international journal of hydrogen energy 33 (2008) 50985105

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Design and process study of Pd membrane reactors

Silvano Tostia,*, Angelo Basileb,1, Livio Bettinalia, Fabio Borgognonia, Fausto Galluccib,1, Claudio Rizzelloc,2
a

ENEA, Dipartimento Fusione Tecnologie e Presidio Nucleare, C.R. ENEA Frascati, Via E. Fermi 45, Frascati, Roma I-00044, Italy Institute on Membrane Technology, ITM-CNR, c/o University of Calabria, Via P. Bucci, Cubo 17/C, I-87030 Rende (CS), Italy c Tesi Sas, Via Bolzano 28, Roma, Italy
b

article info
Article history: Received 13 December 2007 Received in revised form 7 May 2008 Accepted 7 May 2008 Available online 7 September 2008 Keywords: Pd membranes Membrane reactors Hydrogen

abstract
Palladiumsilver thin wall tubes are produced by an innovative procedure based on the diffusion welding: these permeators are proposed for separating and producing high-pure hydrogen in both separators and membrane reactors. The reliability of these dense metallic permeators is strongly related to the design conguration of the membrane modules. In fact, as a consequence of hydrogenation and thermal cycles, the dense metallic tubes vary signicantly in their length: in case of constraints between the membrane and the module, cyclic axial stresses are applied to the thin wall tube involving the rupture of the permeator. In our applications, a nger-like assembly of the permeator tube has been designed: it permits the free elongation and contraction of the palladium alloy tube avoiding any mechanical stress. In this work, different congurations of palladium membrane reactors used for separating ultra pure hydrogen are described and a study of a membrane process for producing ultra pure hydrogen from ethanol reforming is also presented. 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

Palladium and its alloys have been studied for producing hydrogen: in fact, the selective mass transfer of hydrogen through metals permits its separation from gas mixtures. The rst commercial applications of PdAg permeators for producing very pure hydrogen have been studied since 60 [1,2]. Important applications of the PdAg membranes have been proposed in the fuel cycle of the fusion reactors where the purication and the separation of the hydrogen isotopes from gas mixtures [36] are required. In particular, in these applications the complete hydrogen selectivity of the membranes is required beside a good durability.

Other important applications concern the use of Pd-based permeators into membrane reactors for producing hydrogen from reforming of hydrocarbons and alcohols: in these catalytic reactors, the presence of a membrane selective to the hydrogen permits attaining very high conversion values in comparison with the traditional reactors operating under the same conditions. In fact, the continuous removal of one of the reaction product, the hydrogen, promotes the reaction conversion beyond the equilibrium values (shift effect) [79]. Several works, both theoretical and experimental, have demonstrated the effectiveness of the palladium and palladium alloy membranes: especially, the use of palladium based membranes with an innite hydrogen selectivity present the

* Corresponding author. Tel.: 39 06 94005160; fax: 39 06 94005314. E-mail address: tosti@frascati.enea.it (S. Tosti). 1 Tel.: 39 0984 492013; fax: 39 0984 402103. 2 Tel./fax: 39 0697273277. 0360-3199/$ see front matter 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2008.05.031

