CoMETHy - Compact M Energy T drogen converter · CoMETHy: Compact Multifuel Energy To Hydrogen...

ENEA PI Acktar Technion IKTS UNISA CERTH AUTH UNIRM1 ECN GKN UniCampus

June 2016 FP7 – FCH JU – CoMETHy

Project Summary Report (D1.6)

GRANT AGREEMENT N° 279075

CoMETHy - Compact Multifuel-Energy To Hydrogen converter

Project period: 1st December 2011 – 31

st December 2015

Instrument: Collaborative Project

Thematic priority: Seventh Framework Programme, FCH JU

Application Area: Hydrogen production and distribution

Topic: Development of fuel processing catalyst, modules and systems

D1.6: Project Summary Report

Authors: Alberto GIACONIA (ENEA), Giulia MONTELEONE (ENEA), Luca TURCHETTI

(ENEA), Barbara MORICO (PI), Keren SHABTAI (Acktar), Moshe SHEINTUCH

(Technion), Daniela BOETTGE (IKTS), Vincenzo PALMA (UNISA), Spyros

VOUTETAKIS (CERTH), Angeliki LEMONIDOU (AUTH), Maria Cristina

ANNESINI (UNIRM1), Frans van BERKEL (ECN), Harald BALZER (GKN)

Document type Project Deliverable

Diffusion date 49th

Month

WP WP1

Revision Final

Verification CoMETHy Consortium

Organization name or lead contractor for this report: Alberto GIACONIA, ENEA

Due date of deliverable: Project Month 49

Actual submission date: June 2016

Project co-funded by the European Commission within the Seventh Framework Programme (2007-2013)

Dissemination Level

PU Public X

PP Restricted to other programme participants (including the Commission Services)

RE Restricted to a group specified by the consortium (including the Commission Services)

CO Confidential, only for members of the consortium (including the Commission Services)

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TABLE OF CONTENTS

1. Introduction ................................................................................................................................. 4

2. Executive Summary .................................................................................................................... 4

3. Project context and the main objectives ..................................................................................... 6

4. S/T results and foreground ........................................................................................................ 10

5. Impact, dissemination activities and exploitation of results ..................................................... 26

5.1 Impact of CoMETHy results ..................................................................................................... 26

5.2 Exploitation of CoMETHy results ............................................................................................ 29

5.3 Dissemination activities ............................................................................................................ 34

ANNEX 1: List of CoMETHy publications ....................................................................................... 36

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Acronyms and definitions

AIP: Annual Implementation Plan (by FCH JU)

APSS: Asymmetrical Porous Stainless Steel (membrane supports)

AUTH: Aristotle University of Thessaloniki, CoMETHy partner No. 8

CAPEX: CAPital EXpenditure

CERTH: Centre for Research & Technology Hellas, CoMETHy partner No. 7

CoMETHy: Compact Multifuel Energy To Hydrogen Converter, FCH JU Project

CSP: Concentrating Solar Power

CST: Concentrating Solar Thermal

DoW: Description of Work (Annex I of Grant Agreement n. 279075)

ECN: Energy Research Centre of the Netherlands, CoMETHy partner No. 10

ENEA: CoMETHy partner No. 1

FCH JU: Fuel Cells and Hydrogen Joint Undertaking

GHSV: Gas Hourly Space Velocity

GKN: GKN Sinter Metals Engineering GmbH, CoMETHy partner No. 11

IKTS: Fraunhofer Institute for Ceramic Technologies and Systems, CoMETHy partner No. 5

IMR: Integrated Membrane Reactor (Reformer)

IP: Intellectual Property

LHV: Lower Heat Value

LPG: Liquefiable Petroleum Gas

MAIP: Multi Annual Implementation Plan (by FCH JU)

MS: Molten Salt

MSMR: Multi-Stage Membrane Reactor (Reformer)

NG: Natural Gas

OPEX: OPerating EXpenditure

PI: Processi Innovativi Srl, CoMETHy partner No. 2

PV: Photovoltaic

PVD: Physical Vapour Deposition

RES: Renewable Energy Source

RTD: Research and Technological Development

S/C: Steam-to-Carbon (steam-to-methane molar ratio)

SSiC: Sintered Silicon Carbide

Technion: Israel Institute of Technology, CoMETHy partner No. 4

TES: Thermal Energy Storage

TRL: Technology Readiness Level

UNIRM1: University La Sapienza of Rome, CoMETHy partner No. 9

UNISA: Università degli Studi di Salerno, CoMETHy partner No. 6

WGS: Water-Gas-Shift reaction

WP: Work Package

7FP: EU 7th Framework Programme

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1. Introduction

This report summarizes the objectives and results obtained in the framework of the project

CoMETHy, started in December 2011 and was concluded in December 2015.

The content of this report is open to public access. Therefore, it can be distributed by CoMETHy

partners and the FCH JU Offices without any grant of publication rights.

According to CoMETHy Work Plan (DoW in Annex 1 of Grant Agreement) this is a project

Deliverable (D1.6) to be submitted at the end of the project (Month 49). Its content is also

provided with the “Final Publishable Summary Report” in the Final Report (Section 4.1)

submitted at the end of the project.

2. Executive Summary

An innovative technology for hydrogen production has been developed in the project CoMETHy

(Compact Multi-fuel Energy To Hydrogen converter), co-financed by the European Fuel Cells

and Hydrogen Joint Undertaking (FCH JU) and coordinated by ENEA.

The Project, started in December 2011 and concluded in December 2015, has seen 12

organisations between Industries, Research Centres and Universities cooperating in an excellent

collaborative environment: ENEA (Italy), Processi Innovativi Srl (Italy), Acktar Ltd. (Israel),

Technion (Israel), Fraunhofer Institute (Germany), University of Salerno (Italy), CERTH

(Greece), Aristotle University of Thessaloniki (Greece), University “La Sapienza” (Italy), ECN

(the Netherlands), GKN Sinter Metals Engineering GmbH (Germany) and University “Campus

Bio Medico” (Italy).

