. Lee, I.; Kim, M.-S.; Ihm, S.-K., Gasification of Glucose in Supercritical Water. Ind. Eng. Chem. Res. 2002, 41, 1182. Manarungson, S.; Mok, W.S.L.; Antal, M.J., Hydrogen Production by Steam Reforming Glucose in Supercritical Water, In Advances in Thermochemical Biomass Conversion; Bridgwater, A.V., Ed.; Blackie Academic and Professional: London, 1993; p. 1367. Matsumura, Y., Evaluation of Supercritical Water Gasification and Biomethanation for Wet Biomass Utilization in Japan. Energy Convers. Manage. 2002, 43, 1301.

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Matsumura, Y.; Minowa, T.; Potic, B.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M.; van de Beld, L.; Elliott, D.C.; Neuenschwander, G.G.; Kruse, A.; Antal, M.J., Biomass Gasification in Near- and Supercritical Water: Status and Prospects. Biomass Bioenergy 2005, 29, 269. Modell, M.; Gasification and Liquefaction of Forest Products in Supercritical Water. In Fundamentals of Thermochemical Biomass. Overend, R.P.; Milne, T.A.; Mudge, L.K., Eds.; Elsevier Applied Science Publishers Ltd.: London, 1985, p. 95. National Institute of Standards and Technology (NIST), Gaithersburg, MD. Potic, B.; van de Beld, L.; Assink, D.; Prins, W.; van Swaaij, W.P.M., Gasification of Biomass in Supercritical Water. In Proceedings of the 12th European Conference and Exhibition on Biomass for Energy, Industry and Climate Protection; Palz, W.; Spitzer, J.; Maniatis, K.; Kwant, K.; Helm, P.; Grassi, A., Eds.; ETA Florence, WIP Munich: Amsterdam, 2002; p. 777. Potic, B.; Kersten, S.R.A.; Prins, W.; Assink, D.; van de Beld, L.; van Swaaij, W.P.M., Gasification of Biomass in Supercritical Water: Results of Micro and Pilot Scale Experiments. In Proceedings of the 2nd World Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection, van Swaaij, W.P.M.; Fjallstrom, T.; Helm, P.; Grassi, A., Eds.; ETA-Florence and WIPMunich: Rome, Italy, 2004; p. 742. Potic, B.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M., A High-throughput Screening Technique for Conversion in Hot Compressed Water. Ind. Eng. Chem. Res. 2004, 43, 4580. Sarada, R.; Joseph, R., A Comparative Study of Single and Two Stage Processes for Methane Production from Tomato Processing Waste Process. Biochem. (Oxford, U.K.) 1996, 31, 337. Schmieder, H.; Abeln, J.; Boukis, N.; Dinjus, E.; Kruse, A.; Kluth, M.; Petrich, G.; Sadri, E.; Schacht, M., Hydrothermal Gasification of Biomass and Organic Wastes. In Proceedings of the 5th Conference on Supercritical Fluids and their Applications, Garda: Italy, 1999; p. 347. Schmieder, H.; Abeln, J.; Boukis, N.; Kruse, A.; Kluth, M.; Petrich, G.; Sadri, E.; Schacht, E., Hydrothermal Gasification of Biomass and Organic Wastes. J. Supercrit. Fluids 2000, 17, 145. Sinag, A.; Kruse, A.; Schwarzkopf, V., Key Compounds of the Hydropyrolysis of Glucose in Supercritical Water in the Presence of K2CO3. Ind. Eng. Chem. Res., 2003, 42, 3516. Sinag, A.; Kruse, A.; Rathert, J., Influence of the Heating Rate and the Type of Catalyst on the Formation of Key Intermediates and on the Generation of Gases During Hydropyrolysis of Glucose in Supercritical Water in a Batch Reactor. Ind. Eng. Chem. Res. 2004, 43, 502. Soave, G., Equilibrium Constants from a Modified Redlich-Kwong Equation of State. Chem. Eng. Sci. 1972, 27, 1197. Soave, G.; Barolo, M.; Bertucco, A., Estimation of High-Pressure Fugacity Coefficient of Pure Gaseous Fluids by Modified SRK Equation of State. Fluid Phase Equilib. 1993, 91, 87. Van de Beld, L.; Wagenaar, B.M.; Assink, D.; Potic, B.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M.; Penninger, J.M.L., Biomass and Waste Conversion in Supercritical Water for the Production of Renewable Hydrogen. Presented at the 1st European Hydrogen Energy Conference, Grenoble: France, 2003.

76

Van der Drift, A.; van Doorn, J.; Vermeulen, J.W., Ten Residual Biomass Fuels for Circulating Fluidized-bed Gasification. Biomass Bioenergy 2001, 20, 45. Wang, J.A.; Cuan, A.; Salmones, J.; Nava, N.; Castillo, S.; Moran-Pineda, M.; Rojas, F., Studies of Sol-Gel TiO2 and Pt/TiO2 Catalysts for NO Reduction by CO in an Oxigen-rich Condition. Appl. Surf. Sci. 2004, 230, 94. White Paper on Environmental Liability. European Commission, 2000. Xu, X.; Matsumura, Y.; Stenberg, J.; Antal, M.J., Carbon-Catalyzed Gasification of Organic Feedstocks in Supercritical Water. Ind. Eng. Chem. Res. 1996, 35, 2522. Xu, X.; Antal, M.J. Jr., Gasification of Sewage Sludge and Organics in Supercritical Water. Presented at the 1997 AIChE Annual Meeting, 1997. Yoshida, T.; Matsumura, Y., Gasification of Cellulose, Xylan and Lignin Mixtures in Supercritical Water. Ind. Eng. Chem. Res. 2001, 40, 5469. Yoshida, T.; Oshima, Y.; Matsumura, Y., Gasification of Biomass Model Compounds and Real Biomass in Supercritical Water. Biomass Bioenergy 2004, 26, 71. Yu, D.; Aihara, M.; Antal, M.J., Hydrogen Production by Steam Reforming Glucose in Supercritical Water. Energy Fuels 1993, 7, 574.

77

78

Chapter 4
Pilot Plant
Abstract
In this Chapter, a first generation pilot plant for supercritical water gasification with a capacity of 30 litres per hour wet intake is presented. Several experiments with non-fouling feedstock materials such as glycerol and methanol are successfully performed and the results are compared with experiments obtained in continuous and batch microreactors. Experiments with more complex feedstocks such as starch revealed that charring feedstocks cannot be gasified in this pilot plant without operational problems such as fouling and blockages of heat-exchanger and reactor.

79

Introduction
Research on SCWG was started in Twente in the year 2000 in an international program involving the University of Twente, a private Dutch biomass enterprise, BTG B.V., and the Japanese partners NIRE and the University of Hiroshima. At that time, this consortium obtained a research grant from the Japanese NEDO organization to explore the opportunities of SCWG. Part of the NEDO-grant was designated to design, construct and operate a pilot plant facility in Twente to gather process design data. The potential of SCWG has recently been extensively discussed in the literature (Antal et al., 2000; Boukis et al., 2002; Hao et al., 2003; Kruse et al., 2003; Lee et al., 2002; Matsumura et al., 2005; Potic et al., 2002; Potic et al., 2005; Van de Beld et al., 2003) and in some earlier work (Antal et al., 1999; Holgate et al., 1995; Kabyemela et al., 1998; Kabyemela et al., 1999; Manarungson et al., 1993; Modell, 1985; Schmieder, 1999; Xu et al., 1996; Xu and Antal, 1998; Yu et al., 1993). On the other hand, possible problems such as the feeding of slurries and fouling in the reactor and auxiliary equipment are not yet fully identified. The team in Twente, however, anticipated some of the problems and proposed a preliminary concept of a supercritical fluid bed system to prevent fouling and to allow for the introduction of catalytic material and its possible regeneration. Unfortunately, in 2000 there was no information available necessary for a design of a pilot plant based on a supercritical fluid bed. Nevertheless, it was decided to make a start with the pilot plant research program. The strategy was to start with a first generation plant in order to get continuous operation experience with process pressures of ca. 250 bar and temperatures exceeding 600oC. This first generation plant included a shell and tube heat-exchanger and a tubular reactor and was supposed to take in simple non-fouling feedstocks. It was projected that after this initial phase more basic data on SCWG and supercritical fluidization would have been collected, amongst others from the present thesis project. The shell and tube heat-exchanger and the tubular reactor would subsequently be replaced by a fluid bed system to develop the process for more complex feedstock materials. Several foreseen and unforeseen problems such as legislation difficulties, lack of operational experience with some of the high-pressure machinery and the extremely long delivery time of special parts and materials caused delays in the program. In fact, the first satisfactorily runs with the first generation pilot plant could only be performed as late as mid 2004. At the time of writing, the fluid bed system has not been installed in the pilot plant yet. In this chapter, the first generation SCWG pilot plant with a maximal intake of 30 kg wet biomass per hour is presented. Several experiments with non-fouling model compounds are reported and compared with results obtained in the microreactors (see Chapters 3 and 5). In addition, by analyzing the test runs with more complicated feedstocks possible operational problems are identified.

80

The pilot plant

The pilot plant is designed and constructed by BTG B.V. as a part of the consortium activities and is located in a concrete high-pressure safety box in the High-Pressure Laboratory of the University of Twente. It is designed for operation at temperatures up to 650oC and pressures of 300 bar with a maximum capacity of 30 kg/h wet feedstock. A schematic presentation of the plant is given in Figure 4.1. The plant is modular built and consists of a number of units: a pump, a shell and tube heatexchanger, a coiled tubular reactor positioned in an oven, a cooler, a gas-liquid separation section and gas product analysis. Figure 4.2 is a detailed flow sheet of the pilot plant. The feed storage system consists of two vessels (S-002 and S-003, see Figure 4.2). One additional vessel for water (S-001) is installed to facilitate the start-up and shut-down procedure. The effluent liquid stream from the process (mainly water) is collected in a fourth vessel (S-006). To monitor the actual flows out of and into the vessels, weighing balances are installed under each vessel. The feed is supplied to the system by a LEWA piston pump (P-001) with maximum capacity of 30 kg/h and maximum operating pressure of 300 bar. A shell and tube heat-exchanger (HE-001) with a length of 1.5 m is installed between the inlet and outlet streams of the reactor. The feedstock flows through the outer tube (i.d. = 5/4" ~ 30 mm, Incoloy 825), and the reactor effluent through the inner tube (i.d. = 1/2" ~ 1.3 mm, Incoloy 825). The reactor (R-001) is a coiled tube (Incoloy 825) with a total length of 16 m and an inside diameter of 13.84 mm. The coil itself has a diameter of 30 cm and a height of 60cm. It is placed in the center of a gas oven with a maximum capacity of 20 kW. After passing through the heat-exchanger, the reactor effluent is cooled with water in a double wall cooler (C-001). After this cooler, the two-phase product stream is separated in the separation section, which consists of a high pressure (HP) separator (SEP-001 in Figure 4.2), a pressure reducing valve system and two low-pressure (LP) separators (SEP-002 and SEP-003 see Figure 4.2). The high-pressure separator is a vessel of stainless steel with a volume of about 2 L and is operated at the prevailing process pressure. In this vessel the two-phase process stream is separated into a liquid (mainly water) and a gas stream at a temperature of 50 to 100oC. The liquid level in the vessel is controlled with an ultrasonic level indicator in combination with an electropneumatic control valve. After the high pressure separator, the pressure is reduced to ambient conditions by a pneumatically operated ball valve in the gas-phase line. An electronic backpressure controller (PIC-001) placed after this ball valve is used to control the system pressure. Both the gas and the liquid stream from the high pressure separator are again separated at ambient conditions in SEP-002 and SEP-003, respectively. In the low pressure separator SEP-002 handling the gas stream from the HP separator, water is removed down to a level corresponding to atmospheric pressure and ca. 20oC. Dissolved gases in the liquid stream from the HP separator are removed from the liquid stream in SEP-003. The product gas streams from the plant GAS 1 and GAS 2 are monitored
81

separately with respect to composition and flow rate. In the mass balance calculations the component flows in kg/h of the streams are added and together define the gaseous product flow (see below). The pilot plant is started-up by pressuring it with nitrogen. As a result the gaseous product streams GAS 1 and GAS 2 (see Figures 4.1 and 4.2) contain, during the first hours of operation, considerable amounts of nitrogen. The mass balance was derived during stable operation when the nitrogen fraction in the outlet streams was below 10 volume percent. To avoid extremely long run times requested to purge out all the initial nitrogen and because the partial pressure of the water vapor is dominant while the process was found to be relatively insensitive to the absolute pressure (see Chapter 3), for the purpose of the present investigation this remaining nitrogen was accepted.

R-001 Reactor
(in gas heated oven)

GAS 1 C-002
To gas analysis section

SEP-001 HP separator

SEP-002

WATER 1 HE-001 Shell and tube heat exchanger FEED C-001 Cooler P-001 Pump SEP-003 WATER 2 GAS 2
To gas analysis section

GAS-LIQUID separation section

Figure 4.1 Schematic presentation of the pilot plant.

82

NATURAL GAS
FI 006

Water II
17
Produced water
HLA 002

BV 010

QS 001 FS 001 TI 021 TS 021 QS 002 QS 003

NITROGEN
BV 006 FC 005

13

TI 010-1

TIC 001 006

TI Tmax

TI 010 -2

FI 002

QI 003

water / biomass

water / ethanol

LI 001

LI 002

LI 003

QI 004

water

LLA 001

LLA 002

LLA 003

LI 005

FURNACE
TI 014 TS 014

GAS I
PIC 002 TI Tmax PI 002

S-001

S-002

S-003
FI 005-2

S-006 H-002
17

LP-G/L SEPARATOR
Coolant out

TIC TI 009 -7 005-2

TI 009-3

BV 001

BV 002

BV 003

BV 005

R-001 E-1922

12

TI 005 TIC 002 FC 003

003

SEP-002

TI 018 HLA 003 BV 008 TI 011

PIC 001

TI 017 LLA 005

FEEDING SECTION

Water II
TI 003

FC 004

Coolant in

AIR

14

TI 009-6

14
FI 001

S-004
Coolant in

14

C-002
TI 009-2 Coolant out

P-002

WATER I

TI 007

11

HE-001 E-1922

HEAT EXCHANGER

SEP-001 C-1922

HLA 001

HP-G/L SEPARATOR
TI Tmax

LI 004

10
TI 012 -1 002

LLA 004

TIC 007

TI 012 -2

FI 004

QI 009

TI 002

TI 008

TI 009-1

coolant out
TI 016 TS 016

TI 009 -4 BV 007 BV 004 PI 003

16

GAS II

QI 010

LP-G/L SEPARATOR
Coolant out TI 020 BV 009 TI 013 FI 005 -1 QI LLA 006 013

9 SV-001

C-001 D-1922
TI 015

FC 006

FC 002
TI

HLA 004

SEP-003

HPS 001

15

009-5

5 P-001

PI 001 FI 007 FC 001

17

Coolant in TI 019

coolant in

17

S-005

17

TI 001

QI 001

P-003

WATER II

Figure 4.2 Detailed flow sheet of the plant.

