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L. van de Beld1), I. Bouwmans2), P.A.M.Claassen3), K. Hemmes2) *, H de Wit4), N. Woudstra2), Th. Woudstra2) and J.L. Zachariah2) 1) BTG, 2)Delft University of Technology, 3)ATO, 4)HoekLoos The Netherlands
ABSTRACT In this paper we present results of an exploratory study of conventional and new hydrogen production technologies geared towards the mixing of Hydrogen (H2) into the natural gas (NG) network in the Netherlands. The study is part of a large national project aimed at investigating the feasibility providing a H2/NG mixture, which would reduce diffuse CO2 emissions and assist in fulfilling the Kyoto agreement. The production methods considered in this study are assessed on a conceptual design level. In production of H2 from the NG itself, full conversion of hydrogen is no longer necessary as in conventional production technologies, because the H2 is to be mixed with NG. The concept of mixing H2 into the NG network also allows for new optimised and sometimes simplified conversion routes from bio-mass compared to those conversion routes that aim at the production of pure hydrogen and/or pure methane. Two examples, supercritical gasification and a bio-technological route, illustrate this new possibility. Production of H2/NG blends through steam reforming of NG (as well as through plasma decomposition of methane) is included in the study. The interesting option of producing H2/NG blends by internal reforming in a fuel cell, whereby effective heat integration is applied and at the same time electricity is produced, is worked out in more detail. Keywords: Hydrogen, Natural Gas, Biomass, Hydrogen Production NOMENCLATURE DCFC Direct carbon fuel cell HHV Higher heating value HP High pressure i Current density (mA/cm2) IR Internal reforming kg/h Kilogram per hour kWel Kilowatt (electricity) MCFC Molten carbon fuel cell MPa Mega-pascal NG Natural gas Nm3/h Normal cubic metres per hour NOX Nitrous oxides r Specific quasi ohmic resistance (W.cm2) a slope of the linearized Nernst potential as a function of utilisation (V)

SMR SOFC uf Veq(0)

Steam methane reforming Solid oxide fuel cell Fuel utilisation Open cell voltage (V)

INTRODUCTION In the Netherlands a large national project has started to study the feasibility of mixing hydrogen (H2) into the natural gas (NG) network with the initial goal of reducing diffuse CO2 emissions by the end users. From preliminary analysis of the problem a few conclusions can be drawn about the direction in which solutions may be found. The amount of NG consumed in the Netherlands is about 40 x 109 Nm3/year. Because of the lower heating value of hydrogen compared with NG, 3 mol% of H2 is equivalent to only 1% in energy

Corresponding author: Phone +31 (0)15 278 1650 Fax + 31 (0)15 278 3422 E-mail: kash@tbm.tudelft.nl

terms and a 10% substitution in energy requires the addition of approximately 25 mol% of H2. Further, even the modest goal of mixing only 3 mol% of H2 requires an increase in current H2 production of 1.2 109 Nm3 annually. To generate such large quantities of H2 the only industrial scale process available is steam reforming of NG. However, producing H2 from NG for the express purpose reintroducing it to the NG network is, on the surface, an illogical concept for two reasons: 1. A relatively expensive, high-grade gas (H2) would be mixed with a less costly, lower-grade gas (NG) creating a mixture for which more than 90% of the end use would involve just combustion of the gas. 2. The efficiency of the steam reforming process is 70-90%. So energy would be lost in the conversion process and significantly more NG would be needed to provide the same amount of energy to the end users. If the only driver for this change in the energy system were the possibility of capturing CO2 at the H2 production site for sequestration, then the arguments for adopting this approach would seem rather weak. However, there are compelling reasons why the transition to a H2/NG blend would be worthwhile. A 25% by volume addition of hydrogen would reduce the diffuse carbon dioxide (CO2) emissions by approximately 7 to 8 million tons annually, which would realise the full Kyoto goal of the Netherlands set in 1990, the reference year of the Kyoto agreement. Moreover, a system of CO2 emissions trading could provide financial incentives for the change. Although such a system does not yet exist and market prices for a megaton of CO2 have not yet been established, some estimates indicate a price of 25 Euro per ton of CO2. Hence, an annual reduction of 8 megatons of CO2 would be equivalent to a cash flow of 200 million Euro yearly. Furthermore, benefits such as lower nitrous oxide (NOx) emissions in combustion processes and the availability of a fine distribution network coupled with storage possibilities for H2 make the transition to a H2/NG blend even more desirable. In this paper we focus on methods to circumvent the two problems outlined previously, with a view to maximising the overall attractiveness of this approach. A solution may be found in the fact that production of pure H2 is unnecessary. The idea is that by relaxing the constraints on the quality/purity of the H2 to be produced, the