The technology developed in CoMETHy allows to combine different types of energy sources,

like solar, biomass and fossil fuels, to produce pure hydrogen for various applications, permitting

to adapt hydrogen production to the locally available energy mix.

The system has been based on the steam reforming process, a widespread hydrogen production

method, which has been revised to exploit renewable energy: the main aim has been to power the

process with an energy vector that today is widely used to capture, store and dispatch solar heat

in Concentrating Solar plants, i.e. a mixture of molten salts. This fluid, often called “solar salt”,

has several outstanding positive features including low cost, high heat transfer/storage capacity

and minor implications about environmental and safety issues and toxicity.

The steam reforming process has been specifically tailored and re-designed to be combined with

Concentrating Solar plants using “solar salts”: a “low-temperature” steam reforming reactor was

developed, operating at temperatures up to 550°C, much lower than the traditional process

(usually > 850°C). This result was obtained after extensive research, going from the

development of basic components (catalysts and membranes) to their integration in an innovative

membrane reformer heated with molten salts, where both hydrogen production and purification

occurred in a single stage.

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Besides the high degree of compactness, the device developed is also highly flexible as far as

the feedstock to be converted to hydrogen is concerned, which can be either clean methane (e.g.

from natural gas) or a biomass-derived fuel such as clean biogas (methane/CO2 mixtures) or

bioethanol. The steam reforming technology developed in CoMETHy allows for an easy

changeover of both the feedstock and the external heat source (solar or fossil/biomass back up)

whereas start-up, stand-by and shut-down operations are eased.

The reactors developed in CoMETHy were successfully tested with different prototypes, one of

which realized up to the pilot scale (3.5 Nm3/h hydrogen production) and integrated in a molten

salt loop, allowing to prove the concept developed and to reach performance figures above the

initial targets.

In conclusion, with the input of solar energy, CoMETHy technology allows to substantially save

primary fuels and reduce CO2 emissions in hydrogen production (compared to traditional

reforming technology), in a process evaluated to be economically attractive for both

decentralized (1500 Nm3/h) and centralized (> 5000 Nm

3/h) plant schemes. Furthermore,

CoMETHy successfully proved a solar reforming process aided by concentrating solar plants

using mature thermal energy storage system to increase plant utilization compared to the directly

heated solar reformers proposed in the past. Additional advantages would be obtained by the use

of biomass-derived feedstocks, including CO2 capture and re-use.

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3. Project context and the main objectives

CoMETHy (Compact Multi-fuel Energy To Hydrogen converter) is a product-oriented project,

which main objective is the development of an innovative compact and modular steam reformer

to convert reformable fuels (methane, ethanol, etc.) to pure hydrogen, adaptable to several heat

sources (solar, biomass, fossil, etc.) depending on the locally available energy mix.

The system developed within the project is characterized by a high degree of flexibility, both in

terms of:

1) the feedstock that is converted to hydrogen;

2) the primary energy source that powers the energy demanding process.

It is clear that the general strategy for hydrogen production is focused on water (or steam)

electrolysis powered by Renewable Energy Sources (RES). However, in this scenario, reliable

and flexible thermochemical processes can represent complementary hydrogen back up source,

especially if the RES input in the process is still high, as proposed in CoMETHy.

The project logo (Figure 1) recalls the general concept of the project: combining different

sources, depending on the locally available energy mix, to produce hydrogen as the unique

output energy vector. The different colours in the left hand side of the picture represent the

different combined energy and material resources: solar radiation, biomass, and two reformable

molecules of methane (bio-methane or natural gas) and ethanol (bio-ethanol); a water droplet is

represented too, in order to recall that CoMETHy is focused on the steam reforming technology

and that water is a feedstock converted to hydrogen (half hydrogen produced from water). The

circular arrow indicates that all these energy sources are combined together and that most of

them are “renewable” and contribute to the production of a single product on the right hand side

of the picture: “hydrogen”.

Figure 1. CoMETHy logo.

The technology developed in CoMETHy will support in particular the decentralized hydrogen

production (i.e. close to the end-user) thus surmounting the actual lack (and costs) of a reliable

hydrogen distribution pipeline and infrastructure (distribution, storage, logistics and charging

facilities). Besides, solar steam reforming technology is an attracting process route also for

centralized hydrogen production plants in countries with satisfactory solar radiation rates, like

those belonging to the so-called “sun-belt” (which also includes the Mediterranean area).

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CoMETHy proposes a new “low-temperature” steam reforming technology, where a molten salt

(molten nitrates mixture) at maximum temperatures of 550°C is used as heat transfer fluid. This

concept allows the supply of the process heat to the reformer as recovered from different heat

sources like Concentrating Solar Thermal (CST) plants. The hydrogen produced is separated and

purified by means of selective membranes.

More in detail, the general process scheme (Figure 2) involves main heat collection from a

Concentrating Solar Thermal (CST) plant and heat transfer to the thermochemical (steam

reforming) plant. The heat transfer fluid is represented by the so-called “solar salt”, i.e. the

molten salt mixture NaNO3/KNO3 (60/40 w/w) commonly used in commercial CSP plants as

thermal storage medium and, in some cases, as heat transfer fluid up to 565°C. A suitable heat

storage system, based on the use of the solar salt mixture, allows a mismatch between the

fluctuating solar source and the often steady running chemical plant: in principle, this makes

possible to drive the thermochemical plant at steady state, regardless of the effective

instantaneous availability of the solar radiation, even overnight and during cloudy periods.

Figure 2. CoMETHy steam reforming concept. MS: Molten Salts. Feedstock CH4 can be replaced by

CH4/CO2 mixtures, bioethanol or other reformable feedstock (e.g. glycerol, LPG, etc.).