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advantages of maximizing the shift effect and of producing ultra pure hydrogen without the need of any other purication system [1015]. However, at now the major concerns related to the large employ of the Pd-based membrane reactors are their cost and durability when an innite selectivity is required. In fact, an important cost reduction has been obtained by producing composite membranes in which thin palladium layers are deposited over ceramic porous supports: nevertheless, their permselectivity requires a thickness of the metal layers which are incompatible with a long lifetime of the composite membranes [16]. In order to obtain a signicant cost reduction of Pd permeators with complete hydrogen selectivity, a new technique consisting of cold-rolling and diffusion welding PdAg sheets has been developed at ENEA Frascati laboratories [17,18]. These dense metal membranes have been produced in the form of permeator tubes of 5060 mm wall thickness: the amount of the precious metal employed, and then the cost, is reduced with respect to the commercial PdAg permeator tubes of thickness 100150 mm. These dense membrane result defect-free ensuring the production of ultra pure hydrogen: but, as a consequence of the thermal and hydrogenation cycles these thin wall tubes modify signicantly their length and only an appropriate mechanical design of the membrane module can avoid any damage of the thin wall tubes. Longterm tests have demonstrated the long lifetime of the thin wall PdAg tubes when nger-like membrane modules are used [19,20]. Composite Pd-based membranes have been also produced by welding thin PdAg foils with stainless steel and nickel supports in form of grids or perforated foils [21]. A rst membrane reactor using a thin wall PdAg tube of length 500 mm has been produced for purifying gaseous mixtures from tritium (the mass 3 hydrogen isotope) in an application of the fusion reactor fuel cycle [22]. In this reactor the PdAg permeator has been xed at both its ends to a stainless steel module: a special mechanical design using two pre-tensioned metal bellows maintains the permeator tube always under tension avoiding any compression and buckling of the thin wall and long permeator tube obtaining a good durability. In this work, a nger-like assembly of the permeator tubes into the membrane modules is proposed for building PdAg membrane reformers producing ultra pure hydrogen. The devices studied are related to both laboratory and small scale applications of palladium separators and membrane reactors: especially, the study of a membrane process for producing hydrogen from ethanol reforming is also presented. Although PdAg thin wall tubes have demonstrated in long-term laboratory tests good performances in terms of high hydrogen permeation uxes and durability, a wide use of these membranes for producing ultra pure hydrogen in large scale applications needs an engineering approach aimed at both appropriately designing the membrane modules and optimizing the process where the Pd membrane reactors will be employed. This work describes the mechanical design and the process optimization of a Pd membrane reactor for the production of 6 L min1 of hydrogen from ethanol steam reforming. The dense PdAg tubes guarantee the production

of ultra pure hydrogen without requiring purication devices such as a preferential oxidation unit [23].

2.

Single tube modules and reactors

The hydrogen interacts with palladium and its alloys: the use of PdAg for building permeators tubes has to take into account the modications of the metal lattice under thermal and hydrogenation cycling. Several studies estimated both theoretically and experimentally the elongation/contraction of the hydrogenated PdAg when exposed to thermal cycles [24]: a PdAg alloy permeator tube has been operated from ambient temperature up to 400  C with hydrogen pressure of 100150 kPa with a resulting maximum elongation of about 1% [22]. Our PdAg thin wall permeator tubes are produced via cold-rolling and diffusion welding of metal foils for laboratory applications. Each PdAg membrane tube of wall thickness 5060 mm, diameter 10 mm and length 150 mm is joined by brazing at its ends to two stainless steel tubes which ensures a larger stiffness where the permeator will be connected to the membrane module. The characterization tests aimed at measuring the hydrogen permeability of the PdAg membranes have been carried out in the temperature range of 200400  C operating temperature and hydrogenation cycling [19]: especially, the nger-like conguration, in which the thin wall permeator is xed to the module at only one end, permits its free elongation/contraction and avoids any mechanical stress ensuring a long lifetime. In the nger-like conguration the permeator tubes are gas-tight connected to the module without rising excessive mechanical constraints. Accordingly to this mechanical design, inside the PdAg permeator a smaller stainless tube is inserted in order to collect the retentate stream. These permeator tubes can be used to perform dehydrogenation reactions in membrane reactors: in this case a catalyst bed is coupled to the permselective membrane and the continuous removal of the hydrogen permits obtaining higher yields with respect to the traditional reactors operating under the same conditions. On the basis of these experiences, a stainless steel module has been designed for laboratory applications [25].

2.1.

Membrane module

The nger-like stainless steel module has been designed for characterizing PdAg thin wall permeators in terms of hydrogen permeability: in these tests the hydrogen permeation ux is measured under controlled transmembrane differential pressure values while a thermocouple connected to an external heating system permits to control the temperature. As shown in the scheme of Fig. 1, the membrane tube is gas-tight connected to the module by means of a graphite gasket; in this way, the lumen and shell side are separated. The gaseous mixture is fed inside the PdAg permeator via the smaller stainless steel tube: the hydrogen permeates selectively the membrane and is collected in the shell side by a sweep gas stream, while the non-permeated gases (retentate stream) leaves the membrane without mixing the feed

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Fig. 1 Scheme of a nger-like membrane module.

stream. This module permits to evaluate different operating conditions. In fact, co-current or counter-current modes can be operated by easily changing the feed and retentate ows as well as changing the inlet and outlet of the sweep gas streams.