production process can be redefined and optimized. Instead more cost-effective technologies dedicated to the production of H2/NG or H2/methane mixtures may be explored. In specific cases for the H2/NG blends, the final separation step may be completely eliminated since the product is already in a suitable form for introduction to the NG network. We will explore the opportunity for synergy in this direction by focusing on both conventional and more innovative examples firstly using NG as a feedstock and secondly using bio-mass as the feedstock. It is emphasized that there is still a large gap in the order of magnitude between the production capacity of the innovative production technologies explored here and the capacity needed to convert the whole NG network to a H2/NG network. The idea is to explore possible benefits on the production side given that the H2/NG network is realized. PRODUCTION OF H2/NG MIXTURES FROM NG 1. Production of H2/NG using incomplete steam reforming The steam reforming of NG (Steam Methane Reforming or SMR) is a well-known process that can be applied on a large industrial scale. The steps in this process are (i) desulphurization of the feedstock, (ii) reaction of the methane with steam to produce syngas (a hydrogen, carbon monoxide and carbon dioxide mixture), (iii) water shift reaction and (iv) purification. The natural gas contains small quantities of sulphur compounds, which are detrimental to the cobalt-molybdenum catalysts used in the reforming process. These substances must first be removed. The reactions take place at temperatures of 800 1000 C and pressures of 15-30 bar. A by-product of the SMR process is heat in the form of steam. The conversion ratio for large-scale plants is normally 80% of the higher heating value (HHV) of the natural gas. The energy efficiency for these plants is approximately 90%. For producing a H2/NG blend, an alternative process may be adopted: a standard SMR production process with a less efficient conversion ratio. However, there are some issues that must be addressed before this alternative can be adopted. Firstly, the conventional SMR process temperatures are quite high. Heating up the feedstock requires a large amount of energy and, in the case of the alternative process, the whole

feedstock is heated, while only a part of the energy is used in the reaction. However, a smaller conversion ratio allows for a lower reaction temperature. The consequence is that there could be an option that would allow for less energyintensive, lower-cost production of a H2/NG blend which has the potential to be effectively introduced to the natural gas network. Research is already well underway in this area. F.E. Lynch et al. has patented a process for the direct conversion of methane to gaseous mixtures of H2 and methane, called Hythane. They claim to have achieved an effective combustion rate similar to that of gasoline, thereby creating a potentially promising substitute for conventional fuels in spark ignition internal combustion engines as well as in compression ignition engines [1]. The pollution emissions from Hythane powered vehicles has been shown to be well below that of gasoline engines, due to the clean-burning characteristics of the components of Hythane. Secondly, the desulphurization step remains necessary when cobalt-molybdenum catalysts are used. In light of the scale of the process, the cost of the desulphurization step would be significant. On the other hand there is potential for the use of cheaper, more sulphur-tolerant catalysts, which are now allowed to have lower catalytic activity. Thirdly, the physical flows in the SMR process are quite large. This property will manifest itself during the incomplete SMR process as a different heat balance. Enormous piping and vessels are needed to cope with the large physical flows in the alternative process. The direct production of H2/NG blends with significant NG concentration seems unlikely to be feasible due to the unnecessary heating and cooling of large amounts of NG in the process. However, a tentative conclusion from this first analysis is that the relaxed constraints on the H2 production allows for the use of cheaper catalysts and/or lower operating temperature since full conversion is no longer necessary. Also, catalysts with high sulphur tolerance but lower activity for the reforming reaction can be used thereby reducing the constraints on the sulphur removal equipment.