83

Measurements during pilot plant operation

Temperatures, pressures, flow rates and concentrations are measured at several locations of the system (see Figure 4.2). The run time starts from the moment that set process parameters (temperature and pressure) are reached and feeding system is switched from water to the feedstock. All data are collected and processed by an industrial process computer equipped with ADAM data acquisition modules (Adam 5000E, supplier Advantech, GeniDaq software was used). In Figure 4.3 direct read-outs from the weighing balances of the feedstock supply vessel (S002 and S003) and the total liquid effluent collecting vessel (S006) are presented. The total liquid effluent of the pilot plant is the sum of the liquid out-let streams of the low-pressure flash vessels SEP-001 and SEP-002. It can be seen that the inlet stream has a constant rate (after more than 3 h run time), but that the exit flow rate fluctuates requiring a considerable time of averaging. The exit flow rate fluctuates predominantly as a result of control actions of the level controller in the high-pressure separator.

Figure 4.3

Readouts from the weighing balances of the feedstock and total liquid effluent. Liquid

mass in the vessels versus the run time are plotted. Exit gas flow rates (GAS 1 and GAS 2) are measured with mass flow indicators. These flows are fluctuating (see Figure 4.4), also because they are affected by the actions of controllers. The flow rate of GAS 1, being the dried gas from the high-pressure separator, is directly influenced by the system pressure controller. GAS 2 which, is composed of the gases dissolved in the high-pressure liquid (water), is influenced by the level controller in the high-pressure separator. In the mass balance calculations, the last 30 min of gas production are used, which corresponds to the lowest nitrogen level.
84

1.4

3 corrected gas flow rate [m / h]

1.2 1.0 0.8 0.6 0.4 0.2 0.0 3.33

GAS 1 (rich in H2) GAS 2 (rich in CO2)

3.55

3.77

3.99

4.21

4.44

4.66

4.86

time [h]

Figure 4.4 Produced gas flow rates versus the run time. Differential mass balances were made over the boxed time span. As mentioned before, the pilot plant is started up and initially pressurized with nitrogen and as a result nitrogen is present in the exit gas streams during the whole test period. Besides, it has been observed that the decay of the nitrogen concentration in the exit gas does not follow a PFR or a CISTR pattern. In reality, the nitrogen concentration level first drops rapidly and then levels off slowly indicating some dead-zones in the system, which makes mass balancing (using flow rates) over the whole run time difficult. After careful consideration of all options it has been decided that mass balances during the time-span of the experiment in which the nitrogen fraction in the exit gas is less than 10 volume percent will give the most accurate information. The production of gas phase components is calculated based on the actual gas flow rates and concentrations derived from the read-outs of the GCs. Averaged values over a time interval of 30 min are taken. For the calculation of the total product yields and the carbon conversion to gas-phase products, the values of GAS 1 and GAS 2 are added. In Figure 4.6, typical examples are given of the measured gas compositions in both gas-phase flows over a stable run period. On-line GCs are used to determine the product gas composition. Components that can be detected are: H2, CO, CO2, CH4, ethylene, ethane, propylene and propane. Every 5 min, a gas sample is analyzed by the GC and the analysis time is about 3 to 4 min. Typical yields and conversions to gasphase products are only based on the feedstock and the gaseous products. Analyses of the liquid effluent were only performed incidentally. For these analyses a combined liquid sample of WATER 1 and WATER 2 is taken which is analyzed with respect to its C, H and N content. The elemental composition of the liquid effluent samples is determined with an elemental analyzer (Flash EA 1112 Thermo Quest, Rodano, Italy).

85

50

GAS 1
40

gas composition [%]

gas composition [%]

H2 N2 CO CH4 C2H4

C2H6 C3H6 C3H8 CO2

100

GAS 2
80

H2 N2 CO CH4 C2H4

C2H6 C3H6 C3H8 CO2

30

60

20

40

10

20

0 4.4 4.48 4.57 4.67 4.75 4.84

0 4.36 4.45 4.55 4.65 4.75 4.85

time [h]

time [h]

Figure 4.5 Compositions GAS 1 and GAS 2 versus the run time. The carbon conversion to the gas-phase and the product yields are chosen here as the main output parameters of the process. The carbon conversion to the gas-phase is defined as degree of conversion of carbon from biomass to permanent gases:

Xc =

i c,i nr of gaseous compounds

xf

feed x f c,feed
The product yield is defined as:

4.1

Yi =

i /M i feed /M feed

4.2

Like mentioned before, the used mass flow rates in these equations are average values of the last 30 min. of gas production and only experiments are used that have a nitrogen fraction of less than 10 vol % in this period. During the test runs the total pressure in the reactor can be measured accurately by the installed pressure transducers. Definition of the exact reactor temperature is on the other hand extremely difficult. One problem is the presence of a heat up trajectory inside the reactor; the feed stream exits the heat-exchanger at ca. 450C and is then subsequently heated in the oven in the first part of the reactor tube to ca. 600C. A second problem is the temperature profile existing in the gas oven. Scanning experiments have revealed that this temperature gradient is ca. 100C from bottom to the top, the bottom where the gas flame is located being hotter. By the complete lack of an alternative, it is decided to use the temperature at the exit of the reactor as the characteristic process temperature. We are aware of the fact that this imprecise temperature definition makes interpretation of the results cumbersome, because especially in the temperature region below 650C the conversion is affected to a large extent by the temperature (see Chapter 3). On the other hand, it has been observed that it is the

86

final temperature that predominantly determines the conversion and product distribution (see Chapters 2 and 3).

Results
Apart from the limitations mentioned above, successful experiments showing no operational problems have been carried out in the pilot plant with glycerol and methanol as feedstock. Test with starch (a fouling feedstock) have shown severe operational problems in the form of blockages at several locations, for example in the heat-exchanger and in the reactor. These blockages occur rapidly and prevent operation with charring feedstocks.

Mass Balances In Figure 4.6 the measured temperatures, pressures, flow rates and product gas compositions during a gasification test with 9.1 wt % glycerol are presented as a typical example. The actual mass balance of this presented experiment is listed in Table 4.1.

Figure 4.6

Graphical presentation of a typical experiment with glycerol. The presented gas

compositions are normalized leaving nitrogen out.

87

Table 4.1. Mass balance of a typical pilot plant experiment with glycerol. The presented gas composition is normalized leaving nitrogen out.

Feed T [oC] P [bar] Feed concentration [wt %] Catalyst Inlet Feed flow total [kg/h] Feed flow carbon [kg/h] 8.07 0.287 Feed flow organics [kg/h] 0.734

Glycerol (C3H8O3) 602 270 9.1 None Outlet Water flow [kg/h] 7.33 Carbon in water [kg/h] not determined Total gas flow [kg/h] Carbon in gas [kg/h] 0.498 0.221

Gas produced (GAS 1 + GAS 2) H2 CO CH4 C2H4 C2H6 C3H6 C3H8 CO2 28.2 vol.% 33 vol.% 14.5 vol.% 0.6 vol.% 6.7 vol.% 0.0 vol.% 0.0 vol.% 17.0 vol.% 0.0127 kg/h 0.2050 kg/h 0.0516 kg/h 0.0034 kg/h 0.0454 kg/h 2.4E-05 kg/h 2.5E-05 kg/h 0.167 kg/h

Carbon conversion to the gas-phase 0.74 (kg c in gas/kg c in feed) If outlet temperature from the oven is accepted to be representative for the reaction temperature (ca. 602oC), the obtained 74% carbon conversion is in agreement with results obtained in the batch micro reactor (see Chapter 3). In Table 4.2 a more complete mass balance is presented for methanol gasification, including analyses of the liquid effluent streams. The carbon recovery of this experiment with methanol is above 95% (see Table 4.2). This result indicates that despite the many shortcomings of this first generation pilot plant, reasonably good mass balances can be obtained when simple non-charring feedstocks are processed.
88

Table 4.2. Mass balance of an experiment with methanol. The presented gas composition is normalized leaving nitrogen out. Feed T [oC] P [bar] Feed concentration [wt %] Catalyst Inlet Feed flow [kg/h] Feed flow organics [kg/h] Feed flow carbon [kg/h] 8.11 0.341 0.128 Total gas flow [kg/h] Carbon in gas [kg/h] 0.336 0.092 Methanol (CH3OH) 595 270 4.2 Na2CO3, 0.01 wt % added to the wet feed Outlet Water flow [kg/h] 7.70 Carbon in water [kg/h] 0.033

Gas produced (GAS 1 + GAS 2) H2 CO CH4 C2H4 C2H6 C3H6 C3H8 CO2 Carbon conversion to the gas-phase Carbon recovered in the liquid effluent Total carbon recovery 72.1 vol % 2.8 vol % 0.4 vol % 0.0 vol % 0.0 vol % 0.0 vol % 0.0 vol % 24.8 vol % 0.0368 kg/h 0.0196 kg/h 0.0017 kg/h 0.0 kg/h 0.0 kg/h 0.0 kg/h 0.0 kg/h 0.2784 kg/h

0.70 (kg c in gas/kg c in feed) 0.26 (kg c in water effluent/kg c in feed) 0.96 (kg c in products/kg c in feed)

Addition of Na2CO3 During some runs, small amounts of Na2CO3 (0.01 wt %) were added to the feedstock solution. By comparing the results with and without Na2CO3 (see Figure 4.7) it can be seen that it influences the product distribution strongly. In fact, it is shown that already by addition of such small amounts of
89

Na+, the water-gas shift equilibrium is approached to a large extent resulting in a high hydrogen yield and low CO levels. Apart from its affect on the product gas distribution, the results also show that the carbon conversion increases when adding Na2CO3. The influence of Na2CO3 on the carbon conversion was not observed in the batch microreactors. This difference between batch capillaries and the pilot plant results cannot be explained from any existing theory, although it could in principle originate from interaction of the metal wall with Na2CO3..The difference in the measured carbon conversions with and without Na+ may well be ascribed by the imperfect control and definition of the reactor temperature in the pilot plant. From measurements in the capillaries (see Chapter 3) it is known that 20C change in the reactor temperature represents ca. 10% carbon conversion around 600C. As stated before, in the oven of the pilot plant the temperature gradient is 100C.

2.0

glycerol, 10wt%, T = 602 C, 280 bar without additives 0.01 wt%, Na2CO3

100

yield [mole gas/mole glycero]

1.5

80

60 1.0 40 0.5

20

0.0 H2 CO2 CO CH4 C2H6 -Na2CO3

Figure 4.7

Influence of Na2CO3 addition (0.01 wt %) on the product gas yields and carbon

conversion. A 10 wt % glycerol solution has been used as feedstock. T = 602C, P = 280 bar.

Comparison of Pilot Plant Results with Data from Microreactors In Figure 4.8 gasification of 10 wt % glycerol in the pilot plant is compared with results obtained in the batch quartz capillaries (see Chapter 3) and the Inconel micro continuous reactor (see Chapter 5) for the same process conditions.

90

Xc [%]

1.6

yield [mole gas/ mole glycerol]

1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0

H2

Pilot plant (incoloy 825) micro continuous reactor (inconel 625) micro capillary reactor (quartz)

100

80

60

40

20

0
CO2 CO CH4 C2H4 C2H6 C3H6 C3H8 ----

Figure 4.8 Gasification results for 10 wt % glycerol at 600oC and 280 bar. Results from the pilot plant, the micro continuous reactor (see Chapter 5) and the capillary reactor (see Chapter 3) are compared. The highest carbon efficiency is observed in the micro continuous Inconel reactor, which has the highest catalytic wall area (Inconel contains 60% Ni) due to its small internal diameter of only 1 mm. The pilot plant reactor has also a catalytically active reactor wall, but a lower specific wall area (i.d. = 12 mm) resulting in a lower carbon conversion than the micro continuous reactor. Complete absence of catalytic activity in the batch capillary reactors results in the lowest carbon conversion.

Influence of Feed Concentration To investigate the influence of the concentration of the feedstock on the carbon efficiency and gas production, gasification experiments with 4.8, 10 and 17wt % of glycerol including 0.01 wt % Na2CO3 were performed. The results are presented in Figure 4.9.

91

carbon efficiency [%]

4.8 wt% 10 wt% 17 wt% yield [mole gas/mole glycerol]

2

100

80

60

40

20

0 H2 CO2 CO CH4 C2H6 4.8% 10% 17%

Figure 4.9.

Influence of concentration of the glycerol solution on the product gas yields and the

carbon conversion. T = 600C, P = 270 bar. Figure 4.9 shows that, like in the capillary reactors (see Chapter 3), higher feed concentrations (> 10%) cannot be converted completely to the gas-phase. Moreover, the water gas shift reaction is not reaching equilibrium, especially not at 17 wt % resulting in a significant CO concentration in the product gas.