2.2.

Membrane reactor

reactor module has to consider the appropriate conguration (catalyst inside or outside the membrane). Finally, also in the membrane reactor design, the feed and retentate streams as well as the inlet and outlet of the sweep gas can be changed in order to perform the tests under the appropriate operating conditions.

The stainless steel module can be used to test the performances of membrane reactors: appropriately, the catalyst bed may be inserted in the membrane lumen, or in the shell side. Especially, in Fig. 2 the case of a membrane reactor with the catalyst in the shell side is reported. Generally, in designing a membrane reactor an important parameter to be taken into consideration is the permeation surface to catalyst bed volume ratio: in fact, a dimensionless quantity, the product of Damkohler and Peclet numbers, is dened to describe the behavior of a membrane reactor [26]: Da$Pe maximum reaction rate per volume= maximum permeation rate per volume For high values of the product Da$Pe the effect of the membrane can be neglected and the reactor works as a traditional reactor; otherwise, the permeation kinetics results much higher than the reaction kinetics when the product Da$Pe is small. In practice, an optimization of the membrane reactor is attained for a certain range of the product Da$Pe [26,27]. Accordingly, in order to meet the conditions of higher reaction conversion and hydrogen yield, the design of the

3. Ethanol steam reforming into membrane reactors

Several fuels are considered as hydrogen sources for proton exchange membrane fuel cells via reforming [28], among these methanol, natural gas, gasoline, etc. Especially, the production of hydrogen from ethanol reforming results an interesting process. In fact, the ethanol has a relatively high hydrogen content and can be produced from renewable sources such as biomass [29] and its storage is easy and safe. Furthermore, the water removal from the biomass-derived ethanol represents a signicant part of the overall cost of its production: so, when the ethanol is used in a reformer where the feed stream is a water/ethanol mixture, the cost of the hydrogen produced should be reduced with respect to the case in which other hydrocarbons or alcohols are used [30]. A number of works have concerned the catalysts study for the hydrogen production from ethanol steam reforming: especially, the Rh and Ni catalysts have shown the best performances [31,32]. Also a double bed reactor has been considered

Fig. 2 Scheme of a nger-like membrane reactor: catalyst in the shell side.

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for the carrying out in the same device both the ethanol reforming and the water gas shift reaction [33]. The reaction to be considered for the ethanol steam reforming is: C2 H5 OH H2 O 5 2CO 4H2 DH298 K 240 kJ mol1 (1)

The hydrogen production is maximized by the water gas shift reaction where the CO is converted into CO2 and hydrogen: CO H2 O 5 CO2 H2 DH298 K 41 kJ mol1 (2)

And the complete reaction is: C2 H5 OH 3H2 O 5 2CO2 6H2 DH298 K 158 kJ mol1 (3)

3.1.

Multi-tube modules and reactors

The nger-like conguration has been also taken on in order to design hydrogen separators and membrane reactors consisting of a bundle of PdAg tubes [34]. These devices are capable for producing higher hydrogen throughputs than single tube membrane modules and can be used in small scale pilot plants. Especially, Figs. 3 and 4 show schematically two multi-tube membrane reactors proposed for producing hydrogen from ethanol reforming for the case of catalyst in the lumen and shell side, respectively. A membrane reactor consisting of 19 PdAg thin wall tubes has been built at ENEA Frascati laboratories. The catalyst bed has been inserted inside the permeators (i.e., the reaction side is the membrane lumen): in fact, from the mechanical point of view, the thin wall tubes can withstand internal pressure higher than the external one. Figs 5 and 6 show a view and a particular of the multi-tube reactor, respectively. This membrane reactor has been

Fig. 4 Scheme of a multi-tube membrane reactor: catalyst in the shell side.

Fig. 3 Scheme of a multi-tube membrane reactor: catalyst in the lumen side.

Fig. 5 View of the multi-tube membrane reactor.

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Accordingly, an analysis of the Da Pe product [36] conrms this result: Da Pe kr V QP0:5 A

Fig. 6 Particular of the multi-tube membrane reactor: head ange to be connected to the 19 PdAg permeator tubes.

designed for performing the water gas shift reaction in a two steps process proposed for producing ultra pure hydrogen from ethanol reforming.

3.2.