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Selective membranes allow recovery of high-grade hydrogen and increase conversion despite the

relatively low operating temperatures. In the low-temperature steam reformer the catalyst and the

operating conditions also enhance the Water-Gas-Shift (WGS) reaction in a single step with the

main steam reforming reaction: therefore, compared to conventional steam reforming at higher

temperatures (> 850°C), the overall heat duty of the reformer will be reduced and the outlet

retentate (non-permeate) stream will contain a low CO content (< 10%vol.). After cooling and

CO2 separation, the residual H2/CH4 stream from the reactor can be recycled to the reformer. In

this way, when the thermochemical plant is powered by solar heat, in principle, there will be no

combustion in the whole process, nor combustion generated CO2-containing flue gases emitted

to the atmosphere: this will result in a substantial reduction, from 40% to more than 50%, of fuel

consumption and CO2 emissions, compared to the conventional route.

It is worth to be noted that the capture and recovery of the CO2 produced is also enhanced due to

its relatively high concentration in the outlet process stream. Moreover, when bio-fuels (biogas,

bioethanol, etc.) are used as feedstock in the membrane reformer, totally green hydrogen

production is achieved. Alternatively, the residual H2/CH4 stream can be used as back up fuel

when the solar power is not available.

The molten salt stream provides the process heat to the steam reformer, steam generator, feed

pre-heating, etc. Methane, either natural gas or biogas, and bioethanol were studied as feedstock

in a multi-fuel approach: CoMETHy aims at supporting the transition from a fossil-based to a

renewable-based energy economy, providing a flexible technology for different energy

scenarios.

The technology developed in CoMETHy leads to potential benefits also on hydrogen production

costs, operational flexibility and environment impact. Materials cost is reduced by operating at

less than 550°C, and additional process units, such as water-gas-shift reactor(s) and hydrogen

purifiers, avoided by the integration with membranes.

The first challenge to be faced in the development of this technology was the development of

advanced low-temperature steam reforming catalysts and cost-effective selective membranes in

the reference operational range (400-550°C, 1-10 bar). The subsequent technical challenge was

related to the coupling of the membrane with the catalyst in a membrane reactor. Finally, the

project involved the integration of the membrane reformer in a molten salts loop for proof-of-

concept at the 2 Nm3/h hydrogen production scale, and the techno-economical assessment of the

whole system.

CoMETHy Work Plan was divided in 5 RTD work packages (WPs 2 to 6) each including several

tasks and subtasks contributing to the achievement of specific project milestones (Figure 3). The

first project stage was mainly focused on the development of the two key components of the

reformer, i.e. the catalyst (WP2) and the membrane (WP3) to provide basic recommendations

about the catalyst system and the membrane to be applied (Milestones 1 and 2, respectively).

These activities represented an input to the reformer design (Milestone 3) and validation (WP4),

a main activity carried out during the second project year. After construction of the 2 Nm3/h

prototype, the final project period was mostly dedicated to the proof-of-concept (WP5,

Milestones 5) and to the optimization and evaluation of the whole system (WP6, Milestones 6

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and 7, respectively). In the perspective of a multi-fuel application, the identification of specific

catalysts for bioethanol steam reforming was required too (Milestone 4).

Figure 3. Simplified sketch of CoMETHy work plan, with RTD WPs, Milestones and outputs.

It is noteworthy that the activities carried out in CoMETHy and the results obtained contributed

to achieve the following FCH JU targets about hydrogen production:

- Maximizing hydrogen production from Renewable Energy Sources (RES), with CO2 free (or

CO2 lean) routes, specifically for the decarbonisation of transport (with up to 50% of the

hydrogen energy supplied from RES).

- Lowering the hydrogen production costs.

- Introducing and exploiting of higher performance materials (e.g. reforming catalysts with shift

activity and membranes).

- Developing steam reforming processes with efficiencies > 72% (including CO2 capture) for

centralized production, and > 67% for decentralized production from biogas (methane).

- Simplifying the reformer design in terms of compactness and scalability (2 to 750 Nm3/h

hydrogen production rate) and enhance catalyst replacement in less than 4 hours.

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4. S/T results and foreground

Development of new structured, open foam catalysts (WP2).

Fuel-flexible structured catalysts were first developed for the “low-temperature” (<550°C) steam

reforming of methane (natural gas or biogas-like methane/CO2 mixtures) and bioethanol. The

catalysts developed are characterized by minor pressure drops, enhanced heat transfer, and the

ability to simultaneously promote steam reforming and water gas shift reactions.

In order to optimize the performance of the membrane reformer, ceramic foams were considered

as support material for catalysts in the compact steam reformer at 400-550°C. In particular,

ceramic foams were specifically developed and adjusted to the requirements of the steam

reforming process:

- High radial heat transport in the packed bed reactor: especially in low-temperature steam

reforming, thermal gradients should be minimized to avoid temperature performance loss due

to low reaction rates in the coldest parts of the catalyst bed.

- Low pressure drop: especially in a membrane reactor, pressure drops should be minimized to

maximize the hydrogen flow through the membrane.

- High surface-to-volume ratio to reach a high catalyst loading.

The above properties of the foam are substantially influenced by its macro- and micro-structural

properties like type of material, porosity (ceramic content), cell size and cell porosity. Therefore,

hundreds of open-celled foam sample were developed and manufactured to be characterized,

coated with the catalytic material(s) and then tested in the reformers (in WP2, WP4 and WP5).

The manufacturing process was adapted and expanded in order to obtain the open foam

specifications desired, identified as the best compromise between thermal conductivity, high

surface for catalyst deposition, pressure drop and for the application of the slurry washcoating

method.

The structure and different types of porosity of ceramic foams were characterized in detail by

using special light microscopic measurement techniques.

In order to minimize the heat transfer resistance to the reactor wall, foams with different

variations of the external cylindrical surface were produced and evaluated too.

Non-catalytic monolithic foam samples with different materials and geometry were

experimentally tested to determine relevant heat transport pressure drop characteristics and a

mathematical model for heat transport in open cell solid foams was developed

Catalytic materials to be coated on the open foam supports had to be identified.