2. Production of H2/NG mixtures using plasma or thermal decomposition of NG At high temperatures either with or without the assistance of a plasma methane is decomposed into carbon and hydrogen: CH4 C + 2 H2 (1)

Since the beginning of the eighties, the Norwegian firm KVAERNER ENGINEERING S.A. has been developing a plasma-arc process that, at temperatures of 1600C, separates hydrocarbons into pure carbon and hydrogen [2]. This process is said to produce no significant emissions in itself. The process requires a primary energy source (in the form of natural gas or oil), cooling water and electricity. Because of the high temperature of the process, the same conclusion holds for SMR, that is, that production of blends with significant NG concentrations is unlikely to be feasible, because of the heating and cooling of unconverted NG. However, a slip of unconverted NG is now tolerated. The decomposition is an interesting alternative for SMR since it does circumvent the need for CO2 separation. Moreover, Cooper et al. [3] have experimentally shown that direct conversion of carbon black in a direct carbon fuel cell (DCFC) producing pure CO2 is possible. An efficiency of 67% (HHV) was found for the complete conversion route from NG to electricity via decomposition and conversion in a solid oxide fuel cell (SOFC) or a molten carbon fuel cell (MCFC) for H2 and a DCFC for carbon. The hydrogen can of course also be used for mixing into the NG network. 3. Production of H2/NG mixtures using an internal reforming fuel cell. High temperature fuel cells suffer from a large thermodynamically determined (reversible) heat production due to entropy changes (TDS) and the so-called Nernst loss. This heat can be used for reforming of NG. Two concepts are developed for fuel cells: internal and external reforming. In internal reforming (IR) the H2 for the fuel cell anode reaction is produced from NG inside the fuel cell stack. The reforming reaction consumes a significant amount of the reversible and irreversible heat produced in the cell. Yet still the cell needs to be cooled. Often the remaining heat is

transferred to a bottoming (steam) cycle for conversion into power. Although, in principal, high system efficiencies can be obtained in such a combination, it requires two conversion steps; each step is associated with large investment costs. Here we will explore the option to use an IR fuelcell to produce a surplus of H2 above the amount for its own consumption thus using the surplus of heat effectively and circumventing the need for a costly bottoming cycle. A beneficial side effect is the increase in electric efficiency of the fuel cell due to the lower utilisation of the fuel gas and thus a lower Nernst loss. Vollmar et al. note the flexibility of such a system for producing hydrogen and electricity in various ratios. Operating conditions can be rapidly adjusted to meet changing demands and hence a better economic optimisation can be achieved [4]. In a first order but very good approximation the cell voltage can be calculated as [5]:

Vcell = Veq (0) - i.r -

1 a .u f 2


The Nernst loss is given by the third term on the right hand side. For high temperature fuel cells in which internal reforming is possible the Nernst loss is significant. Since a is of the order of 200 mV Nernst loss approaches 100 mV for near full utilisation i.e. of the same order as all irreversible losses (ir) together. So by using the fuel cell as a reformer producing hydrogen (or H2/NG blends) the utilisation is reduced. Hence, proportional to the utilisation the Nernst loss is reduced and efficiency of the fuel cell increased. This concept is worked out in more detail, yet still on a conceptual design level using the flowsheeting program Cycle Tempo. The program deals with the proper mass and energy balancing and calculates chemical equilibrium in the gas compositions. For simplicity the fuel cell is modelled as a SOFC (solid oxide fuel cell) allowed to operate in the temperature range 600 to 1000oC. The calculation focuses on the fuel cell only and the surroundings are modelled using sources and sinks where the sources provide gas streams of the appropriate temperature chosen as 600, 800 and 1000oC respectively). The oxidant utilisation is fixed at 50% and the fuel utilisation is adjusted so that the temperature of the output gases equals the operating temperature. In Figure 1 the schematic of the fuel cell with sources and sinks is shown.