92

carbon efficiency [%]

Conclusions and recommendations

The conclusions from this chapter can be summarized as follows: A first generation pilot plant for supercritical water gasification with a maximal throughput of 30 kg/h wet feedstock has been used for conversion tests. This plant is based on a shell and tube heat-exchanger and a tubular reactor and is designed to process non-fouling feedstock materials (in this case glycerol and methanol). Tests with glycerol and methanol as feedstock have shown that the pilot plant can be run without operational problems. While built for other purposes, the pilot plant is however not suited for very accurate measurement under well defined conditions like for the reactor temperature. With glycerol several experiments have been performed and the results have been compared with similar test conducted in the micro capillary reactors (see Chapter 3). It can be concluded that the trends observed in both systems are identical, viz.: Complete conversion of the feedstock to the gas-phase is only possible for very diluted feedstock solutions (< 5 wt %). Addition of Na2CO3 promotes the water gas shift reaction resulting in a high hydrogen yield and low CO levels. On the other hand, in absolute sense there is a clear difference between the results obtained in the pilot plant and in the capillaries. In the pilot plant, a higher carbon conversion from feedstock to gas phase products and more H2 production is achieved under similar conditions. This is ascribed to the catalytic activity of the wall of the Incoloy reactor of the pilot plant. The pilot plant, however, shows a lower carbon to gas phase conversion in comparison with the metal continuous micro system presented in Chapter 5 which can be explained by the lower specific catalytic wall area of the pilot plant reactor compared to the continuous micro reactor (i.d. pilot plant is 1.38 cm vs i.d. micro continuous is 1 mm) Test with starch (a fouling feedstock) showed severe operational problems in the form of blockages at several locations. It has been decided to stop the pilot plant program for the time being. The focus is shifted towards the development of a micro continuous plant that provides the essential information, but is much cheaper and allows much faster experimentation (see Chapter 5). In similar micro systems the research on fluidization under supercritical conditions is continued and this will hopefully pave the way to efficient SCWG while allowing for fouling feedstocks.

93

Notation
fc,i

Carbon fraction (mass basis) of component i Lower heating value of feed dry and ash free, MJ/m3 Lower heating value of permanent gas, MJ/m3 Molar mass, kg/mole Reaction pressure, bar Reaction time, s Reaction temperature, oC Carbon conversion, % Gas yield Mass flow rate of organics in the feed, kg/h Mass flow rate of component i, kg/h

LHV feed LHV product gas ,i

M
P T T

Xc
Y product gas

feed i
References

Antal, M.J.; Allen, S.; Lichwa, J.; Schulman, D.; Xu, X., Hydrogen Production from High-Moisture Content Biomass in Supercritical Water. In U.S. DOE Hydrogen Program Review, 1999. Antal, M.J.; Allen, S.G.; Schulman, D.; Xu, X.; Divilio, R.J., Biomass Gasification in Supercritical Water. Ind. Eng. Chem. Res. 2000, 39, 4040. Boukis, N.; Diem, V.; Dinjus E.; Galla U.; Kruse A., Advances with the Process of Biomass Gasification in Supercritical Water. Presented at the 4th International Symposium on High Pressure Technology and Chemical Engineering, Venice: Italy, 2002. Hao, X.H.; Guo, L.J.; Mao, X.; Zhang, X.M.; Chen, X.J., Hydrogen Production from Glucose used as a Model Compound of Biomass Gasified in Supercritical Water. Hydrogen Energy 2003, 28, 55. Holgate, H.R.; Meyer, J.C.; Tester, W.J., Glucose Hydrolysis and Oxidation in Supercritical Water. AIChE J. 1995, 41, 637. Kabyemela, B.M.; Takigawa, M.; Adschiri, T.; Malaluan, R.M.; Arai, K., Mechanism and Kinetics of Cellobiose Decomposition in Sub- and Supercritical Water. Ind. Eng. Chem. Res. 1998, 37, 357. Kabyemela, B.M.; Adschiri, T.; Malaluan, R.M.; Arai, K., Glucose and Fructose Decomposition in Subcritical and Supercritical Water: Detailed Reaction Pathway, Mechanisms, and Kinetics. Ind. Eng. Chem. Res. 1999, 38, 2888. Kruse, A.; Henningsen, T.; Sinag, A.; Pfeiffer, J., Biomass Gasification in Supercritical Water: Influence of the Dry Matter Content and the Formation of Phenols. Ind. Eng. Chem. Res. 2003, 42, 3711. Lee, I.; Kim, M.-S.; Ihm, S.-K., Gasification of Glucose in Supercritical Water. Ind. Eng. Chem. Res. 2002, 41, 1182.
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Manarungson, S.; Mok, W.S.L.; Antal, M.J., Hydrogen Production by Steam Reforming Glucose in Supercritical Water. In Advances in Thermochemical Biomass Conversion; Bridgwater, A.V., Ed.; Blackie Academic and Professional: London, U.K., 1993; p. 1367. Matsumura, Y.; Minowa, T.; Potic, B.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M.; van de Beld, L.; Elliott, D.C.; Neuenschwander, G.G.; Kruse, A.; Antal, M.J., Biomass Gasification in Near- and Supercritical Water: Status and Prospects. Biomass Bioenergy 2005, 29, 269. Modell, M., Gasification and Liquefaction of Forest Products in Supercritical Water. In Fundamentals of Thermochemical Biomass, Overend, R.P.; Milne, T.A.; Mudge, L.K., Eds.; Elsevier Applied Science Publishers Ltd.: London, 1985, p. 95. Potic, B.; van de Beld, L.; Assink, D.; Prins, W.; van Swaaij, W.P.M., Gasification of Biomass in Supercritical Water. In Proceedings of the 12th European Conference and Exhibition on Biomass for Energy, Industry and Climate Protection; Palz, W.; Spitzer, J.; Maniatis, K.; Kwant, K.; Helm, P.; Grassi, A., Eds.; ETA Florence, WIP Munich: Amsterdam, 2002; p. 777. Potic, B.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M., Gasification of Model Compounds and Wood in Hot Compressed Water. Submitted to Ind. Eng. Chem. Res., 2005 Schmieder, H. Abeln, J.; Boukis, N.; Dinjus, E.; Kruse, A.; Kluth, M.; Petrich, G.; Sadri, E.; Schacht, M., Hydrothermal Gasification of Biomass and Organic Wastes. In Proceedings of the 5th Conference on Supercritical Fluids and their Applications, Garda, Italy, 1999; p. 347. Van de Beld, L.; Wagenaar, B.M.; Assink, D.; Potic, B.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M.; Penninger, J.M.L., Biomass and Waste Conversion in Supercritical Water for the Production of Renewable Hydrogen. Presented at the 1st European Hydrogen Energy Conference, Grenoble, France, 2003. Xu, X.; Matsumura, Y.; Stenberg, J.; Antal, M.J., Carbon-Catalyzed Gasification of Organic Feedstocks in Supercritical Water. Ind. Eng. Chem. Res. 1996, 35, 2522. Xu, X.; Antal, M.J. Jr., Gasification of Sewage Sludge and Other Biomass for Hydrogen Production in Supercritical Water. Environmental Progress 1998, 17, 215. Yu, D.; Aihara, M.; Antal, M.J., Hydrogen Production by Steam Reforming Glucose in Supercritical Water. Energy Fuels. 1993, 7, 574.

95

96

Chapter 5
SCWG Experiments in a Micro Continuous Flow Reactor
Abstract
This chapter is dealing with SCWG of glycerol and glucose in a continuous reactor. For this investigation a continuous micro reactor system has been developed. The reactors used are stainless steel 316 and Inconel capillaries with an internal diameter of 1 mm and a length of 1 meter. One goal of this investigation is to show the catalytic effect of the reactor construction material and to show the influence of the process conditions on the carbon conversion and the product gas distribution. In addition, selected catalysts, namely 3 wt % Ru on TiO2 and charcoal of beech wood, are tested in a fixed bed micro reactor system. This investigation has revealed that the carbon conversion and product gas distribution strongly depend on the selected reactor construction material. Moreover, it is confirmed that pressure has no effect on the carbon conversion and gas yield and that an increase of concentration of organics in the feed results in a lower carbon conversion and less hydrogen production. Addition of Ru catalyst provokes cracking/reforming of oxygenated hydrocarbons that without catalyst would slip trough the reactor and end-up as liquid product. Demonstration of combustion with air under realistic process conditions of produced carbonaceous deposits from glucose gasification, represents an important aspect of an industrial SCWG reactor system.

97

Introduction
With a quartz batch capillary technique (Potic et al., 2004) more than 700 experiments have been performed to investigate the gasification of organic compounds in supercritical water (Chapter 2 and 3). These data form the basis of a complete map of the SCWG operating window for glucose and glycerin under non-catalytic conditions. However, for catalyst screening and to study possible ways to recover or to avoid carbonaceous deposits when processing realistic feedstock materials, also tests under continuous operating conditions are required. For these purposes, several tests have been performed in a pilot-plant with a nominal throughput of 10 kg wet feedstock per hour (see Chapter 4). Operation of this pilot-plant is labor intensive and very costly. Besides, the results are not yet accurate enough to serve as a basis for process development. To enable quick and cheap experimentation under supercritical conditions a continuous micro tubular reactor (1 mm internal diameter) has been developed and tested. Both an empty tube and an empty tube in series with a packed bed of catalyst particles have been used as reactor system. Experiments have been done to investigate the catalytic effect of the construction material and the influence of the process conditions. Besides, some preliminary tests have been performed with selected catalysts (3 wt % Ru on TiO2 and charcoal of beech wood), including burn-off of carbonaceous deposits.

98

Experimental
The continuous micro reactor for SCWG has been developed to allow simple, safe and cheap experimentation without using a special high-pressure infrastructure. Such a system should be flexible with easy to replace parts allowing fast cleaning and short experimental runs at steady state. These demands were met by miniaturization and by elimination of a complex multi-phase pressure reduction valve. The continuous SCWG reactor system consisted out of a HPLC piston pump, a tubular reactor, an electrical oven, a cooler, a pressure vessel, a liquid collection vessel and a sampling bag for gases. Figure 5.1 is a schematic representation of the experimental set-up. Stainless steel 316 and Inconel capillaries with an internal diameter of 1 mm and a length of 1 meter were used as tubular reactors (V = 0.785 mL). Quartz reactors were also tested but these were found to be too fragile for continuous operation. The set-up could in principle be operated with a catalytically inert reactor like quartz but this could not yet be technically solved. The flow rate of the feedstock was controlled accurately with a HPLC pump (LabAlliance). This pump could deliver flow rates of water in the range of 0.01 to 24 mL per minute at a maximum pressure of 500 bar. The pressure directly after the pump was measured and monitored with the in-built pressure sensor of the pump. For the rapid cooling of the reactor effluent a cooler was placed just after the oven. The cold liquid, gases and entrained solids (if any) were collected in a high pressure vessel (V = 30 mL), which was connected to a pressure sensor. Between the cooler and the pressure vessel a simple valve was placed. This pressure vessel was also used to start-up the system in the following way. While the valve was closed, the vessel was pressurized with helium and water was pumped into the reactor and cooler until the pressures up and downstream the valve equalized. Then the valve was opened and the helium in the vessel maintained the pressure in the system. Hereafter, the experiment was started by switching from water to the feedstock solution. During a typical experiment the pressure increased ca. 50 bar. The representative pressure of an experiment was defined as the average of the start and end pressure of that tests (<p>). We allowed for this pressure increase, because in the batch capillaries it was observed that the operating pressure did not effect the results in the range of 40 to 400 bar (see Chapter 3). During operation, the temperature was measured with three thermocouples (tip = 0.5 mm) placed on the outer wall of the capillary. The temperature difference between these thermocouples never exceeded more than 3C during operation. Additionally, the axial temperature profile inside the reactor was initially measured by a movable thermocouple. By these measurements it was shown that the first 11 cm of the reactor (total length is 1 meter) were needed to reach the final reactor temperature for a typical flow rate of 0.04 mL/min. For all employed flow rates the length of the heating zone was determined. In this way, the reaction time, defined as the time that the fluid was at
99

the final reactor temperature, could be calculated. For all investigated cases the heating time was about the same as the reacting time. After the experiments, the gas products were collected in a sampling bag, which was then connected to a GC for the gas analysis. On the basis of the readings of the GC, the total number of moles present in the pressure-vessel (calculated from the known T, P and V of this vessel), and the amount of feedstock, the mass balance (yields and conversion) was calculated. The carbon conversion and the product yields, are chosen here as the main process qualifiers. The carbon conversion is defined as degree of conversion of carbon from biomass to permanent gases:

Xc =

N c , product gas ,i N c , feed x 100

The product yield is defined as:

Y product gas ,i =

N product gas ,i N feed

For the catalytic tests, the last 30 cm of the capillaries were filled with catalyst. The catalyst zone was placed between two supports to ensure fixed bed operation. Ru (3 wt %) on TiO2 (dp = 150 micron) and charcoal (dp = 150 micron) from beech wood were tested as catalysts. In this way, in first 70 cm of the reactor heating non-catalytic gasification is taking place. The reaction time in this zone is about 45 s , which is, according to earlier results (Chapter 3), enough to reach the maximum carbon conversion at temperatures of 600oC and higher. In catalytic zone, all primary reaction products (gas, liquid and solid) are brought in contact with catalyst. The residence time in the catalytic bed was ca. 10 s.

100

Thermocouples
TI

Electrical oven

Reactor

TI

Fixed bed

TI

Cooler

HPLC pump Feed tank

PI

Pressure sensor Gas bag

Pressure vessel

Collecting vessel

Figure 5.1. Schematic representation of the experimental set-up. Burn-off of carbonaceous deposits was done by leading pressurized air through the system. At the start of these experiments, the system was at atmospheric pressure and the air-cylinder at 180 bar. The burn-off tests were ended when the pressure in the air-cylinder and the pressure vessel equalized (ca. 40 bar).

101

Validation of the Technique Mass balance closure was checked by experiments with formic acid, which according to the literature (Yu and Savage, 1998) should be converted completely to gas-phase components at temperatures above 650oC and low feed concentrations. Several runs were performed at 700oC and feedstock concentrations below 2.5 wt %. The observed carbon conversion (fraction of carbon in the feedstock converted to gas-phase components) varied between 98 and 102%. As an example, Table 5.1 lists the results of two identical experiments. These results are typical for the obtained reproducibility. It can be concluded that all produced gases can be recovered with the method used and the reproducibility is satisfactorily. In the tables and figures of this Chapter individual data points are reported, although always a duplo was performed. The relative deviation of the duplos was never higher than 5%. Table 5.1. Result of two identical tests with formic acid in the stainless steel continuous flow reactor. Feedstock: 1.3 wt % formic acid in water, T = 700oC, <p> = 300 bar, and 60 s reaction time. Formic acid 1.3 wt % Run T [oC] P [bar] t [s] Gas composition [%] H2 CO2 CO Carbon conversion [%] 55.92 42.94 1.14 98.7 55.20 43.67 1.13 101.1 1 700 300 60 2 700 300 60

102

Results
Catalytic Effect of the Reactor Wall The material of construction of the SCWG reactor is suspected to influence the conversion results in case reactors with a high specific wall area are compared. By adding Inconel powder to the quartz capillaries, the effect of an Inconel reactor wall was mimicked. In these experiments the catalytic activity of Inconel was clearly observed (see Chapter 3). In well-defined experiments in the micro continuous flow reactor the influence of the reactor wall material on the SCWG process has been confirmed and quantified. Using Inconel instead of stainless steel 316 as construction material resulted in an increase of the carbon conversion from 62 to 82% when processing a 10 wt % glycerol solution at 600oC. Also the product gas composition is affected significantly; SS316 seems to promote the water-gas shift reaction (low CO yield), Inconel not (see Figure 5.2). These results on the catalytic influence of the reactor wall are inline with earlier observations of Yu et al. (Yu et al., 1993), who reported results of gasification of glucose in the same experimental set-up under identical conditions, but using other metals for the reactor. They found large differences between experiments carried out in Inconel, Hastelloy and corroded Hastelloy reactors.