Initially, an extensive state-of-the-art review on steam reforming catalysts at 400-550°C was

made. Based on this, a review paper was published in the International Journal of Hydrogen

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Energy with the title “State-of-the-art Catalysts for CH4 Steam Reforming at Low Temperature”

(ref.: Int. J. Hydrogen Energy, 2014, vol.39, p.1979-1997).

For the steam reforming at 400-550°C of pure methane and CH4/CO2 mixtures (50/50 v/v, to

simulate a biogas with high CO2 content, to assess the effect of CO2) the catalysts needed to be

active and stable; moreover, the catalyst should promote the water-gas-shift reaction under the

same operative conditions, in order to increase the hydrogen concentration, decrease the CO

content, and reduce the overall heat demand of the reformer.

Therefore, based on literature and partners’ experience, 16 catalyst formulations were initially

proposed, with different active metals (Ni, Rh, Pt) supported on different oxides (Ce, La, Zr, Ca,

Al oxides). Fresh catalysts were fully characterized with several methods. Then, all catalysts

developed were tested for methane steam reforming, under representative conditions, to evaluate

the initial activity. After this pre-screening phase, the catalyst formulations showing best

performance were further tested over a wider operational range (1-7 bar, 400-550°C, several

space velocities), for the steam reforming of the CH4/CO2 mixtures (50/50 v/v) and in durability

tests (up to 250 hours-on-stream).

As a result of this process, four possible chemically active species/chemical support

combinations were finally selected for the CoMETHy reactor, based on Ni(10%), Rh(1%) or

Ni(10%)Pt(3%) (bimetallic) active species on CeO2 or CeZrLa oxide supports.

The catalysts selected showed high activity, allowing to obtain an output gas composition close

to the equilibrium condition at Gas Hourly Space Velocity (GHSV) of 30,000 h-1

. Since the

contact time expected in the designed membrane rector is much higher, these results prove that,

in terms of activity, the selected catalysts are suitable for CoMETHy application. These catalysts

also showed good activity towards the water-gas-shift reaction, allowing an outlet CO

concentration always lower than 3%vol.

Due to the importance of coke formation, this effect was better investigated and hydrogenation

was identified as a possible regeneration method.

For the selected catalysts, a suitable kinetic rate expression was validated, suitable to be applied

to the design and modelling of the low-temperature catalytic steam reformer.

Several catalyst formulations were proposed, developed and tested also for bioethanol steam

reforming. In this case, the bimetallic catalyst Ni(10%)Pt(3%) supported on CeO2 or CeZrLa

oxide was identified as the “best” option: despite the higher material cost (due to the minor Pt

content) this catalyst proved to be active and stable in ethanol, methane and simulated biogas

steam reforming, thus permitting to the CoMETHy reactor to work in the multi-fuel mode. In

this case, the possibility to use raw bioethanol (with large water content and contaminants) was

also evaluated.

A coating procedure was developed to obtain homogeneous, thin, and stable layers of the

selected catalytic materials (developed in the form of powders) on the pressureless Sintered

Silicon Carbide (SSiC) foam supports, without blocking the open-celled structure.

For catalytic applications the specific surface of these ceramic foams with less than 0.5 m²/g is

too low. In order to give ceramic foams their catalytic properties, they need to be coated with

http://dict.leo.org/ende?lp=ende&p=DOKJAA&search=pressureless&trestr=0x8004

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thin layers of highly porous materials, the so called washcoat (Figure 4). This surface-enlarging

washcoat layer is then impregnated with the effective amount of above mentioned selected

catalytic materials. In this way, the ceramic foam mainly fulfils requirements like mechanical

stability and high thermal conductivity, while the washcoat acts as a surface-enlarging support

that enables a finely dispersion of the catalytic active particles. The effect special binders and

additives was studied too in order to improve adhesion of the washcoat layers on the support

material.

Figure 4. Catalytic coating of open-celled ceramic foams.

Hence, using the developed components, materials and procedures, several catalytic foam

samples were manufactured and tested (with respect to stability and catalytic properties) to

validate performances in small reactors: a parametric experimental study at different operative

conditions (temperature, pressure, space velocity, etc.) was carried out to obtain relevant data for

reactor design and modelling. Durability tests (up to 250 hours-on-stream) were carried out too,

in order to validate the stability of the system.

In the end, the “best” combinations between catalyst formulation, foam type (SSiC solid foams

with a cell density of 30 ppi and 85% total porosity) and deposition method were defined for the

CoMETHy reactor. Ni(10%)/CeZrLaOx and Ni(10%)Pt(3%)/CeZrLaOx were identified as the

“best” performing systems. The bimetallic Ni-Pt based catalytic foam was finally chosen for the

final membrane reformer because of the good catalytic activity showed not only in methane but

also in ethanol steam reforming.

Combining the heat transport model obtained with the (non-catalytic) foam, the kinetic

expression obtained with the catalytic pellets and the results obtained with the small catalysed

samples, it was possible to obtain a complete mathematical model of foam packed fixed bed

reactor.

The developed catalysts were also assessed with respect to their performances in a “real”

environment, i.e. when the gas feedstock is contaminated with typical contaminants. This is the

case of catalyst poisoning due to higher hydrocarbons and/or sulfur compounds in

methane/biogas feedstock, or acetaldehyde and higher alcohols in bioethanol. Results showed

that methane steam reforming catalysts rapidly deactivate with few ppm of H2S. Therefore,

sulfur removal units to << 1 ppm should be applied in any case in order to avoid membrane

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failure. Moreover, selected catalysts showed high activity towards the alkane feedstock with no

apparent deactivation during the experiments. Also in-situ catalyst’s regeneration procedures

were defined.

Figure 5. Catalysed ceramic foams developed in WP2.

Development, characterization and selection of hydrogen separation membranes (WP3).

Different types of Palladium (Pd) based membranes were initially considered as potential option

to be applied in CoMETHy reactor, with different support (ceramic or metal supports, or self-

supported ones), selective layer composition (pure Pd or Pd-Ag) and selective layer deposition

method (electroless plating, sputtering, roll-to-roll of Pd foils, self-supported membranes).