Sufficient steam is added to the NG to prevent carbon deposition in the fuel cell. Carbon deposition inside the fuel cell is of course disastrous for a proper functioning of the anode. However, the process of carbon deposition itself is highly desired in the context of our study where we are looking at decreasing the carbon content of the NG. If it were possible to deposit the carbon in a controlled manner in a separate unit this concept would be very interesting to explore further. In Figure 2 and Figure 3 the gas compositions as calculated are indicated for three operating temperatures at a pressure of 1 and 30 Bar respectively. Also the calculated cell voltage and the adjusted fuel utilisation are shown. The off-gas typically contains 50% of steam but in the figures the dry gas compositions are indicated. Under most conditions an almost full conversion of methane to hydrogen occurred. Only at higher pressure and the lowest operating temperature a mixture containing a significant amount of methane results. At the other operating conditions also some methane is not converted which in our case is not a problem. In the calculations equilibrium is assumed so in practice methane concentrations may be higher. As for conventional reforming a further CO shift to H2 is necessary as well as separation of CO2 for sequestration or for use as feedstock in a chemical process. PRODUCTION OF H2/NG MIXTURES FROM BIOMASS 1. Production of Hydrogen/NG mixtures using a bio-reactor The microbial production of bio-gas (a mixture of CH4 and CO2) is a well-known phenomenon. Presently, it can be implemented at any scale and in any place as an anaerobic treatment for wastewater purification to couple energy production and wastewater treatment [6]. This technology is based on the conversion of organic matter in organic acids and H2, followed by the conversion into CH4 and CO2 by a large consortium of bacteria operating synergistically at ambient temperatures and pressure. The main endproducts are CH4 and CO2 since the produced H2 is immediately consumed to enable further conversion of the feedstock [7]. Because of the increasing interest in hydrogen as a non-carbonaceous energy carrier, a bio-process has been designed in which H2 and CH4 production have been uncoupled. This process entails two

fermentative steps optimised for the production of H2 and CH4 respectively. The first step (Equation 2) is the conversion of carbohydrates in bio-mass to acetic acid, H2 and CO2 by hyperthermophilic bacteria at relatively high temperatures (70-90C) and neutral to low pH, preventing growth of methanogenic bacteria and yielding a high H2 per mole of carbohydrate. The second step (Equation 3) is the conversion of acetic acid to CH4 and CO2 by methanogenic bacteria at ambient temperatures. C6H12O6 + 4 H2O 2 CH3COO- + 4 H2 + 2 HCO3- + 4 H+ G0 (kJ/mole) = -206 (2) CH3COO- + H2O CH4 + HCO3G0 (kJ/mole) = -31 (3) The standard Gibbs Free Energy shows that the reactions provide enough energy to allow microbial growth. When these reactions occur freely, the offgas composition of the hyperthermophilic fermentation would grow to 67 mol% H2 and 33 mol% CO2, whereas the off-gas of the methanogenic fermentation would yield 50 mol% CH4 and 50 mol% CO2. However, H2 producing hyperthermophilic bacteria, studied until now, showed severe feed-back inhibition at a partial H2 pressure of 20 kP [8]. This means that H2 has to be actively removed from the reactor, possibly by stripping the fermentation broth using a gas. In line with the general aim discussed here, the off-gas of the methanogenic fermentor is a promising candidate. Because of stoichiometric considerations, this would yield a final composition of 40 mol% H2, 20 mol% CH4 and 40 mol% CO2, which is not sufficient to overcome the constraints of the hyperthermophilic H2 production. Other gaseous additions to dilute the H2 concentration for the hyperthermophilic conversion will still be necessary. NG from the network can be used for this purpose. Until now, the production process described above has not yet been demonstrated. However, proof of the principle (conversion of the carbohydrate fraction in hydrolysate of domestic organic waste to H2, CO2 and acetic acid in a hyperthermophilic reactor, followed by the conversion of the acetic acid in the effluent to CH4 and CO2) has been established.