1.6

100 Inconel 625 SS 316

gas yield [mole gas/mole glycerol]

60 0.8 40 0.4

20

0.0
H2 CO2 CO CH4 C2H6 Inconel SS --

Figure 5.2 Influence of the reactor wall material on the gas production and carbon conversion for 10 wt % glycerol, T = 600 C, <p> = 300 bar and 60 s reaction time.

103

carbon conversion [%]

1.2

80

Effects of the Process Conditions Concentration organics in the feed solution From the capillary tests it has become clear that for non-catalytic SCWG the concentration of organics in the feedstock affects the carbon conversion to a large extent (see Chapter 3). At 650oC, a high carbon conversion (> 98%) turned out to be possible only with low concentrated feedstocks (< 2 wt %). Higher concentrations resulted in an incomplete carbon conversion. In the Inconel micro continuous flow reactor, the observed carbon conversions are higher than in the quartz capillaries for identical conditions, probably due to the catalytic activity of the wall. However, the trend with respect to the influence of the concentration on the feedstock is also observed in the continuous Inconel reactor (see Figure 5.3). At 600C glycerol solutions of up to 5 wt % can be gasified nearly completely, while for a 10 wt % solution the carbon conversion is limited to 82%.

100

glycerol 600 C, 300 bar, 60s 1 wt% 5 wt% 10 wt%

carbon conversion [%]

gas composition [%]

80

60

40

20

0
H2 CO2 CO CH4 C2H6 Cefficiency --

Figure 5.3. Influence of the glycerol concentration on the gas distribution and carbon conversion. Inconel reactor, T = 600 oC, P = 300 bar and 60 s reaction time.

Process pressure Although it has been suggested that supercritical water properties would be beneficial for the gasification reaction, experimental results from the capillary reactors (see Chapter 3) showed that the pressure has no influence on the carbon efficiency and product distribution. In the SS 316 micro continuous flow reactor these tests have been repeated. Again, it can be concluded that the pressure has no significant effect on the carbon conversion and product distribution. Figure 5.4 shows the two extremes of the investigated pressure range (100 to 300 bar) for 10 wt % glycerol at 700oC and 60 s reaction time.
104

100

glycerol 10 wt%, 700 C, 60s 100 bar 300 bar

80 gas composition [%] carbon conversion [%]

60

40

20

0 H2 CO2 CO CH4 C2H6 Cefficiency

Figure 5.4 Influence of the pressure on the product gas composition and carbon conversion. 10 wt % glycerol, stainless steel 316 reactor, T = 700oC and 60 s reaction time.

Catalytic fixed bed reactor These tests were performed with glycerol as feedstock. When glycerol is not completely gasified, only liquids are formed as by-products never carbonaceous deposits (Buhler et al., 2002). This makes interpretation of the results easier. The potential and necessity of heterogeneous catalysis for the SCWG process has been demonstrated already with the batch capillaries (Chapter 3). However, the undefined contacting efficiency of the catalyst particles in the capillary made the experiments difficult to interpret and to compare with the limited available results form literature. In this chapter well-defined catalytic experiments have been done in a fixed bed reactor with a length of 30 cm and an internal diameter of 1 mm. Charcoal of beech wood (produced at 600C) and 3 wt % Ru on TiO2 were tested as catalysts. A 10 wt % glycerol solution was used as feedstock. In these tests no carbonaceous deposits products (not soluble in acetone) were observed in the collecting vessel and the reactor after the experiments. When passing the (intermediate) reaction products over a charcoal bed with a residence time of ca. 10 s, the carbon conversion increases slightly viz. from 65 to 74% (see Figure 5.5). Antal and coworkers (Xu et al., 1996) observed complete carbon conversion by leading the effluent of their tubular reactor over a bed of coconut shell activated carbon at 600C and 15 s residence time. The results are difficult to compare because different types of charcoal were used under different process conditions (residence time in catalyst bed, location of catalyst bed, temperature profile in the reactor). Using the Ru catalyst, the carbon conversion increased to nearly 100%. Another interesting observation is that with this cat C2-compounds are not found in the product gas, while the yield of CO, CO2, CH4 and H2 increases. These results indicate that the Ru catalyst cracks/reforms oxygenated

105

hydrocarbons, including those being liquids at ambient conditions, to smaller molecules such as CO, CO2, CH4 and H2.
2.5 glycerol 10 wt.% glycerol 10 wt.%+ char glycerol 10 wt.% + Ru/TiO2 100

yield [mole gas/mole glucose]

2.0

80

1.5

60

1.0

40

0.5

20

0.0
H2 CO2 CO CH4 C2H6 10% 10%+C10%+Ru

Figure 5.5 Influence of different catalysts on the gas production and the carbon conversion for 10 wt % glycerol, SS 316 reactor, T = 600oC, P = 300 bar and 60 s reaction time.

Burn-off of carbonaceous deposits In a real system, using waste streams as feedstock, the formation of fouling in the form of carbonaceous deposits is inevitable. To study the SCWG process under such conditions glucose was used as feedstock, because it is know to produce carbonaceous deposits. Combustion of these deposits is proposed as a feasible remedy in an industrial reactor (see Chapter 7). In this way, a by-product is removed from the system and heat is generated to drive the endothermic process, provided a suitable reactor/process design is made. At 600C a 10 wt % glucose solution was processed without catalyst. The carbon conversion during this test was ca. 63% (see Table 5.2, first column). After passing air through the system an additional 15% of carbon was recovered in the form of CO2 and tracer of CO (see Table 5.2, second column). However, in an identical experiment but with the Ru catalyst bed included, 100% of the carbon in the feedstock is recovered. 85% is directly gasified and 15% is recovered after burn-off (see Table 5.2, third and fourth column). This result indicates that carbonaceous deposits do not slip trough the reactor, but apparently remain on the reactor wall and the catalyst particles. The increase in carbon conversion when using the Ru catalysts again points in the direction that this catalyst converts oxygenated hydrocarbons to permanent gases. Without Ru catalyst these oxygenated hydrocarbons would have slipped through the system and would be recovered as liquid products after the experiment.

106

carbon conversion [%]

Table 5.2 Results of gasification and gasification and combustion process as for 10 wt % glucose at 600oC, 280 bar and 60 s reaction time Glucose 10 wt % gasification C conv.[%], C-recovery H2 CO2 CO CH4 C2H4 C2H6 C3H6 C3H8 26.6 39.9 14.0 12.8 0.8 3.7 1.0 1.1 63.3 77.4 Gas composition 41.2 42.5 1.1 15.1 0.0 0.0 0.0 0.0 gasification + combustion 85.2 103.1 Glucose 10 wt % + Ru/TiO3 gasification gasification + combustion

In the capillary tests, complete gasification of 10 wt % glucose was achived at 600oC when adding the Ruthenium catalyst. The 15% difference in conversion between the batch and continuous tests may be explained by: Deactivation of the catalyst in the continuous reactor. In the batch tests always fresh catalyst was used and the test only lasted for 60 s, whereas the continuous reactor was operated for two hours without regeneration of the catalyst. The life time of the catalyst was not investigated by the developers (Elliott et al., 1997) under SCWG condition. However, it was reported that at the designed conditions (24 MPa, 360oC) the catalyst showed a tendency towards de-activation (Elliott et al., 2004). The presence of carbonaceous deposits in the inert section before the catalytic section. When these deposites are not entrained with the main flow through the catalytic bed, their catalytic conversion is obviously not possible.

107

Conclusion
A simple continuous micro-scale SCWG reactor system has been designed and demonstrated for fast and cheap experimentation. It avoids the use of a cumbersome pressure relief valve and is suitable for empty tube, packed bed and potentially fluid bed reactors. The conclusions from this work can be summarized as follows: The catalytic activity of metal reactor construction materials has been confirmed in the empty tube continuous flow reactor. To different materials, viz. Inconel and stainless steal showed considerable differences in carbon conversion and product distribution under identical process conditions. Despite the catalytic influence of the wall, all trends found in the inert quartz batch capillaries were observed also in the metal continuous flow reactors. The most important ones being that the pressure does not affect the product distribution and carbon conversion and that increasing the concentration of the feedstock results in a lower carbon conversion and less hydrogen production. The tested Ru catalyst increases the carbon conversion considerable. There is evidence that this catalyst cracks/reforms organic components that without catalyst would slip through the reactor and end-up as liquid product. Glucose produces carbonaceous by-products in the SCWG process. These deposits can be combusted with air under realistic process conditions, which may be an important aspect of an industrial SCWG reactor system.

Notation N c, product-gas,i N c, feed N product-gas,i N

feed

Number of moles C in product gas i produced, mol Number of moles C in feedstock fed, mol Number of moles product gas i component produced, mol Number of moles of feedstock fed, mol Carbon conversion, % Yield of product gas component i, mol produced gas/mol feed

Xc Yproduct-gas,i

108

References

Buhler, W.; Dinjus, E.; Ederer, H.J.; Kruse, A.; Mas, C., Ionic Reactions and Pyrolysis of Glycerol as Competing Reaction Pathways in Near- and Supercritical Water. J. Supercrit. Fluids 2002, 22, 37. Elliott, D.C.; Sealock, L.J. Jr.; Baker, E.G., Method for the Catalytic Conversion of Organic Materials into a Product Gas. U.S. Patent 5616154, 1997. Elliott, D.C.; Neuenschwander, G.G.; Hart, T.R.; Butner, R.S., Low-Temperature Catalytic Gasification of Wet Biomass Residues. In Proceedings of the 2nd World Biomass Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection; van Swaaij, W.P.M.; Fjallstrom, T.; Helm, P.; Grassi, A., Eds.; ETA-Florence and WIP-Munich: Rome, Italy, 2004; p. 746. Potic, B.; Kersten, S.R.A.; Prins, W.; Assink, D.; van de Beld, L.; van Swaaij, W.P.M., Gasification of Biomass in Supercritical Water: Results of Micro and Pilot Scale Experiments, In Proceedings of the 2nd World Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection, van Swaaij, W.P.M.; Fjallstrom, T.; Helm, P.; Grassi, A., Eds.; ETA-Florence and WIPMunich: Rome, Italy, 2004; p. 742. Potic, B.; Kersten, S. R.A.; Prins, W.; van Swaaij, W.P.M. A High-throughput Screening Technique for Conversion in Hot Compressed Water. Ind. Eng. Chem. Res. 2004, 43, 4580. Potic, B.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M., Gasification of Model Compounds and Wood in Hot Compressed Water. Submitted to Ind. Eng. Chem. Res., 2005. Xu, X.; Matsumura, Y.; Stenberg, J.; Antal, M.J., Carbon-Catalyzed Gasification of Organic Feedstocks in Supercritical Water. Ind. Eng. Chem. Res. 1996, 35, 2522. Yu, D.; Aihara, M.; Antal, M.J., Hydrogen Production by Steam Reforming Glucose in Supercritical Water. Energy Fuels 1993, 7, 574. Yu, J.; Savage, P.E., Decomposition of Formic Acid under Hydrothermal Conditions. Ind. Eng. Chem. Res. 1998, 37, 2.

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110

Chapter 6
Fluidizat ation with Supercritical Water in Microreactors
Abstract
In this chapter the concept of micro-uidized beds is introduced. A cylindrical quartz reactor with an internal diameter of only 1 mm is used for process conditions up to 500oC and 244 bar. In this way, fast, safe, and inherently cheap experimentation is provided. The process that prompted the present work on miniaturization is gasication of biomass and waste streams in hot compressed water (SCWG). Therefore, water is used as uidizing agent. Properties of the micro-uid bed such as the minimum uidization velocity (Umf), the minimum bubbling velocity (Umb), bed expansion, and identication of the uidization regime are investigated by visual inspection. It is shown that the micro-uid bed requires a minimum of twelve particles per reactor diameter in order to mimic homogeneous uidization at large scale. It is not possible to create bubbling uidization in the cylindrical micro-uid beds used. Instead, slugging uidization is observed for aggregative conditions. Conical shaped micro-reactors are proposed for improved simulation of the bubbling regime. Measured values of Umf and Umb are compared with predictions of dedicated 2D and 3D discrete particle models (DPM) and (semi)-empirical relations. The agreement between the measurements and the model predictions is good and the model supports the concept and development of micro-uid beds.

This chapter has been published in Chemical Engineering Science, 60 (2005), 5982-5990.