Two steps process

A membrane process for producing ultra pure hydrogen that feeds a polymeric fuel cell of power 500 W has been studied [35]: it produces a stream of about 6 L min1 of hydrogen via ethanol reforming by using two reactors. A traditional reformer operating at high temperature where ethanol reacts with an excess of water is followed by a PdAg membrane reactor in which the water gas shift reaction takes place (Fig. 7). In this second device the carbon monoxide coming from the reformer reacts with the water and produces further hydrogen completing the ethanol conversion to hydrogen: at the same time all the hydrogen produced in both reactors is selectively separated by the membrane and collected in the shell side. A preliminary design assessment of the reforming process has been carried out for the case of one membrane reactor (performing the overall reaction of ethanol steam reforming and water gas shift) and the case of the two steps process: this analysis showed that the two steps process requires a reduced number of PdAg permeator tubes thus involving a reduced cost of the devices.

where kr is the reaction rate constant (mol m3 Pa1 s1), V is the catalyst volume (m3), Q is the PdAg tube permeance (mol m2 Pa0.5 s1), P the reactor pressure (Pa) and A the membrane surface area (m2). In fact, in our case V/A and Q are xed by the geometrical and design characteristics (tubular PdAg membranes and presence of the catalyst inside the tubes) and the Da Pe number depends on the reaction rate constant: this parameter is higher for the ethanol stem reforming reaction than the water gas shift one. The case of one membrane reactor (ethanol steam reforming and water gas shift) involves too high Da Pe numbers and the membrane reactor behaves like a traditional reactor. In other words, when one membrane reactor is used for both reactions, a larger membrane area is needed only to contain the catalyst (being the ratio V/A xed) and the membrane reactor is not optimized. The process has been designed on the basis of the literature data reported for an ethanol reformer using an Rh catalyst supported on alumina and operating at 650  C [37]. With a H2O/C2H5OH feed molar ratio of 8.4 and a space velocity (GHSV) of 5000 h1 are produced about 5.5 moles of hydrogen per each ethanol mole reacted: high selectivity of CO2 (75%) and CO (23%) is attained with small amounts of minor products like methane (<2%). The composition of the gaseous stream leaving the reformer and calculated from literature data is reported in Table 1. Therefore, in our proposed process the ethanol reformer is a traditional xed bed tubular reactor operating the reactions (1)(3) at 650  C and 200 kPa, while, in the membrane reactor the water gas shift reaction (2) takes place at 350  C and 200 kPa for converting all carbon monoxide into carbon dioxide and separating all the hydrogen produced both in the reformer and in the membrane reactor. This reactor consists of 19 PdAg tubes of diameter 10 mm, wall thickness 0.050 mm and length 300 mm: the hydrogen permeated is collected in the shell side by a nitrogen stream at 100 kPa in counter-current mode. This purge stream operates in a loop including the anode of the polymeric fuel cell where the hydrogen reacts and the sweep nitrogen gas is sent back to the membrane reactor shell. By referring to the process scheme shown in Fig. 8, the molar ow rates resulting from the mass balances are reported in Table 1. In this assessment, the ethanol has been assumed to react almost completely: in

Fig. 7 Scheme of the two steps process.

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Table 1 molar ow rate (mol hL1) of the two steps process (L [ Liquid; G [ Gas)
Stream State T, K P, kPa H 2O N2 O2 H2 CO CO2 C2H5OH 1 L 293.15 200.00 21.00 2 G 923.15 200.00 21.00 3 G 923.15 200.00 15.06 4 G 623.15 200.00 15.06 5 G 623.15 200.00 13.70 6 G 293.15 200.00 13.70 7 G 623.15 100.00 20.00 13.25 1.37 3.50 0.06 13.25 1.37 3.50 0.06 14.61 0.01 4.86 0.06 0.01 4.86 0.06 8 G 373.15 100.00 20.00 14.61 14.61 9 G 373.15 100.00 10 G 373.15 100.00 20.00 11 G 623.15 100.00 20.00 12 G 293.15 100.00 31.17 8.04 13 G 373.15 100.00 31.17 8.04 14 G 373.15 100.00 14.61 31.17 0.73