Moreover, the theoretically maximum amounts of products in the separate fermentation processes have been achieved. The future aim is to study process integration to supply the most desired gas composition, within the constraints of the microbial fermentation process. Furthermore, as microbial fermentation is only suited for converting carbohydrates in bio-mass, there is a need to design a process for the utilisation of approximately 25% of the bio-mass (depending on the composition) which remains inaccessible for anaerobic microbial conversion. Combustion of this fraction to provide the energy for the fermentation processes seems to be one of the more obvious applications. 2. Production of Hydrogen/NG mixtures using super critical gasification Wet biomass and organic residues can be treated in supercritical water (T>374C, P> 22MPa) to produce a clean fuel gas rich in hydrogen and methane. A simplified process flow diagram is depicted in Figure 2. The first step in the process is to prepare a pumpable slurry from bio-mass and pressurise it to 300 bar. The pressurised feedstock is heated by the reactor outlet stream in a heat exchanger. This is essential for the process to achieve high thermal efficiencies. The reactor operating temperature is typically between 600 and 650 C; the operating pressure is around 300 bar. Depending on the type of feedstock [9], a residence time of to 2 minutes is required to achieve complete carbon conversion. The two-phase product stream is released from the reactor, and separated in a high-pressure (HP) gasliquid separator (T = 25 - 300 C). Because of these conditions, a significant part of the CO2 remains in the water phase. From a theoretical point of view, possible contaminants like H2S, NH3 and HCl are even more likely to be captured in the water phase due to their higher solubility. In fact in-situ gas scrubbing is part of the process. It is therefore expected that the gas stream from the HP separator contains mainly the H2, CO and CH4 and part of the CO2. Depending on the application, the fuel gas can be further conditioned in downstream equipment or in

the process itself. By adding an appropriate shift catalyst (for example NaOH or KOH) nearly all CO is shifted towards H2 [10,11]1. The high process pressure favours the formation of methane. High methane concentrations (30-40%) were achieved by Vogel et al. [12] by using nickel catalysts. Overall thermal efficiencies2 above 70% can be achieved. So in this process methane/hydrogen blends are produced that are suited for mixing into the NG network without the need for hydrogen and or methane separation thus simplifying overall system requirements and thus cost. CONCLUSIONS The concept of using H2/NG blends instead of NG in the national NG network is an interesting option in the pathway to a sustainable hydrogen society. It offers a whole new perspective on the hydrogen society and the hydrogen production technologies needed. Since the constraints are relaxed, the production processes can be operated in more efficient and cost effective ways offering positive incentives for market introduction of those technologies. REFERENCES [1] Lynch FE, Egan GJ. U.S. Pat. No. 5,139,002 In: Proceedings of the 4th Canadian Hydrogen Workshop, Nov. 1-2, 1989. [2] Zittel W, Wurster R. Ludwig-BlkowSystemtechnik GmbH, Hydrogen in the Energy Sector 1996 (8.7)

[5] Au SF, Woudstra N, Hemmes K and Uchida

Verification of a Simple Numerical Fuel Cell Model in a Flow Sheeting Program by Performance Testing of a 110 cm2 Molten Carbonate Fuel Cell. Energy Conversion and Management in print (2002) [6] Lettinga G. Sustainable integrated biological wastewater treatment. Water Science & Technology 1996; 33:85-98. [7] Claassen PAM, van Lier JB, Lopez Contreras AM, van Niel EWJ, Sijtsma L, Stams AJM, de Vries SS, Weusthuis RA. Utilisation of biomass for the supply of energy carriers. Applied Microbiology & Biotechnology 1999; 52:741-55. [8] Van Niel EWJ, Claassen PAM, Stams AJM Substrate and Product Inhibition of Hydrogen Production by the Extreme Thermophile, Caldicellulosiruptor saccharolyticus. Biotechnology & Bioengineering 2003; 81:255-262. [9] Antal MJ, Allen S, Lichtwa J, Schulman D, Xu X, Hydrogen production from high moisture content biomass in supercritical water. Proceedings of the 1999 U.S. DOE Hydrogen Program Review, NREL/CP-570-26938. [10] Boukis N, Abeln J, Kruse A, Schmieder H, Dinjus E, Biomass treatment in supercritical water. The way from total oxidation to the gasification, p. 109-121. [11] Watanabe M, Inomata H, Arai K, Catalytic hydrogen generation from biomass (glucose and cellulose) with ZrO2 in supercritical water. Biomass & Bioenergy 2002; 22: 405-410 [12] Vogel F, Hildebrand F, Catalytic hydrothermal gasification of woody biomass at high feed concentrations. Chemical Engineering Transactions 2002; (2): 771-777.