111

Introduction
Miniaturization of chemical reactors is receiving increased interest (Kolb and Hessel, 2004; Maharrey and Miller, 2001). Micro-reactors are specifically suitable for high throughput screening, on-demand chemical synthesis, and carrying out reactions under conditions that would normally lead to unsafe operation. In general, miniaturization leads to lower capital and operational costs, less energy consumption, improved safety, and less pollution. In this chapter, the miniaturization principle is applied to fluid bed research. At present, laboratory (10 - 100 mL reactor volume) and pilot-scale (0.1 - 1000 l reactor volume) research and development concerning fluidised bed systems is expensive and labour intensive. In fact, it is anticipated here that this type of research will become too expensive in the future, especially if it involves high temperature and pressure. The objective of this work is, therefore, to develop a new experimental method based on micro-fluid bed reactors with an internal diameter of only a few millimetres. Possible applications of micro-fluid beds are high-throughput screening of catalysts, establishing the operating window of a certain process, or study of specific hydrodynamic phenomena. Investigating chemical fluid bed processes in micro-fluid beds, for instance, is preferable over testing in high-throughput fixed beds. Translating fixed bed data to fluid bed operation is not straightforward, particularly when adsorption/desorption of reactants and products, decompositions on the catalyst, and fast-aging catalyst are involved. Under these conditions, fixed beds suffer from the fact that strong spatial gradients in the composition of the fluid phase and the catalyst properties will make interpretation of the data troublesome. The typical characteristics and conditions of a large-scale fluid bed, being 5 to 15 s gas residence time, 2 - 3 mixing units, and 1 - 5 mass transfer units (De Vries et al., 1972; Van Swaaij and Zuiderweg, 1973), should be mimicked in micro-systems. It is, however, not necessary that exact mapping is achieved at every level. The similarity should be based on the overall (chemical) performance of the process under consideration. The micro-fluid bed can have every desired shape, ranging from a uniform cylindrical tube to a conical bed and a staged reactor configuration (see Figure 6.1). In cylindrical micro beds of only several millimeters, it will be difficult to create stable bubbling fluidization, because slug formation will occur immediately after entering the aggregative regime. Conical micro-fluid beds are considered to suppress slugging and to simulate a bubbling bed. Somewhat larger conical fluid beds (1 - 4 cm), showing intense back mixing of both the solid and the fluid phase, have been discussed by Kersten et al. (Kersten et al., 2003). Conical fluid beds can also be applied if more fluid phases are to be processed together. The process that prompted the present work on miniaturization is gasification of biomass and waste streams in hot compressed water (SCWG). SCWG is foreseen to require fluid bed technology operated in severe conditions (Kersten et al., 2004). Gasification in hot compressed water is a novel process for the conversion of wet biomass and waste streams (> 80 wt % moisture) into hydrogen or methane rich gas. The operating pressure is typically above 200 bar and temperatures in the range of 300 - 650C
112

are considered (Antal et al., 2000; Elliott et al., 1994; Hao et al., 2003; Kruse, 1999; Potic et al., 2004; Potic et al., 2004; Schmieder et al., 2000; Yu et al., 1993). The SCWG process is at an early stage of development. In the laboratory and pilot plant work carried out so far, next to batch autoclave reactors, tubular flow reactors have been used in connection with a shell and tube heat-exchanger. Not much information has been published on the practical design of a reactor for a commercial plant. Simple non-fouling model compounds have been used frequently as feedstock. However, thermal composition of real biomass (e.g. verge grass paste) results in carbon formation and ash deposition (Yoshida et al., 2004). This implies that catalysis is required to achieve complete conversion to gases and to steer the product distribution (Antal et al., 2000; Potic et al., 2005). To cope with such fouling conditions in combination with catalysis an integrated reactor/heat-exchanger concept, based on fluid beds and circulating solids, has been proposed (Kersten et al., 2004). For quick, safe and cheap experimentation with such a system the micro-fluid bed technique has been developed. Sufficient mass balance closure of experiments with a chemical reaction using such a small system has been established already with a comparable batch method (Potic et al., 2004). Available data on fluidization with high-pressure CO2 cover a broad range of fluid densities and viscosities (Liu et al., 1996; Marzocchella and Salatino, 2000) and can be used, as a starting point, for the investigation of fluidization with hot compressed water. In fact, using CO2 of much less severe conditions can approximate the density and viscosity of water used for the gasification process. To study the chemical process it is, however, essential that the actual reaction medium, viz., hot compressed water, can be used in the experimental method.

Cylindrical micro two phase reactor

Conical micro two phase reactor

Conical three phase reactor

Figure.6.1 Different microreactors in the fluid bed program. In the present contribution, cylindrical micro-fluid beds are discussed. It is investigated whether or not the classical design equations for Umf, Umb, Ut and bed expansion can be used for the micro-system. Fluidization of A and B powders with water in the range of 1 - 244 bar and 20 - 500C is reported. Also the differences and similarities between gas, liquid, and supercritical fluids in fluidization are shown. The experimental results are compared with both literature correlations and the predictions of a state of the art 3D Euler-Lagrange (DPM) model (Ye et al., 2004, 2005).
113

Experimental
The central part of the micro reactor system presented here is a fluid bed with an internal diameter of only a few millimetres (say one to three millimetres). For testing under high pressure and temperature, all kinds of special alloys (e.g. Inconel) and quartz can be used as construction material of the fluid bed. In case of quartz, visual inspection of the fluid bed reactor under process conditions is possible even under extreme circumstances. Due to their small size, the quartz capillaries used are strong enough to withstand extremely high pressures (300 bar) and high temperatures (900oC). Other advantages of the small dimensions are intensive heat transfer from the surroundings (oven) to the reactor, the very small amount of catalyst needed, low costs, and the fact that the system is inherently save. The experimental system used for this investigation on fluidisation consisted basically out of a HPLC piston pump, a quartz capillary used as fluid bed, an electrical oven, and a pressure vessel. Figure 6.2 is a schematic representation of the experimental set-up. The flow rate of water was controlled accurately with a HPLC pump (LabAlliance). This pump could deliver flow rates of water in the range of 0.01 - 24 mL/min at a maximum pressure of 500 bar. A quartz capillary of 1 mm ID, 6 mm OD and a length of 1 m was used as fluid bed. The actual settled height of the bed was 20 mm. These dimensions lead to an aspect ratio of the bed of 20, which is high compared to industrial practice. Twenty millimetres fixed bed height was selected in order to keep the error on the measurement of the fluid bed level below 10%. This was necessary to obtain accurate estimates of Umf and Umb from the expansion curve. In case of homogeneous fluidization, it is known that the aspect ratio does not influence the fluidization behaviour to a large extent. For bubbling fluidization, the aspect ratio is an important parameter. However, the overall heat and mass transfer rates of beds with high and low aspect ratio may approach each other by tuning of the operating conditions. Some 30 cm of length before and after the bed were required to account for heating the incoming water and to prevent back-mixing effects of cold water from the down stream side.

114

Section A Thermocouple
TI

Window Reactor Distributor

PI

Pressure sensor

Thermocouple

Section A

TI

Glass window Pressurized vessel

Reactor

TI

Electrical oven

HPLC pump Water tank

Figure 6.2 Scheme of the experimental set-up. Application of a conventional gas distributor turned out not to be possible in such a small system. To solve this problem, a quartz ball (~ 0.9 mm) that just fitted inside the 1mm i.d. capillary placed on a thermocouple was used as an alternative to a regular distributor plate. Raining of bed particles through the gap between the inner wall and the ball distributor was never observed. The quartz capillary set up was heated in an electrical oven. A glass window was placed in this oven at the location where the fluid bed was positioned. This allowed for visual inspection of the fluid bed and photography. A ruler was placed behind the fluid bed for measurement of the bed height. Connections of the quartz capillary to the steal tubing, connecting it to the pump and the pressure vessel, were placed outside the oven. The capillary was connected to the pressure vessel via a one-way valve in order to prevent that the content of the pressure vessel could flow back into the reactor. Nitrogen was used to pressurize this vessel. Upstream the pressure vessel, the system was pressurized by pumping water, with the valve closed, into the quartz capillary and tubing until the pressure prevailing inside the pressure vessel was reached. Then the valve was opened and the nitrogen in the vessel maintained the pressure in the system. Due to the much higher volume of the vessel compared to the capillary (500:1), the pressure
115

remained almost constant during operation. By employing this semi-batch method of operation, the need for a complex two-phase pressure-release valve was omitted and large samples could be collected at nearly constant conditions. Monitoring of the pressure was done with the built-in sensor of the HPLC pump and a pressure sensor placed at the entrance of the pressure vessel. During operation, the temperature was measured with three thermocouples (tip = 0.5 mm) placed on the outer wall of the capillary and one thermocouple (tip = 0.5 mm) inside the reactor. The latter was the one used as support for the quartz ball serving as a distributor. One of the three thermocouples on the outer wall was placed at the location of the fluid bed. The temperature difference between this thermocouple and the one inside the bed never exceeded more than 3C during fluidization and their average value was defined as the bed temperature. Additionally, the axial temperature profile inside the quartz tube was measured, in the absence of the fluid bed, by a movable thermocouple inserted via the top. By these measurements it was shown that up to 20 cm downstream the ball distributor the temperature inside the capillary was constant for all investigated flow rates. Sand with a density of 2450 kg/m3 was as bed material. Four different particle sizes were used: 60 - 70 m, 80 - 90 m, 100 - 150 m, and 150 - 250 m. To investigate the effect of the reactor diameter the 1 mm diameter quartz tube was replaced by tubes of 12 and 26 mm.

Measurement Procedure A digital camera was used to take snapshots of the fluidization behaviour. All derived numbers in this work were based on visual observations. In case of homogeneous fluidization (investigated range f = 500 - 1200 kg/m3), Umf, Ut, and n were determined from the bed expansion curve. The superficial velocity was fixed by the flow rate of the HPLC pump and the prevailing temperature and pressure in the fluid bed. The minimum velocity increment corresponded to an increase of the flow rate of liquid water by 0.01 mL/min. The bed expansion curve was constructed by reading the height of the bed at different velocities. The error on reading the bed level was 1 - 2 mm. By measurement of the amount of bed material and the fixed bed height, the initial (fixed bed) porosity was determined. The voidage and the superficial velocity were correlated according to the Richardson and Zaki equation:

U =n Ut

(1)

Figure 6.3 shows a typical measured expansion graph and the derived Richardson and Zaki curve. Umf was determined by extrapolating the expansion curve to the fixed bed height. Extrapolation was necessary, because in all cases, Umf corresponded to flow rates below the lower limit of the HPLC pump. Due to the need for extrapolation and the error on reading the bed height, the statistical error on
116

Umf was around 50%. Extrapolation was not required for determining Ut and n, and consequently the related error was much lower, namely ca. 10%. Bed expansion was measured visually also in case of fluidization with water vapor (investigated range f = 16 230 kg/m3). For superficial velocities higher than 12 mm/s aggregative fluidization, in the form of slugs, was observed in this regime. In case of slugging, the height of the expanded bed was more difficult to determine. A time-averaged bed height taken over a time period of 1 min was then used.
1.5

3.0

1.0

2.5

(H-H )/H0 [-]

ln (U)

2.0

0 0.5

1.5

0.0 0 5 10 15 20 25

1.0 -0.6 -0.5 -0.4 -0.3 -0.2

U [mm/s]

ln()

(a) curve. b) Plot of the Richardson-Zaki equation constructed expansion curve.

(b)

Figure 6.3 Example of the liquid fluidization: T = 320oC, P = 160 bar, = 682 kg/m3: a) Expansion

Due to the limitation of the pump with respect to minimum achievable flow rate (0.01 mL/min), determination of Umf was principally not possible for densities below 100 kg/m3. The minimal flow rate of 0.01 mL/min corresponded to a linear velocity in the range of 2 - 14 mm/s for densities below 100 kg/m3, whereas according the Abrahamsen and Geldart relation, Umf should range between 2 and 3 mm/s for these conditions. For the density range of 100 - 230 kg/m3 it turned out that Umf could also not be determined. The reason for this was that the observed bed expansion between the fixed bed state and the slugging velocity was only 2 - 3 mm, which was too little to serve as basis for an accurate estimate of Umf. The minimum bubbling velocity was defined as the average value of the velocity at which the first slugs were observed and the velocity before that one. Discrete Particle Model The micro-fluid bed was modeled by the volume-averaged Navier-Stokes equations (Kuipers et al., 1992) combined with the Newtonian equations of motion for a single particle taking into account possible collisions with other particles and the confining walls. In this study, the contact force between two particles was calculated by use of the soft-sphere model (Cundall and Strack, 1979). The details
117

can be found elsewhere (Ye et al., 2004, 2005). Compared to the code recently described (Ye et al., 2004, 2005), one additional force, namely the added mass force, was added to allow simulation of systems involving high-density fluidizing agents. The added mass force is essential if the fluid is a dense gas or a liquid. There are different expressions for the added mass forces in the literature (Auton et al., 1988; Chang and Maxey, 1995; Clift et al., 1978; Maxey and Riley, 1983). In this study, we followed the derivation of Maxey and Riley, where the added mass force was given by:

Fm = Cm f V p
with:

D( v u) Dt

(2)

D = + u Dt t

(3)

In most previous studies the added mass coefficient Cvm was simply assumed to equal 0.5, being the theoretical value for a sphere moving in an unbounded fluidum. This value, however, is in addition only valid for very dilute systems where the influences of neighbouring are not important. In this research, the added mass coefficient was taken from the Zuber equation for the added mass force of a particle in a homogeneous dispersion in an non-rotational flow (Batchelor, 1988), given by:

Cvm =

3 2 2

(4)

Together with the added mass force, there also exists a history force, which is also known as memory force or Basset force. It takes into account the vorticity diffusion in the surrounding fluid, and the disturbance effect caused by the acceleration of the sphere. The calculation of this force is complicated since it involves the integral of the derivative of fluid velocity and particle velocity. In all simulations reported in this paper the Basset history force was neglected. In the presented simulations, the geometries of the system were taken as either a box with a size of 1 1 40 mm3 in 3D or a rectangle with a size of 1.5 50 mm2 in 2D. The choice of such simplified geometries was made to enable the DPM simulations. The parameters used in the simulations are summarized in Table 1. The water properties were taken from the database of the National Institute of Standards and Technology (NIST) in the form of polynomials.

118

Table 6.1 Parameters used in the DPM simulations. Parameters Particle number Particle diameter Particle density Initial bed height CFD time step Number of CFD cells Coefficient of restitution Coefficient of friction Fluid temperature Fluid pressure Value 36000 (3D) and 3440 (2D) 85 m (3D) and 80 m (2D) 2495 kg/m3 (3D) and 2600 kg/m3 (2D) 2.00 cm (3D) and 1.36 cm (2D) 2.010-6 s 44100 (3D) and 4100 (2D) 0.9 (3D) and 0.95 (2D) 0.2 (3D) and 0.1 (2D) 873.16 K; 773.16 K; and 673.16 K Varying from 0.6 to 28.4 MPa

119

Results
Visual Presentation In Figure 4 snapshots of the micro-fluid bed in operation are presented. Figure 6.4a shows a typical series of homogeneous fluidization experiments with liquid water in which the velocity is increased. The length of the expanded bed for different velocities is used for the derivation of the expansion curve. In the case of fluidization with water vapor slugging is observed. The slugs can be clearly seen in the capillaries (see Figure 4b). The bed level is fluctuating under slugging conditions (see Figure 6.4b).

(a) Figure 6.4. fluidization, same bed at different time.