2.50

2.50

particular, 2.5% of non-reacted ethanol and the absence of secondary products (methane, acetaldehyde, etc.) are the main hypotheses. The membrane reactor has been designed in order to maximize the hydrogen recovered in the shell side. A computer code developed for simulating a water gas shift reactor has been used [38]. The model accounts for the kinetic of water gas shift reaction, the hydrogen diffusion through the PdAg membrane and for the partial pressure gradients of hydrogen generated at the permeate side of the membrane when a ow of purge gas is introduced. The model is based on the following main assumptions: steady state conditions, constant longitudinal temperature, negligible pressure losses, perfect gas behavior, negligible radial temperature and concentration proles (one dimensional model),  negligible effect of competitive reactions.      Pressure losses are not of concern as they are usually negligible in the range of ow rates usual for the application of the reactor. The tubular membrane reactor is divided into nite volume elements where composition of the gas, the rate of reaction and the permeation of hydrogen through the walls can be considered constant (perfect mixing). Assuming

as inlet boundary conditions for each stage the outlet values of the previous one, the mass balance for each component of the mixture is performed. The computation of axial mass balances both at the feed and at the strip side of the reactor requires the evaluation of the reaction rate and of the permeation rate. These, in turn, depend on the partial pressures of the gases in the reactor; e.g. on their concentrations. Moreover the permeation rate depends on the partial pressure of hydrogen at the strip side of the reactor. Therefore an iterative method of computation has been set up. From a preliminary prole of gas concentrations assumed along the bed the model evaluates the reaction rate and the permeation rate of hydrogen. These are introduced in the mass balance equations and a new prole of concentrations results. The calculation is iterated up to convergence. An appropriated convergence algorithm gives a quick solution. By using the code, the molar ow rates of the gaseous species inside a permeator tube of the membrane reactor have been evaluated (see Fig. 9). All the carbon monoxide reacts with water producing hydrogen: this gas permeates almost completely the membrane into the reactor shell where it is recovered by the sweep nitrogen gas. This process produces ultra pure hydrogen from ethanol reforming: the hydrogen will feed a polymeric fuel cell of power 500 W. The adopted mechanical design ensures the long lifetime while the thin wall of the permeators used

Fig. 8 Scheme of the system consisting of the membrane reformer and the polymeric fuel cell.

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2.50e-4 H2O

Acknowledgments
This work has been supported by the MIUR (Italian Ministry of Education, University and Research) in the framework of the research project no. RBAU01K4HJ.

Molar flow rates, mol/s

2.00e-4 H2 1.50e-4 1.00e-4 CO2 5.00e-5 CO 0.00 0 5 10 15 20 25 30

references

Permeator length, cm
Fig. 9 Calculated molar ow rate proles inside the PdAg tubes of the water gas shift membrane reactor.

maintains the cost of the reformer unit lower than the fuel cell one [39].

4.

Conclusions

Experimental long-term tests have demonstrated that PdAg permeator tubes produced via cold-rolling and diffusion welding are able to produce ultra pure hydrogen: their thin wall (thickness 5060 mm) has permitted to reduce their cost with respect to the commercial permeator tubes (thickness 100150 mm). The reliability of these thin wall tubes is strongly depending on the mechanical design of the membrane modules: in fact, under thermal and hydrogenation cycling the PdAg permeators modiy signicantly their length and excessive mechanical constraints between the module and the membrane tubes may produce compressive and buckling stresses with the failure and the loss of the selectivity. In practice, the mechanical design of the modules hosting PdAg thin wall tubes has both to ensure the gas-tight connection between the membrane and the module and to let free the membrane tube in its elongation/contraction. The nger-like conguration has been successfully adopted for designing both single tube and multi-tube membrane reactor for laboratory and small scale applications. In particular, a membrane reactor module consisting of a bundle of 19 PdAg permeators has been built for producing ultra pure hydrogen form ethanol reforming. The studied process uses a traditional reformer coupled with a membrane reactor where the water gas shift reaction takes place: in this optimized process, a reduced number of PdAg permeators is employed and the almost complete recovery of the hydrogen is obtained without requiring any other purication system. This work describes an engineering study that applies Pd Ag thin wall tubes to membrane reactors producing ultra pure hydrogen: especially, an appropriate mechanical design as well as a process optimization have been performed in order to ensure the better performances in terms of hydrogen yield, durability and reduced costs.

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