Considering the final design of CoMETHy membrane reformer, self-supported membranes were

considered not suitable for this application because of mechanical issues, scale up implications

and costs. Differently, composite membranes with a thin Pd-based layer (2-5 µm) on a porous

support tube are considered as the best scale up choice.

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Figure 6. Composite membrane.

The membranes produced by sputtering (PVD technique) did not show sufficiently dense noble

metal layers: the roughness of the support significantly affected the densification, but an extra-

smooth support led to peeling of effects on the selective Pd-based layer.

Initially, CoMETHy was focusing on the development of Pd-Ag membranes on asymmetrical

porous stainless steel supports (APSS). Unfortunately, this development was hindered by

technical issues about the preparation of the APSS support (including the intermetallic ceramic

layer) with satisfactory quality for Pd-Ag deposition. Specifically, main issues were dealing with

the support roughness and the defects caused by the welding procedure in the connection area

between the porous tube and the solid metal ends.

As a consequence, the surface smoothness was significantly improved applying an outer

compaction technique. The application of the ceramic layer (TiO2, zirconia or TiN) was also

improved, introducing the film coating of ZrO2 as deposition technique and optimizing the

sputtering procedure for TiN, in order to minimize peeling off and roughness. However, in both

cases improvements are still necessary to obtain reliable supports.

Another required improvement on APSS supports was the reduction of defects in the connection

area between the porous tube and the solid metal flanges at the end, caused by the welding

procedure: the welding area between porous and non-porous metal support parts is still

insufficiently smooth.

In conclusion, metal supported membranes showed not to be mature enough to be incorporated

into the CoMETHy reactor. In any case, improvements to come to a hydrogen selective

membrane are very promising and potentials for further improvements exist.

However, the final readiness level obtained was not satisfactory for application in the membrane

reformer and further developments are necessary.

Differently, Pd membranes on a ceramic support by electroless plating were evaluated so far as

the “best” option currently available for the membrane reactor. For this reason, membrane

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reformer prototypes constructed and tested in CoMETHy were equipped with this kind of

membranes.

Despite some permeance inhibition effects (about 65%) by other mixture components (basically

methane) ceramic supported membranes produced by electroless plating allowed > 20

Nm3/m

2/h/bar

0.5 hydrogen permeability, above the initial targets (10 Nm

3/m

2/h/bar

0.5). Some

selectivity loss (< 20%) was measured over 1,000 hours-on-stream, but still within the project

targets.

Commercially available ceramic-supported Pd-based membranes were also purchased and tested

for more comprehensive evaluation and benchmarking. It was concluded that the ceramic-

supported Pd membranes selected and studied in CoMETHy have a good hydrogen permeance

when compared to other available membranes.

Progress in the development of metal-supported membranes shows to be very promising,

although it is unclear whether sputtering or electroless plating will be the most preferable

deposition method: both methods have advantages and disadvantages, and the suitability of both

deposition techniques on metal supports still has to be determined and is considered an essential

investigation task for future projects.

Finally, membrane performance results were successfully modelled considering different effects

like concentration polarization, competitive adsorption, inhibition effects, etc. The model was

validated with experimental results and literature data and applied to understand the results

obtained with the prototype and pilot membrane reactors developed in the project: by combining

the catalyst models with the membrane transport models it is possible to obtain the integrated

membrane reformer model.

Figure 7. Supported Pd-based membranes developed in WP3.

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Design and laboratory test of the fuel-flexible reformer (WP4).

Different design options for the molten salts heated membrane steam reformer were conceived

and evaluated. The first design was based on a Multi-Stage Membrane Reformer (MSMR) where

the membrane unit is separated from the catalytic bed, in a multi-stage reactor-membrane train

arrangement. The second design was an Integrated Membrane Reformer (IMR) where the

membrane is integrated with the catalyst bed and the molten salts heat exchanger.

Besides technical considerations, the selection of the optimal configuration depends on the final

application and optimization criteria. The IMR design, also called “closed” reactor, represented a

major engineering challenge in CoMETHy. On the one hand, Pd-based membranes are

compliant with the reactor temperatures, so an integrated system represented an attractive choice:

it is more compact and allows single-pass higher efficiency. On the other hand, challenges such

as catalyst/membrane integration and thermal/mechanical integration of components needed

thorough consideration and validation in innovative compact reformer prototypes.

Therefore, two IMR were assembled and tested in two dedicated test rigs. These prototypes

represented the final outcome of a close cooperation between different project partners involved

in the development of catalysts (WP2) and membranes (WP3), each bringing some fundamental

elements specifically and jointly developed. Noteworthy, both IMR prototypes developed and

tested in WP4 had cross sections with similar size and geometry than the 2 Nm3/h pilot unit

developed in WP5: reactor tube inlet (or foam outlet) diameter in the range 34-41 mm and 40-43

mm in the small prototypes and pilot reactor, respectively (membrane outer diameter is always

14 mm). This allowed the study and validation of the basic mechanisms involved in the process.

In preliminary tests, catalysts and membranes developed in CoMETHy were individually studied

and compared with commercial options for benchmarking.

Afterwards, both prototypes were successfully tested under representative conditions. Several

experimental tests were carried out in order to determine the effect of different operating

parameters, mainly the sweep gas flow rate, the steam-to-methane (S/C) feed ratio, methane feed

flow rate, and the operating pressures and temperatures on the reaction and permeation zones. In

this way it was possible to experimentally determine the IMR performance characteristics.

Experimental results showed that methane conversion and hydrogen production rates are highly

sensible to the sweep gas flow rate, permeate pressure and the feed methane flow rate.

Differently, the S/C ratio has slight effect on the single-pass conversion.

The experimental results obtained in the two laboratories were qualitatively consistent, showing

the reliability of the developed system.

Additionally, during the experimental campaigns, no evidence of reactor performance drop were

detected over hundreds operational hours: after 8 weeks of consecutive 24 h/24 h operation, no

methane conversion efficiency loss (due, for example, to catalyst deactivation) was evidenced.