(b) Photographs of (a) homogeneous fluidization at different flow rates and, (b) slugging

Minimum Number of Particles per Reactor Diameter It is expected that there should be minimum number of particles present per reactor diameter for a micro-fluid bed to mimic a large-scale bed under otherwise identical conditions. To investigate this, glass balls of 60 - 200 m diameter have been fluidized with water at ambient conditions in three glass tubes with different internal diameters, viz. 26 mm, 12 mm and, 1mm. The homogeneous expansion curves of these fluid beds have been recorded while using sand particles of different size. Unfortunately, the data cannot be compared over the full velocity range. Due to limitations of the pump with respect to its minimum achievable flow rate, the lowest velocities in the 12 mm and 26 mm bed could not be reached in the 1mm capillary.

120

Figure 6.5a shows the bed expansion and the voidage versus the velocity for the 1 mm and the 12 mm ID bed while using particles of 60 - 70 m diameter. It can be seen that the curves obtained in the 1 mm and the 12 mm bed are nearly identical. Also for the particles of 80 - 90 m, there is a good agreement between the expansion curves obtained in the three beds of different sizes, although the agreement seems less satisfactory than for the 60 70 m particles. In case of particles of 100 - 150 m, expansion in the 1 mm bed differs significantly from expansion in the 12 mm bed. This deviation is ascribed to wall effects. Finally, when using particles larger than 150 m, it has been observed that the particles appear to move irregularly in clusters in stick-slip flow and a fluidized state cannot be clearly recognized anymore. These results lead us to the conclusion that micro-fluid beds need 12 or more particles per diameter in order to resemble a large-scale fluid bed in case of homogeneous fluidization.
1

particle size 60-70micron

particle size 80-90micron

ln(e), ln(H-H0)/H0

-1

ln(e), ln(H-H0)/H0
-9 -8 -7 -6 -5

-1

-2

-2

-10

ln(U)

-10

-9

-8

-7

-6

-5

ln(U)

(a)
1

(b)

particle size 100-150micron

ln(e), ln(H-H0)/H0
0

o
-1

1mm voidage 1mm expansion 12mm voidage 12mm expansion 26mm voidage 26mm expansion

-2

-10

-9

-8

-7

-6

-5

ln(U)

(c) Figure 6.5 Expansion and voidage curve for the different i.d. reactors with particles of: (a) 60 - 70 micron, (b) 80 - 90 micron and (c) 100 - 150 micron. Homogeneous systems.
121

Fluidization with Water: f = 500 to 1020 kg/m3 Measurements have been done in the range of 20 - 360C and 1 - 221 bar. In this density range, the observed fluidization is always particulate. With increasing velocity, homogeneous expansion of the bed is observed and bubbles (slugs) are never present. These observations are in agreement with the discrimination number (Dn) criterion of Liu et al. (Liu et al., 1996) which states that for Dn < 104, fluidization is homogeneous. For the conditions presented here, Dn is always smaller than 3500. In the considered range, the viscosity of water at a certain density hardly depends on the prevailing temperature and pressure. This allows constructing a characteristic velocity map with the fluid density on the x-axis. Such a plot for particles with dp = 85 m and p = 2450 kg/m3 is presented in Figure 6. As mentioned before, the measurement error for Umf is rather large. Nevertheless, it can be concluded that the measured Umf values are in reasonable good agreement with predictions, obtained on basis of the Ergun equation (Ergun, 1952) provided that the measured fixed bed porosity of 0.5 is used in the calculations. The sharp increase of one decade in Umf when going down in density from 1020 to 900 kg/m3 as predicted by theory is also observed experimentally. Values of Ut derived from the expansion graphs are close, although systematically higher, to theoretical values calculated according to Haider and Levenspiel (Haider and Levenspiel, 1989). Correlations for Umf and Ut are based on measurements in larger fluid beds ranging from several centimetres to metres. Because the measurements obtained in the 1 mm fluid bed are reasonably well described by these correlations, it can be concluded that large-scale fluidized operated in the homogeneous regime can be mimicked in micro-fluid beds. However, for this to hold the micro-fluid bed should to satisfy the condition of D/dp > 12 (see above).
0.1

Ut Haider & Levenspiel

0.01

U [m/s]

Umf
1E-3

Ergun (0=0.50)

1E-4

500

600

700

800
3

900

1000

fluid density [kg/m ]

Figure 6.6. Umf and Ut measured for water in the 1 mm i.d. FB versus f. f = 500 - 1050 kg/m3, p = 2450 kg/m3, dp = 85 m. Measurements as well as correlations are plotted.
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Fluidization with Water Vapor: f = 16 to 230 kg/m3 Measurements have been done as well in the range of 345 - 485C and 50 - 245 bar. In the density region below 90 kg/m3, only slugging is observed. This region corresponds to discrimination numbers exceeding 4 x 104, which is indicative for the aggregative fluidization regime. For higher densities, two regimes are observed. From zero velocity up to approximately 2xUmb, fast slugging is observed. Upon increasing the velocity, the slugs become smaller and their frequency increases. Eventually, this leads to fluidization in which the slugs cannot be observed anymore and the bed level becomes constant. For instance, for water vapor of 113 kg/m3 such a regime is observed for velocities higher than 26 mm/s. This phenomenon has been described also by Li on the basis of simulations with a Euler-Lagrange CFD model (Li, 2003). The corresponding Dn values for 100 kg/m3 and U 2xUmf range from 0.5 x 104 up to 1.8 x 104 describing homogeneous and transitional regimes. It is not possible to create bubbling fluidization in the cylindrical micro-fluid beds used. Conical shaped micro-reactors, geometrical similar to those of Kersten et al. (Kersten et al. 2003), will be developed for improved simulation of bubbling and three-phase fluidization as may prevail in catalytical gasification in hot compressed water. As mentioned before, Umf cannot be determined for these conditions and Umb is estimated from the velocity at which the first slugs are observed (see section 2.1). Measured values of Umb are compared with the Abrahamsen and Geldart relation and predictions of a 3D DPM model (see Figure 6.7). It should be noticed that the A and G correlation must be extrapolated outside the validated regime for the conditions investigated here. In the DPM model, the fluid velocity is increased linearly with time. At the point where the overall pressure drop equals the bed weight per unit area, the minimum fluidization velocity is reached. Via visualization of the computed results using animation techniques, the minimum bubbling velocity can be established. At Umb larger voids appeared in the generated pictures of the fluid bed. The details of the DPM model are presented elsewhere (Ye et al., 2004, 2005). Both the A and G relation and the DPM model predict that, in the investigated density regime, Umf and Umb hardly (10%) depend on the temperature (viscosity) for a certain water vapor density (pressure). Within the experimental error, the experimental estimates of Umb agree with the DPM results, which are also somewhat higher than predictions from the empirical relations of A and G (see Figure 6.7).

123

25 experimental data for Umb o DPM model Umb 400 C o DPM model Umb 500 C o DPM model Umb 600 C o DPM model Umf 400 C o DPM model Umf 500 C o DPM model Umf 600 C

superficial fluid velocity [mm/s]

20

15

10 Umb (A&G correlation) 5 Umf (A&G correlation) 0 0 50 100 150 200 250

density [kg/m3]

Figure 6.7 Comparisons of the Umf and Umb calculated from empirical correlations with DPM model results and experimental values.

2D Simulation Results In addition, 2D simulations have been carried out to visualize the flow patterns and the transition of the flow regimes. Snapshots of the simulated fluidization behavior at a set pressure of 153.0 bar are shown in Figure 6.8. At first, homogeneous bed expansion is observed. Then void structures in the top and bottom of the bed can be clearly observed, but no obvious bubbles appear. At a velocity of 36 mm/s, more or less clear bubbles can be found. For a still higher fluid velocity, the bubbles develop quickly and form clear slugs. The snapshots of the fluidization at the same fluid velocity but at different fluid pressures are shown in Figure 6.9. It can be seen that with an increasing pressure, the fluidization behavior becomes more smooth and large bubbles or slugs are transformed into microvoids. Visually this may be interpreted as homogeneous fluidization.

124

Figure 6.8

Snapshots of the simulation results in a 2D supercritical water fluidized bed. Particle

diameter d = 80 m, particle density = 2600 kg/m3, fluid temperature T = 783 K, fluid pressure p = 153.0 bar, and fluid density 50 kg/m3. Superficial fluid velocities U are 0.0, 0.012, 0.024, 0.036, and 0.048 m/s respectively.

Figure 6.9

Snapshots of the simulation results in a 2D supercritical water fluidized bed. Particle

diameter d = 80 m, particle density = 2600 kg/m3. Fluid temperature T = 783 K. Fluid pressures are, from left to right, 34.5, 67.1, 97.5, 126.3, 153.0, 178.1, 201.4, 223.2, and 262.4 bar, respectively, which corresponds with fluid densities of, from left to right, 10, 20, 30, 40, 50, 60, 70, 80, and 100 kg/m3. Superficial fluid velocity U is 0.036 m/s.

125

Conclusions
The conclusions of this work can be summarized as follows: A quartz micro-fluid bed set-up has been developed and operated up to 5000C and 244 bar. With these reactors, biomass gasification in hot compressed water can be studied. The method is safe and cheap. Visual observation of the bed position and fluidization regime is possible as well as the occurrence of different phases, carbon deposition in case of gasification, etc. Full control of pressure, temperature, and flow rates is possible and relatively easy. Homogeneous fluidization, slug flow and more or less homogeneous turbulent beds have been observed roughly in line with the Dn criterion of Kwauk and Li and empirical correlations. Despite the small diameter of the fluid bed, the expansion of the homogeneous fluid bed is similar to those of larger beds provided Dt/dparticles >12. 2D and 3D soft-sphere simulations, including added mass effects for high density fluids, were able to simulate the micro-fluid beds well. In the future, this model will be used to assist the further development of micro-fluid bed reactors.

Notation Ar Cm D Dn dp F m g k mf n Remf t u U Umb Umf Ut Archimedes number, Ar = gdp3 (p - f)f/2, dimensionless added mass coefficient, dimensionless reactor inside diameter, m discrimination number , Dn= Ar/ Remf (p - f)/ f, dimensionless particle diameter, m added mass force, N acceleration of gravity =9.81 m/s2 slope,m/s2 mass, kg numerical exponent in Richardson-Zaki equation, dimensionless Reynolds number at minimum fluidization velocity, Remf= Umf dp f /, dimensionless time, s local gas velocity, m/s fluid velocity, mm/s minimum bubbling velocity, mm/s minimum fluidization velocity, mm/s terminal velocity, mm/s
126

v Greek letters f p

particle velocity, m/s

void fraction, dimensionless fluid density, kg/m3 particle density, kg/m3 fluid viscosity, Pa.s

References

Antal, M.J.; Allen, S.G.; Schulman, D.; Xu, X.; Divilio, R.J., Biomass Gasification in Supercritical Water. Ind. Eng. Chem. Res. 2000, 39, 4040. Auton, T.R.; Hunt, J.; Prud'Homme, M., The Force Excerted on a Body in Inviscid Unsteady NonUniform Rotating Flow. J. Fluid Mech. 1988, 197, 241. Batchelor, G. K., A New Theory of the Instability of a Uniform Fluidized Bed. J. Fluid Mech. 1988, 193, 75. Chang, E.J.; Maxey, M.R., Unsteady Flow about a Sphere at Low to Moderate Reynolds umber. Part 2: Accelerated Motion. J. Fluid Mech. 1995, 303, 133. Clift, R.; Grace, J.R.; Weber, M.E., Bubbles, Drops and Particles. Academic Press, New York, 1978. Cundall, P.A.; Strack, O.D., A Discrete Numerical Model for Granular Assemblies. Geotechnique 1979, 29, 47. De Vries, R.J.; van Swaaij, W.P.M.; Mantovani, C.; Heijkoop, A., Design Criteria and performance of the Commercial Reactor for the Shell Chlorine Process. In Proceedings of the 5th Eur. Symposium on Chemical Reaction Engineering; Elsevier Publ. Corp.: Amsterdam, The Netherlands, 1972. Elliott, D.C.; Sealock, L.J., Jr.; Baker, E.G., Chemical Processing in High-Pressure Aqueous Environment. 3. Batch Reactor Process Development Experiments for Organics Destruction. Ind. Eng. Chem. Res. 1994, 33, 558. Ergun, S., Fluid Flow Through Packed Columns. Chem. Engng. Prog. 1952, 48, 89. Haider, A.; Levenspiel, O., Grag Coefficient and Terminal Velocity of Spherical and Non-Spherical Particles. Powder Technology 1989, 58, 63. Hao, X.H.; Guo, L.J.; Mao, X.; Zhang, X.M.; Chen, X.J., Hydrogen Production from Glucose used as a Model Compound of Biomass Gasified in Supercritical Water. Hydrogen Energy 2003, 28, 55. Kersten, S.R.A.; Prins, W.; van der Drift, B.; van Swaaij, W.P.M., Principles of a Novel Multistage Circulating Fluidized Bed Reactor for Biomass Gasification. Chem. Eng. Sci. 2003, 58, 725.