[3] Cooper, JF, Cherepy N, Upadhye, R., Pasternak A, & Steinberg M. Direct Carbon Conversion: Review of Production and Electrochemical Conversion of Reactive Carbons, Economics and Potential Impact on the Carbon Cycle. UCRL-ID-141818. 12-12-2000. CA, USA, Lawrence Livermore National Laboratory [4] Vollmar,H.E., Maier,C.U., Nolscher,C., Merklein,T. & Poppinger,M. Innovative concepts for the coproduction of electricity and syngas with solid oxide fuel cells. Journal of Power Sources 2000; 86: 90-97

CO is often not allowed in Substitute Natural Gas Energy content of fuel gas divided by the energy content of the feedstock

123 1.013 Pel,AC = 1315.51 kW 2 A fc = 1200.00 m 1.14 kW/m f= 2 Rfc = 0.0001 W m


1000.84 0.329

104 123 103

1.013 980.49

1000.84 1.148



h Fm p = Pressure [bar] T = Temperature [C] h = Enthalpy [kJ/kg] Fm = Mass flow [kg/s] Pel,AC = AC Power [kW] A fc = Cell area [m ]

103 A C 1.038 983.16 102 122 122 102 121 101 1.038 121 101 983.16 Air 1000.00 1.297 1000.00 1.297

V fc = 0.7613 V 2 ifc = 1500.00 A/m uF = uO = 52.00 % 50.00 %

1.033 -5670.90 1.033 -11329.38 111

999.97 0.180 1000.00 0.085 111

Rfc = Cell resistance [W m ] V fc = Cell voltage[V] uF = Fuel utilisation[%] uO = Oxidant utilisation[%] f = Power density [kW/m ]

ifc = Current density [A/m ]


1.033 -578.27

1000.00 0.095

Natural gas

Figure 1 Solid Oxide Fuel Cell Used in the Co-production of H2/NG Blends and Electricity from NG.

1.0000 0.9000 0.8000 0.7000 0.6000 0.5000 0.4000 0.3000 0.2000 0.1000 0.0000 CH4 H2 CO2 CO Vcell uf 600 800 1000

Figure 2 Fuel Cell Anode Output Dry-Gas Compositions at Atmospheric Pressure for Three Operating Temperatures (600, 800 And 1000 C). Cell voltage (in volts) and fuel utilization, Uf, are also indicated.

1.0000 0.9000 0.8000 0.7000 0.6000 0.5000 0.4000 0.3000 0.2000 0.1000 0.0000 CH4 H2 CO2 CO Vcell uf 600 800 1000

Figure 3 Fuel Cell Anode Output Dry-Gas Compositions at P= 30 Bar for Three Operating Temperatures (600, 800 And 1000 C). Cell voltage (in volts) and fuel utilization, Uf, are also indicated.

Product upgrading H2O and CO2 removal SNG

Heat Exchanger

CO2-rich fuel gas

Feed Pump Feedstock preparation and pressurizing Supercritical water gasification process Water

Figure 4 Simplified Process Flow Diagram of the Treatment of Wet Bio-mass and Organic Residues in

Supercritical Water to Produce a Clean, Hydrogen- and Methane-Rich Fuel-Gas.