This result suggests the robustness of the reactor assembly and confirms the positive results

previously obtained about catalyst and membrane stability over > 250 hours-on-stream.

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The fuel-flexible (multi-fuel) approach was successfully proved too with feed methane/ethanol

changeover over the same catalyst. Specifically, the open foam supported Pt(3%)Ni(10%)/CeO2

catalyst was applied which, as mentioned above, is active towards both methane and ethanol

steam reforming. Therefore, the “multi-fuel” feature of CoMETHy reactor was successfully

demonstrated, obtaining complete conversion of ethanol with CO, CO2, CH4, and H2 as the only

products.

At the end of this preliminary design and experimental validation stage, it was concluded that the

optimal multi-fuel design of the process is a single Integrated Membrane Reactor (IMR)

equipped with the multi-fuel catalyst. In the final design a pre-reformer (i.e. a low-temperature

steam reformer without membranes) was also introduced, in order to get some hydrogen

concentration in the inlet gas feed to the IMR as well as to reduce thermal gradients in this

section.

Mathematical models for the membrane reactor were developed to be applied as design and

optimization tools, facing the key challenge to synchronize the heat transfer rate with the

reaction kinetics and the hydrogen permeation through the membrane. The models developed

were validated considering different aspects of the IMR (heat and mass transfer mechanisms,

reaction kinetics, hydrogen permeance through the membrane, etc.) and applying the catalyst and

membrane performance data obtained in WP2 and WP3 respectively.

One major conclusion is that membrane reformer’s performances are significantly affected by

concentration polarization and inhibition of the membrane by other species (that can be

amplified at higher pressures).

Based on the results obtained and validation of the IMR design, the detailed engineering design

of the pilot steam reformer was developed.

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Figure 8. Catalyst/membrane integration and laboratory reformer tests in WP4.

Pilot plant construction and proof of concept (WP5).

According to the design, pilot plant components, including catalysts and membranes, were

manufactured and supplied by CoMETHy partners with the defined size and geometry (Figure

9). Then, the pilot plant was built and commissioned at ENEA-Casaccia research centre in

Rome, integrated in an existing molten salts loop using electrical heaters to simulate the

Concentrating Solar Thermal (CST) plant.

The plant scheme (Figure 10) involves two molten salts heated steam reformers connected in

series: a pre-reformer (R-01) and an Integrated Membrane Reformer (IMR, R-02). Both reactors

are based on a shell-&-tube heat exchangers layout, with the molten salts stream flowing on the

shell side.

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Figure 9. Steam reformer components developed for the pilot reactors in WP5: reactor heat exchanger

(top left), catalysts (bottom left), membranes (right).

The membrane reformer (Figure 11) includes ten reactor tubes, each including the catalyst and

the membrane. The reactor includes six gates: molten salt inlet/exit gates, feed mixture inlet,

retentate exit, sweeping steam inlet and the hydrogen permeate exit ports.

The pre-reformer allows the production of a H2-containing gas mixture (roughly corresponding

to thermodynamic equilibrium) leading to the following advantages on the process:

- maximizing the utilization of the membranes also at the feed inlet section on the IMR;

- minimizing the thermal stresses on the inlet section of the IMR due to high reaction rates;

- minimizing the risk of fouling of membrane and catalyst in the IMR thanks to higher

hydrogen concentration.

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Process steam from a steam generator is first pre-heated at the desired temperature in a heat

exchanger E-01 and then split in two streams:

- sweep steam directly injected on the permeate side of the IMR;

- process steam to be mixed with the CH4 feed (from gas cylinders) and pre-heated to reactors’

inlet temperature, usually in the range 420-480°C.

The produced permeate and retentate streams are recovered and analysed after excess steam

condensation. Molten salts are counter-currently flowed through the two reactors, entering firstly

in the IMR reactor at the desired temperature and flow rate from the MO.S.E. plant facility at

ENEA-Casaccia research center in Rome.

Some pictures of the pilot plant are shown in Figure 12 and Figure 13.

Figure 10. Chemical section scheme of CoMETHy pilot plant.

The pilot plant operation included a preliminary phase with the validation of start-up, shut down

and stand-by strategies. The study also included an assessment of plant performances and a

macroscopic analysis of the experimental results.

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In total, including the start-up, stand-by and shut down stages, the plant was operated with

molten salts for about 700 hours. Continuous operation of the plant was achieved for about 150

hours. During this period the plant performances were assessed under several operative

conditions: molten salts inlet temperature, sweep steam flow rate and steam-to-carbon feed ratio.

A macroscopic result analysis was carried out too.

Results can be summarized as follows:

- the application of the membrane reformer following a pre-reformer allows to get more than

double the conversion that can be obtained with a non-membrane reformer under the same

conditions;

- proof-of-concept of CoMETHy technology was successfully achieved at the pilot scale in

relevant environment, obtaining up to 3.5 Nm3/h pure hydrogen production under design

conditions, higher than the project quantitative target of 2.0 Nm3/h;

- > 99.8% hydrogen permeate was produced with < 100 ppm CO content and the conditions to

minimize CO concentration in the permeate were identified;

- catalysts and membranes were assembled and replaced in the reactor(s) in less than 4 hours;

- no macroscopical signs of reactor performance loss were evidenced over the experimental

operation period, despite the above mentioned handling of catalysts and membranes (the

reactor was opened during the experimental phase) and the several switches of operative

conditions;

- start-up, shut down and stand-by strategies were validated and the good practice (for full-scale

plants) to keep reactor(s) “hot” during stand-by periods, by the use of molten salts as

thermostatic fluid, was assessed, thus facilitating start-up and extend lifetime of components

(e.g. membranes);

- the effectiveness of the WGS reaction in the reactor(s) resulted in an outlet retentate stream

with low CO concentration (< 2%);

- a relatively high CO2 concentration (32-39%) was obtained in the outlet retentate stream at

9.5 bar, enhancing CO2 capture for its recovery and/or reuse, demonstrating the application of

CoMETHy technology to fuels pre-combustion decarbonisation.