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Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M., Reactor Design Considerations for Biomass Gasification in Hot Compressed Water. In Proceedings of the 2nd World Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection, van Swaaij, W.P.M.; Fjallstrom, T.; Helm, P.; Grassi, A., Eds.; ETA-Florence and WIP-Munich: Rome, Italy, 2004; p. 777. Kolb, G.; Hessel, V., Micro-stuctured Reactors for Gas Phase Reactions. Chem. Eng. J. 2004, 98, 1. Kruse, A. Abeln, J.; Dinjus, E.; Kluth, M.; Petrich, M.; Schacht, E. Sadri, E.; Schmieder, H., Gasification of Biomass and Model Compounds in Hot Compressed Water. Presented at the International Meeting of the GVC-Fachausschu "Hochdruckverfahrenstechnik", Karlsruhe, Germany, 1999; Paper No. 107. Kuipers, J.A.M.; Duin, K.J.; van Beckum, F.P.H.; van Swaaij, W.P.M., A Numerical Model of Gasfluidized Beds. Chem. Eng. Sci. 1992, 47, 1913. Li, J., Euler-Lagrange Simulation of Flow Structure Formation and Evolution in Dense Gas-Solid Flows. University of Twente, The Netherlands, 2003. Liu, D.; Kwauk, M.; Li, H., Aggregative and Particulate Fluidization - The Two Extremes of a Continuous Spectrum. Chem. Eng. Sci. 1996, 51, 4045. Maharrey, S.P.; Miller, D.R., Quartz Capillary Microreactor for Studies of Oxidation in Supercritical Water. AIChE J. 2001, 47, 1203. Marzocchella, A.; Salatino, P., Fluidization of Solids with CO2 at Pressures from Ambient to Supercritical. AIChE J. 2000, 46, 901. Maxey, M.R.; Riley, J.J., Equation of Motion for a Small Rigid Sphere in a Nonuniform Flow. Phys. Fluids 1983, 26, 883. National Institute of Standards and Technology (NIST), Gaithersburg, MD. Potic, B.; Kersten, S.R.A.; Prins, W.; Assink, D.; van de Beld, L.; van Swaaij, W.P.M., Gasification of Biomass in Supercritical Water: Results of Micro and Pilot Scale Experiments. In Proceedings of the 2nd World Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection; van Swaaij, W.P.M.; Fjallstrom, T.; Helm, P.; Grassi, A., Eds.; ETA-Florence and WIPMunich: Rome, Italy, 2004; p. 742. Potic, B.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M., A High-throughput Screening Technique for Conversion in Hot Compressed Water. Ind. Eng. Chem. Res. 2004, 43, 4580. Potic, B.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M., Gasification of Model Compounds and Wood in Hot Compressed Water. Submitted to Ind. Eng. Chem. Res., 2005. Schmieder, H.; Abeln, J.; Boukis, N.; Kruse, A.; Kluth, M.; Petrich, G.; Sadri, E.; Schacht, E., Hydrothermal Gasification of Biomass and Organic Wastes. J. Supercrit. Fluids 2000, 17, 145. Van Swaaij, W.P.M.; Zuiderweg, F.J., Investigation of Zone Decomposition in Fluidized Beds on the Basis of Two Phase Model. In Int. Symposium on Fluidization and its Applications, Toulouse, France, 1973. Ye, M.; van der Hoef, M.A.; Kuipers, J.A.M., A Numerical Study of Fluidization Behaviour of Geldart A Particles Using a Discrete Particle Model. Powder Technology 2004, 139, 129.
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Ye, M.; van der Hoef, M.A.; Kuipers, J.A.M., The Effects of Particles and Gas Properties on the Fluidization of Geldart A Particles. Submitted to Chem. Eng. Sci., 2005. Yoshida, T.; Oshima, Y.; Matsumura, Y., Gasification of Biomass Model Compounds and Real Biomass in Supercritical Water. Biomass Bioenergy 2004, 26, 71. Yu, D.; Aihara, M.; Antal, M.J., Hydrogen Production by Steam Reforming Glucose in Supercritical Water. Energy Fuels 1993, 7, 574.

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130

Chapter 7
Reactor Design Con onsiderations for Biomass Gasification in Hot Compressed Water
Abstract
This chapter deals with the design of a reactor for biomass gasification in hot compressed water. Starting from the experimental results obtained in this thesis and those available in the open literature, the requirements for an optimal design are identified, listed and discussed. An integrated reactor/heat-exchanger concept, based on fluid beds and circulating solids, is proposed that can cope with catalysis under fouling conditions, combustion of carbonaceous deposits, and ash removal.

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Introduction
Biomass gasification in supercritical water (SCWG) is a novel process, under development after the pioneering work of Modell (Modell, 1985) and Antal and co-workers (Yu et al., 1993) since the mid eighties of the last century. In the laboratory (Antal et al., 2000; Hao et al., 2003; Kruse et al., 2003; Lee et al.; 2002, Yu et al., 1993) and pilot-plant work (Boukis et al., 2002; Van de Beld et al., 2003) that was reported so far, metal tubular reactors were used frequently in connection with a shell and tube heat-exchanger. This thesis adds the following items to the experimental knowledge on SCWG: The work described in Chapters 2 and 3 deals with mapping of the SCWG operating window under catalytically inert conditions in batch microreactors. Continuous test including catalyst testing and burn off of carbonaceous deposits is investigated at micro (Chapter 5) and pilot scale (Chapter 4). Fluidization under SCWG conditions is investigated in Chapter 6. Experiments have been performed with glycerol and glucose solutions. Glycerol does not produce carbonaceous deposits under SCWG conditions and is consequently a model compound that represents feedstock materials that do not cause fouling problems (e.g. very diluted streams). Glucose does produce carbonaceous deposits and thus embodies more complex feed streams. Tests with glucose solutions have provided information on the problems (fouling and blocking) that such feedstock materials can cause in the heat-exchanger and reactor (Chapters 3 and 5). Not too much attention has been paid to the practical design of a SCWG reactor (including heatexchanger) for continuous operation in a future commercial plant. While looking for the best reactor, a number of requirements, characteristic for the SCWG process, should be taken into account. They are listed and discussed in this chapter. Based on the list of these design aspects, a reactor concept for SCWG is proposed. Such an analysis has been presented earlier by Kersten et al. (Kersten et al., 2004) in the initial stage of the SCWG project at the University of Twente, based primarily on data available in the open literature. In this chapter, the results of this thesis are added to the discussion, in particular those results that provide new insights. Only the reactor/heat-exchanger is discussed here, other challenging units of SCWG plant like the feedstock pump are not considered in this analysis.

132

Design aspects
1. Temperatures of above 800oC are needed in the reactor to allow non-catalytic thermal degradation of the biomass molecules, and subsequent cracking or gasification of the intermediate sized fragments to only the desired small molecules H2, CO, CH4 and CO2 (Antal et al., 2000 and Chapter 3 and 5). Complete conversion of the model solutions to the gas-phase is only possible under inert conditions for solutions with a concentration of organics of less than 5 wt %; higher concentrations produce liquid and solid by-products (Chapters 3 and 5). By applying catalysis, the required operating temperature can be reduced to 600oC and more concentrated solutions (up to 17 wt % glucose has been tested) can be gasified completely (Chapter 3). Recently, Cortright et al. (Cortright et al., 2002) and Elliot et al. (Elliott et al., 1993) demonstrated the potential of catalysis. Cortright et al., for instance, obtained a high yield to hydrogen from diluted solutions (1 wt % model compound in compressed water) at temperatures as low as 265oC by using Pt/Al2O3. It is, however, not evident that at such low temperatures also high concentrations of organic matter can be treated. 2. High pressures. Although it has been suggested sometimes that supercritical water properties would be beneficial for the gasification reactions, experiments at micro scale have shown little influence of the pressure on either the carbon conversion degree, or the product yield and distribution (Chapter 3). It is crucial for the process that the heat content of the reactor effluent is utilized as far as possible to pre-heat the feedstock stream (mainly water) to reaction conditions. However, heat exchange between these streams is not practical at low pressure, because of the high heat of evaporation at nearly isothermal and isobaric conditions. Heating of the feedstock stream to the desired gasification temperatures in a heat-exchanger without evaporation, requires operation at high pressures. This is the true incentive of the high pressures involved in wet gasification (Chapter 1). 3. Additional heat. In practice, a hundred percent transfer of the available heat in the reactor effluent to the feedstock stream is impossible. In fact, efficiencies of ca. 75% are typical for liquid-liquid shell and tube heat-exchangers (Woods, 1995) resulting in a heat-exchanger outlet temperature of the feed stream of ca. 450oC. The required temperature rise to the reactor conditions may be generated by the exothermicity of the reactions. This is however only possible for highly concentrated feedstocks in combination with a considerable methane production being a combination that is only possible by applying catalysis. In all other cases additional heat input is required for the reactor. This heat can be supplied externally and/or by in-situ generation by the heat of oxidation reactions. For the latter, oxygen has to be added to the process. In-situ oxidation is preferable over external heating because of efficiency and construction reasons. But it is then crucial to do it selectively, that is without consuming any desired products. This is discussed further in the next part.
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4. Incomplete conversion of the biomass is something that has to be taken into account in reactor design considerations. Thermal decomposition of most wet feedstocks will result in carbon formation, either simultaneously with the production of tars (condensable vapors) and gaseous compounds, or as a result of secondary reactions of tar. It was found that, even under the high water pressure prevailing in the SCWG process, steam gasification of char is still extremely slow (Van Swaaij, 2003). This result excludes recycling of the carbon from the water outlet stream, or applying very long residence times, as a reactor design option. In-situ oxidation of the carbon looks indeed interesting, because of the corresponding heat production inside the reactor. Besides, in case of catalyst addition (discussed in the next part), regeneration will be required to burn off any carbon deposited on the catalyst surface. While considering in-situ oxidation of the carbon, it should be realized that oxygen introduced into the SCWG reactor will react preferentially with gaseous products and dissolved organic molecules, while leaving the carbon largely unconverted. Reactor staging, or creating separate combustion and gasification zones inside a single reactor, may be a solution (Kersten et al., 2003). Alternatively, a secondary wet-oxidation reactor can be used to clean the effluent water from the SCWG reactor. Burnoff of carbonaceous deposits on the reactor wall and /or catalyst particles has been tested successfully in a continuous micro reactor (Chapter 5) under realistic process conditions. 5. Catalysis is needed to lower the required gasification temperatures for complete conversion and to improve the selectivity to either H2, or CH4 in case substitute natural gas is aimed at (Elliott et al., 1993). From the work done in Japan, by researchers of NIRE (Minowa et al., 1998), it appears that alkali metals as well as nickel-based catalysts promote the production of hydrogen at the cost of the carbon monoxide yield. Elliott and co-workers from the Pacific Northwest National Laboratory (Sealock et al., 1996) used a ruthenium catalyst for methane production from organic waste streams. In both cases the conditions were subcritical, that is within the temperature range from 200 to 350oC and at pressures up to 350 bar. Catalysis for supercritical conditions has been applied by Antal (Antal et al., 2000) who found in his laboratory reactor increased carbon conversions when activated carbon derived from coconut shells was used as a catalyst in a fixed bed. By adding 3 wt % Ru on TiO2, a catalyst developed for conversion of waste water (Elliott et al., 1999), to the quartz capillary reactors complete conversion of 1 to 17 wt % glucose solutions has been achieved at 600oC (Chapter 3). These experiments clearly show the potential of heterogeneous catalysis. However, this catalyst may not suitable for the actual process because of degeneration problems as discussed in Chapter 3 of this thesis and by Elliot et al. (Elliott and Chapter 3). It is important to realize that, at the time of writing, the potential of noble metal catalysts has been shown, but that stable systems with a long life time are not available yet. This chapter focuses on catalytic gasification of feedstock stream containing more than 5 wt % organics at 600oC, being a realistic temperature in view of the current status of catalyst development. For reactor design the application of a heterogeneous catalyst has complicating
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consequences, e.g. regeneration is required (see above). On the other hand, it also creates the opportunity for additional removal of minerals that are deposited together with the coke on the catalyst surface. Moreover, particle circulation can be used further to prevent the heat-exchanger from coking and plugging. The formation of ash and coke occurs in a temperature range of roughly 200 - 400C, and perhaps mainly in a confined region of the tubular heat-exchanger. 6. Mixing pattern inside the reactor. At present, most of the continuous reactors in operation are tubular with little or no backmixing. Available literature results (Antal et al., 2000; Kruse et al., 2003; Lee et al., 2002), and our own experimental data (Potic et al., 2004 and Chapter 3), demonstrate clearly that when the weight percentage biomass is increased, less permanent gases and more liquids and chars are produced. As this situation is undesired, low feed concentrations are preferred. However, it is not the concentration in the feed that is important, but the (local) concentration in the reactor. When using an ideally stirred reactor it is possible to have a low reactant concentration in the reactor while feeding a high concentration. It has been observed that, for non-catalytic gasification, the time needed to reach the maximum conversion at temperatures above 650oC is about 30 s (Chapter 3). Following the rules of David and Villermaux (David and Villermaux, 1978), this means that the mixing time in the stirred cell should be around 3 s when ideal micro-mixing is aimed at. The question is however, whether or not ideal micro-mixing is really required. Probably, a less-ideally mixed reactor (partial segregation) could also result in higher conversions than can be achieved in reactors with plug-flow. This will have to be established experimentally. A fluidized bed with turbulent solids mixing (e.g. a spouted bed) is known to have reasonably good mixing of the fluid phase. 7. Ash treatment is an important issue in SCWG as most ashes are completely unsolvable in supercritical water. Ash removal from the reactor as deposits on bed particles is a better option than entraining it with the reactor effluent. Removal of these deposits together with the bed particles may prevent blockage and corrosion/erosion problems. 8. Fouling and Corrosion. Corrosion is a serious problem at high temperatures, especially if oxygen and sulfur are present. This is one of the reasons to develop catalysts that can reduce the required gasification temperatures. With respect to the selection of the construction material for a commercial plant, a two-barrier solution could be adapted from the technology of SCW oxidation that has been developed earlier (Fauvel et al., 2003). Up to now it is recommended to construct the essential parts from a custom-made alloy like for instance Inconel 625. A problem of general nature in SCWG is the required heat exchange between the reactor outlet and inlet streams. Heating of the biomass slurry in a heat-exchanger is likely to cause fouling/plugging problems because the thermal decomposition starts already at ca 200oC producing oily products (tars) and, more seriously, polymers (char).
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Reactor design
The following integrated reactor/heat-exchanger concept is proposed here for the SCWG process (see Figure 7.1). It is assumed that heat is required in the main reactor. This concept consists of: A fluidized bed (FB) reactor is used as main reactor to carry out the gasification/cracking of biomass to permanent gases and by-products. Fluid bed operation has been tested and demonstrated in this thesis (Chapter 6). It has become clear that a supercritical fluid bed can be designed with available design relations derived for much less severe conditions. The particles in the FB are catalytically active in order to lower the temperature at which maximal conversion to the desired product is reached and to steer the product distribution. The reactor is operated at ca. 600oC; the total system runs at approximately 230 bar. This fluidized bed is designed and operated with a conical bottom and/or drafttube to ensure good mixing of the phases.

Products Off gas

Fluidized Bed Reactor

O 2 / air Feed Heat exchanger

Solids Purge

Product

Off gas

Figure 7.1 Proposed reactor/heat-exchanger for SCWG. In the upper section of the main reactor, the solids are transported via a drainpipe to a separate combustor. The fluid phase is stripped from particles by conventional means (e.g. cyclones) and is available for heat exchange.