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Figure 11. Pilot membrane reformer arrangement during construction in WP5.

Figure 12. External view of CoMETHy pilot plant during a visit of project partners (May 2015).

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Figure 13. Pilot plant sections in operation during experimental tests in WP5.

Figure 14. Pilot plant experimental results. Effect of molten salts inlet temperature on CH4 conversion,

CO concentration in the permeate stream and H2 permeate flow rate (S/C: steam-to-methane

feed ratio, kg/kg).

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Techno-Economical assessment of the process (WP6).

Based on the results obtained with the pilot reformer, the best strategies to couple this reformer

with a CST plant were studied and evaluated from a techno-economic perspective. Several

process schemes were conceived, simulated and evaluated, under different scenarios.

Specifically, decentralized and centralized solar steam reforming plant schemes (1500 and 5000

Nm3/h, respectively) were developed and evaluated. Results were compared to a conventional

steam reforming process with the same capacity and scenarios, including CO2 recovery.

In general, two process options were considered:

- “full solar” steam reforming process, where the process heat is entirely provided by the CST

plant, with or without electrical power co-generation;

- “hybrid” steam reforming process, where part of the process heat is provided by retentate off-

gas combustion with oxygen or air, and partly by the CST plant.

In both cases, the continuous operation of the steam reforming plant is primarily ensured by

means of a molten salts based heat storage system and then by a gas fired back-up heater to drive

the process when the solar heat is no longer available.

For larger scale plants with hydrogen production capacity of 5,000 Nm3/h (or more) a Multi-

Stage Membrane Reformer (MSMR) was considered for the evaluation, provided that this

arrangement is considered more suitable for larger scale plants. However, the general

conclusions of this study were not affected by the membrane reactor design type (either

integrated or not).

Since the results obtained were strictly related to the economic assumptions, a sensitivity

analysis was carried out too, changing different economic input parameters like the depreciation

factor or unit costs of feedstock/fuel (NG), catalysts, membranes, CST plant, by-products, etc.

In general, integration of solar energy through a CST system based on molten salts in a steam

reforming process seems to be a promising approach to minimize hydrogen production costs and

the CO2 emitted.

Compared to conventional steam reforming processes, the solar processes developed in

CoMETHy require higher initial investment costs (CAPEX) due to the rather relevant investment

for the CST plant and ancillary items: the CAPEX impact on the hydrogen cost is, in most cases,

> 45%, while the CAPEX impact in conventional steam reforming routes is usually < 25%. This

larger CAPEX is however balanced by savings in operative costs for the feedstock and the fuel

in the solar process. As a result, the overall hydrogen production cost obtained by CoMETHy

solar steam reforming technology does not significantly differ from conventional routes.

In the 5,000 Nm3/h solar steam reforming schemes, hydrogen COP is within the range of 1.09-

1.22 €/kg, considering a 5,000 hours/year full-solar operation. These values are rather close (<

±10% difference) to the value of 1.19 €/kg estimated for a conventional steam reforming process

(i.e. without solar input) under similar assumptions (including CO2 recovery).

Considering that CoMETHy process is highly capital intensive, the impact of the annual

depreciation factor was evaluated too.

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After preliminary evaluation of different solar steam reforming schemes with 5,000 Nm3/h

hydrogen production capacity, based on the MSMR design, a process scheme with 1,500 Nm3/h

hydrogen production capacity was evaluated. In this case, the Integrated Membrane Reformer

(IMR) design successfully proved in CoMETHy pilot plant was considered, and a more detailed

analysis carried out.

First, the relationship between the size of the solar field, the Thermal Energy Storage (TES)

capacity and the annual operational hours when the process is fully powered by solar energy was

determined by increasing the number of hours/year operated with solar power the back-up fuel

demand proportionally drops and the energy efficiency (produced H2 energy (LHV) divided by

NG feed + fuel + power input) increases up to 80%.

Merging these results with those from the sensitivity study (by changing the economic

parameters) the hydrogen production costs obtained were always within the range of 2.02-3.36

€/kg, a cost that is rather close to the one obtained in conventional steam reforming of 1.74 €/kg.

The higher hydrogen production costs are mainly due to the above mentioned higher CAPEX

impact (in the range of 46-58%) on COP compared to the 21% CAPEX in conventional steam

reforming.

The contribution of the different cost items to the overall hydrogen production cost was

identified. The CST plant represents the package with the largest impact (49%) on the total

equipment cost, followed by the membrane steam reformers (23%). Therefore, a trade-off should

be identified to minimize the hydrogen production costs while maintaining high the solar power

impact in the process. Differently, membranes, catalysts and maintenance costs have a minor

impact (< 11%) on production costs. As for the impact of feedstock and fuel (NG), different

scenarios were considered, referring to the NG market price in Europe and USA.

It is noteworthy that, in CoMETHy’s “multi-fuel” approach, biogas and/or bioethanol were

envisaged as feedstock too. In both cases, the biomass-derived feedstock is usually derived by

low-cost refuses, but a biogas up-grading unit or a bioethanol pre-reformer should be introduced

in the process, affecting the cost of the methane-rich gas effectively fed to the main membrane

reformer. Therefore, the sensitivity analysis of the impact of feedstock cost will be helpful to

predict also the effect of alternative fuels in the multi-fuel cases.

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5. Impact, dissemination activities and exploitation of results

CoMETHy is a product-oriented project which main objective is the development of an

innovative compact and modular steam reformer. As such, the potential impact of the technology

developed, as well as the exploitation scenarios, can be analysed at the end of the project, when

measurable and final results are available, concretely showing the outcomes of the research and

of the technological activities carried out. All the starting assumptions, declared objectives and

expected outcomes can be measured against concrete results. The approach to the project can

thus be innovative and pioneering, and the achievements of the 4 year work can be looked

through the lenses of concrete exploitation.