136

The carbon deposits are removed from the catalyst particles in the combustor by reaction with oxygen. Also for this reaction a fluidized bed is a suitable reactor. In the combustor, heat is produced and the catalyst particles are regenerated. Separate reactors for the main reaction and heat generation/catalyst regeneration, ensures that combustion of the desired product does not take place. This results in a higher thermal efficiency and effective conversion of the by-product. For an operating temperature of ca. 600oC in the main reactor, a suitable temperature of the combustor would be around 650oC. Just like in the main reactor, the solids are transported out of the reactor via drainpipe to the heatexchanger and the main reactor. The solids transported to main reactor provide the heat that is necessary to raise the temperature of the feed stream after leaving the heat-exchanger to reactor conditions. The off gas is available for heat exchange after separation of the solids. At the tube side of the heat-exchanger, the solids phase from the combustor is mixed with the fresh feed. It is wise to mix the particle phase with the fresh feed when the temperature level of this feed is around 200oC. Below this temperature, biomass does not decompose. Above 250oC, normally, produced char particles and tar deposits would cause blocking and fouling problems. However, in the proposed design this is counteracted by the scouring action of the particles, which keeps the heatexchanger clean. At the shell side of the heat-exchanger, the effluent from the main reactor and the off gas from the combustor are available. A special layout must be considered to keep the product and the off gas from the combustor separated. Ashes deposited on the bed particles surface can be withdrawn from the system at several locations in the solids-loop.

137

Conclusions
From the results obtained in this thesis on the SCWG of biomass and from previous literature results, a preliminary plant design concept is described which can cope with heat exchange and reaction under fouling conditions dealing with catalysis, coke combustion, and ash removal. The concept is based on fluid beds and circulating solids. The system will be further developed in micro systems.

References

Antal, M.J.; Allen, S.G.; Schulman, D.; Xu, X.; Divilio, R.J., Biomass Gasification in Supercritical Water. Ind. Eng. Chem. Res. 2000, 39, 4040. Boukis, N.; Diem, V.; Dinjus E.; Galla U.; Kruse A., Advances with the Process of Biomass Gasification in Supercritical Water. Presented at the 4th International Symposium on High Pressure Technology and Chemical Engineering, Venice: Italy, 2002. Cortright, R.D.; Davda, R.R.; Dumesic, J.A., Hydrogen from Catalytic Reforming of Biomass-derived Hydrocarbons in Liquid Water. Nature 2002, 418, 964. David, R.; Villermaux, J.J., De Chimie Physique 1978, 75, 656. Elliott, D.C.; Sealock, L.J.; Baker, E.G., Chemical Processing in High-Pressure Aqueous Environment: 2. Development of Catalyst for Gasification. Ind. Eng. Chem. Res. 1993, 32, 1542. Elliott, D.C.; Neuenschwander, G.G.; Phelps, M.R.; Hart, T.R.; Zacher, A.H.; Silva, L.J., Chemical Processing in High-Pressure Aqueous Environment. 6. Demonstration of Catalytic Gasification for Chemical Manufacturing Waste Water Cleanup in Industrial Plants. Ind. Eng. Chem. Res. 1999, 38, 879. Elliott, D.C.; Neuenschwander, G.G.; Hart, T.R.; Butner, R.S., Low-Temperature Catalytic Gasification of Wet Biomass Residues. In Proceedings of the 2nd World Biomass Conference, Biomass for Energy, Industry, and Climate Protection; van Swaaij, W.P.M.; Fjallstrom, T.; Helm, P.; Grassi, A., Eds.; ETA-Florence and WIP-Munich: Rome, Italy, 2004; p. 746. Fauvel, E.; Joussot-Dubien, C.; Pomier, E.; Guichardon, P.; Charbit, G.; Charbit, F.; Sarrade, S., Modeling of a Porous Reactor for Supercritical Water Oxidation by a Residence Time Distribution Study. Ind. Eng. Chem. Res. 2003, 42, 2122. Hao, X.H.; Guo, L.J.; Mao, X.; Zhang, X.M.; Chen, X.J., Hydrogen Production from Glucose Used as a Model Compound of Biomass Gasified in Supercritical Water. Hydrogen Energy 2003, 28, 55. Kersten, S.R.A.; Prins, W.; van der Drift, B.; van Swaaij, W.P.M., Principles of a Novel Multistage Circulating Fluidized Bed Reactor for Biomass Gasification. Chem. Eng. Sci. 2003, 58, 725. Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M., Reactor Design Considerations for Biomass Gasification in Hot Compressed Water. In Proceedings of the 2nd World Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection;, van Swaaij, W.P.M.; Fjallstrom, T.; Helm, P.; Grassi, A., Eds.; ETA-Florence and WIP-Munich: Rome, Italy, 2004; p. 777.
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Kruse, A.; Henningsen, T.; Sinag, A.; Pfeiffer, J., Biomass Gasification in Supercritical Water: Influence of the Dry Matter Content and the Formation of Phenols. Ind. Eng. Chem. Res. 2003, 42, 3711. Lee, I.; Kim, M.-S.; Ihm, S.-K., Gasification of Glucose in Supercritical Water. Ind. Eng. Chem. Res. 2002, 41, 1182. Minowa, T.; Zhen, F.; Ogi, T., Cellulose Decomposition in Hot-Compressed Water with Alkali or Nickel Catalyst. J. Supercrit. Fluids 1998, 13, 253. Modell, M., Gasification and Liquefaction of Forest Products in Supercritical Water. In Fundamentals of Thermochemical Biomass, Overend, R.P.; Milne, T.A.; Mudge, L.K., Eds.; Elsevier Applied Science Publishers Ltd., London, 1985; p. 95. Potic, B.; Kersten, S.R.A.; Prins, W.; Assink, D.; van de Beld, L.; van Swaaij, W.P.M., Gasification of Biomass in Supercritical Water: Results of Micro and Pilot Scale Experiments. In Proceedings of the 2nd World Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection; van Swaaij, W.P.M.; Fjallstrom, T.; Helm, P.; Grassi, A., Eds.; ETA-Florence and WIPMunich: Rome, Italy, 2004; p. 742. Potic, B.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M., Gasification of Model Compounds and Wood in Hot Compressed Water. Submitted to Ind. Eng. Chem. Res., 2005. Potic, B.; Kersten, S.R.A.; Ye, M.; van der Hoef, M.A.; Kuipers, J.A.M.; van Swaaij, W.P.M., Fluidization of Supercritical Water in Micro Reactor. Chem. Eng. Sci 2005, 60, 5982. Sealock, L.J. Jr.; Elliott, D.C.; Baker, E.G.; Fassbender, A.G.; Silva, L.J., Chemical Processing in High-Pressure Aqueous Environments. 5. New Processing Concepts. Ind. Eng. Chem. Res. 1996, 35, 4111. Van de Beld, L.; Wagenaar, B.M.; Assink, D.; Potic, B.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M.; Penninger, J.M.L., Biomass and Waste Conversion in Supercritical Water for the Production of Renewable Hydrogen. Presented at the 1st European Hydrogen Energy Conference, Grenoble, France, 2003. Van Swaaij, W.P.M., Technical Feasibility of Biomass Gasification in a Fluidized Bed with Supercritical Water. University of Twente: The Netherlands 2003, 160. Woods, D.R., Process Design and Engineering Practice. PTR Prentice Hall, New Jersey, 1995. Yu, D.; Aihara, M.; Antal, M.J., Hydrogen Production by Steam Reforming Glucose in Supercritical Water. Energy Fuels 1993, 7, 574.

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ACKNOWLEDGEMENTS

And now, after five years of learning how to fit into a new scientific environment, but also how to fit in every-day Dutch life, I have the opportunity to express my gratitude to the many people that helped me on my way to the dr title. To start with, I would like to thank my promoter prof.dr.ir. Wim van Swaaij, and the assistantpromoters dr.ir. Wolter Prins and dr. Sascha Kersten for giving me an opportunity to learn from them and to develop my expertise in reactor engineering and particularly biomass gasification processes. I am also grateful to prof.dr.ir. J.A.M. Kuipers, dr.ir. M.A van der Hoef, and dr. M. Ye for collaboration and support in CFD modeling of supercritical water fluidization, which resulted in a joint paper. Dr. Sascha Kersten, who also became a good friend of mine, should be mentioned especially. I would like to thank him for his generous moral support, patience and understanding. Sascha, I really learned a lot from you. Not just how things should be done in a PhD project, but also how an honest friendship can enrich ones life. Regarding the technical support, I was really lucky to have in the High Pressure Laboratory the kind assistance of Johan Agterhorst, who was always ready to help me at once. Daan Asink, an expert from BTG, enabled the pilot plant investigation and I sure need to thank him for his valuable support. Mrs. Yvonne Bruggert-ter Huurne and Wies Elfers, both secretaries in the TCCB group, helped me a lot with everyday problems at work. During the last few months Yvonne has put much effort in editing the style and text of my thesis for which I am very grateful. It was a great pleasure to work with her. My first contact at the UT was Rik Akse. He always took care of the financial and administrative aspects of my PhD project, which made my PhD-life a lot easier. I had a great time with all the other colleagues in the TCCB group, Xiaoquan Wang, Mariken Bleeker, Guus van Rossum, Dragan Knezevic, Marco Rep. And I should of course also acknowledge the staff of the High Pressure Laboratory, Gert Banis, Fred ter Borg, Karst van Bree and Geert Monnink for their pleasant support. Last but not least I would like to mention my students Mariken, Johny, Stefan and Sander who made a significant contribution to my research results.

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Apart from colleagues from the University, I received a lot of support and help from my personal friends. My best Dutch girlfriend and paranimf Diana Wulms enriched my life in many aspects, in particular regarding the Dutch culture. She accepted my family and me and helped us to adapt to a Dutch lifestyle. Thank you Diana! During the last year of my PhD work, Dennis Schipper fortunately opened to me the door of his company Demcon, and with that to the real professional life. I have now the opportunity to work with highly skilled people who are also very kind and helpful. Dennis, Bianca, Helena, HenkJan, Twan, Rini, Peter, Sjoerd, Mathijn, Philia, Reinier, Gert (Nanomi bv), Jeroen (Medspray bv) and all the others, I would like to thank you here as well. Finally I would like to thank Harry Slaghuis who played a special role in my familys life. Harry, only you know how many problems my family and I had since we arrived in Enschede. You brought to us a life that we never could dream of, peaceful and organized with lots of joyful moments. Having you as a friend makes me a rich person. To my Serbian friends (in Serbian) Hvala svima koji ste se potrudili da ulepate vreme koje smo proveli zajedno. Naroito bih elela da se zahvalim Vesni Smiljani na dizajnu koji je osmislila za ovu knjigu. To my parents Bora i Stojanka Vinjiki (in Serbian) Stigli smo do kraja i ove uzbudljive prie. Posle toliko godina vae bezuslovne podrke a pre svega vae beskrajne ljubavi, dobila sam ansu da vam se zahvalim. Mama, ta kap vode na dlanu koju si toliko uvala postala je vir oslikan na koricama ove knjige. Hvala ti to si uvek bila uz mene. Tata, postoji samo jedan nain da ti kaem koliko sam ponosna na sve to to smo zajedno proli: Naa kola ide napred! This book I dedicate to my daughters Luna and Mila and to my husband Goran. They give me all the strength and joy in my life. Their support and understanding also helped me to arrive at this very last part of my book. Luna, Mila and Goran, you are my life and my orientation. I love you!

Biljana Potic Enschede, May 2006.

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LIST OF PUBLICATIONS

Potic, B., van de Beld, L., Assink, D., Prins, W., van Swaaij, W.P.M., Gasification of Biomass in Supercritical Water. In Proceedings of the 12th European Conference and Exhibition on Biomass for Energy, Industry and Climate Protection; Palz, W.; Spitzer, J.; Maniatis, K.; Kwant, K.; Helm, P.; Grassi, A.; Eds.; ETA Florence, WIP Munich., Amsterdam, 2002, p.777. Van de Beld, L., Wagenaar, B.M., Assink, D., Potic, B., Kersten, S.R.A., Prins, W., van Swaaij, W.P.M., Penninger, J.M.L., Biomass and Waste Conversion in Supercritical Water for the Production of Renewable Hydrogen. Presented at the 1st European Hydrogen Energy Conference, Grenoble, France, 2003. Potic, B.; Kersten, S.R.A.; Prins, W.; Assink, D.; van de Beld, L.; van Swaaij, W.P.M., Gasification of Biomass in Supercritical Water: Results of Micro and Pilot Scale Experiments. Proceedings of the 2nd World Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection; van Swaaij, W.P.M.; Fjallstrom, T.; Helm, P.; Grassi, A., Eds.; ETA-Florence and WIPMunich: Rome, Italy, 2004; p. 742. Potic, B.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M., A High-throughput Screening Technique for Conversion in Hot Compressed Water. Ind. Eng. Chem. Res. 2004, 43, p.4580. Matsumura, Y.; Minowa, T.; Potic, B.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M.; van de Beld, L.; Elliott, D.C.; Neuenschwander, G.G.; Kruse, A.; Antal, M.J.; Biomass Gasification in Near- and Supercritical Water: Status and Prospects. Biomass and Bioenergy 2005, 29(4), 269. Potic, B.; Kersten, S.R.A.; Ye, M.; van der Hoef, M.A.; Kuipers, J.A.M.; van Swaaij, W.P.M., Fluidization of Supercritical Water in Micro Reactor. Chem. Eng. Sci. 2005, 60, 5982. Potic, B.; Kersten, S.R.A.; Prins, W.; van Swaaij, W.P.M.; Gasification of Biomass in Supercritical Water: Catalytic and Non-catalytic Batch Results. Accepted for publication in Ind. Eng. Chem. Res.

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CURRICULUM VITAE
Biljana Potic was born on September 20th 1970, in Novi Sad, Serbia and Montenegro. She studied Chemical Engineering at the University of Belgrade, Serbia and Montenegro and graduated in September 1994. Her master studies she did at the same University. During that period, she worked as research assistant in Process Thermodynamics group headed by Prof. Serbanovic. On 8th March 1998 she obtained her master degree on the subject of Heat transfer phenomena in the process furnaces. From 1996 till 2001 she worked as process engineer for Stark, Belgrade, Serbia and Montenegro. In 2001 she started her PhD work at the University of Twente with Prof. Van Swaaij and Dr. Prins on the subject: Biomass Gasification in Supercritical Water. Since February 2005 she works as a Project Manager in Demcon Twente B.V.

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