In the second part of this section the dissemination activities aimed at fostering the exploitation

of the results are reported.

5.1 Impact of CoMETHy results

Steam reforming is the leading technology for large scale hydrogen production: today, more than

25 million tons of hydrogen per year are produced primarily by steam reforming of natural gas.

CoMETHy developed and proved a new steam reforming process characterized by several

innovative features compared with the traditional route, including:

- compact layout of the reactor;

- operation at lower temperatures (< 550°C, compared to traditional SMR > 850°C);

- possibility to power the process with solar energy, reducing CO2 emissions and save primary

fuel;

- flexibility of operation in terms of rapid start-up and shut down;

- flexibility of application in terms of primary fuel and feedstock to be converted to hydrogen

(natural gas, biogas, bioethanol, etc.).

The reactor developed in CoMETHy is by itself the first of its kind, based on a membrane

reformer and molten salts as heat transfer fluid. Moreover, new plant schemes were conceived

and positively evaluated from technical and economical perspectives, adaptable to different

industrial and energy scenarios, for both centralized and decentralized hydrogen production.

With these results and the activities implemented, it is noteworthy that CoMETHy contributed to

achieve some of the FCH JU Programme objectives and targets dealing with “Hydrogen

Production and Distribution”. In the following paragraphs it is reported how CoMETHy’s results

would endorse the implementation of the FCH JU Programme and its roadmap.

Hydrogen production processes from Renewable Energy Sources.

The general strategy on hydrogen production aims at maximizing the production from

Renewable Energy Sources (RES), with CO2 free (or CO2 lean) routes, in particular for the

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decarbonisation of transport. Specifically, the FCH JU MAIP published for 2008-2013 targeted

up to 50% of the hydrogen energy supplied from RES.

CoMETHy’s reactor prototypes and pilot plant proved the feasibility of the solar steam

reforming of methane, resulting in a 38-53% reduction of CO2 emissions and equivalent methane

savings compared to the traditional process.

Additionally, considering the energy balance of developed Natural Gas (NG) steam reforming

plant schemes developed in CoMETHy, more than 40% of total energy input in the process

derives from solar heat.

Reforming of biofuels (biogas, bioethanol) was proved too, obtaining 100% renewable

hydrogen.

Current strategies for future hydrogen production are chiefly focused on the exploitation of

electrolysis mainly powered by renewable sources (e.g. PV and wind). This trend is supported by

the growing impact of renewable sources in the electrical grid mix. However, it is important to

notice that energy systems with major impact of intermittent renewable sources (e.g. PV and

wind) need some extent of “predictable” back-up sources and technologies available to

compensate fluctuations and satisfy power demand. In electrical power systems this is usually

achieved by NG and/or biomass power plants. Similarly, in hydrogen production the back-up

option can be represented by decentralized steam reforming plants powered by NG and/or

renewable sources: in this context, CoMETHy offers a technological solution: the novel

membrane steam reforming reactor made available by CoMETHy is expected to pave the way to

new opportunities for distributed hydrogen generation, alternative to electrolysis and allowing

the use of different fuels and energy sources depending on local availability.

Reduction of hydrogen production costs.

Lowering the hydrogen production costs represents a key target for hydrogen production

technologies (MAIP 2008-13).

Compared to traditional steam reforming, the reduction of operating temperatures obtained

allows savings in construction material costs for the reactor.

The techno-economic assessment of CoMETHy solar steam reforming technology demonstrated

that the hydrogen production costs reached are close to the hydrogen production costs of

traditional steam reforming processes on the 1,500-5,000 Nm3/h scale. Though, the

environmental benefits and the lower impact of primary fuel cost should be considered in the

balance.

Additionally, by increasing the solar energy share in the process, the cost of hydrogen is less

subject to the cost of fossil source compared to the traditional process.

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Development of higher performance materials.

The introduction and exploitation of higher performance materials (e.g. reforming catalysts with

shift activity and membranes) represent another key target in hydrogen production technologies

(MAIP 2008-13).

The catalysts developed in CoMETHy were proved to be stable over 250 hours-on-stream, with

combined steam reforming and water-gas-shift activity: these steam reforming catalysts lead to

CO content < 5%vol, thus avoiding the need of water gas shift reactors and reducing the

reformer heat duty.

The effectiveness of the WGS reaction has also been demonstrated in the pilot reactor where <

2% CO concentration was obtained in the outlet retentate stream.

As for the membranes, solutions were identified and significant advancement has been achieved

on metal supported membranes. Nevertheless, ceramic-supported palladium membranes

represented an alternative option successfully demonstrated in CoMETHy up to the pilot scale.

However, long-term durability of membranes needs to be further assessed in future projects

Process performances.

The FCH JU implementation plan for 2008-2013 targeted the development of steam reforming

processes including CO2 capture with efficiencies > 72% for centralized production and > 67%

for decentralized production from biogas (methane).

CoMETHy process evaluations and experimental results lead to steam reforming thermal

efficiency in the range of 68-80% (produced H2 thermal power, LHV, divided by feed + fuel +

thermal power input) for a 1,500 Nm3/h methane steam reforming plant (decentralized

production) including CO2 capture.

Simplification of the plant and the process.

The FCH JU implementation plan published in 2010 called for a simplification of reformer

design in terms of compactness and scalability (2 to 750 Nm3/h hydrogen production rate).

Additionally, catalyst replacement should be easily achieved in < 4 hours (AIP 2010).

In CoMETHy a highly compact reactor has been developed and demonstrated, with steam

reforming, water-gas shift and hydrogen separation achieved in a single unit. The use of a liquid

heat carrier like molten salts (with high heat capacity per unit volume) allows further reduction

of reformer volumes compared to conventional furnaces. The concept has been proved with a

pilot plant producing from 1.5 to more than 3.5 Nm3/h of pure hydrogen.

Modular and scalable reactor designs were conceived. The shell-and-tube heat exchanger

configuration will ease scalability from the 2 Nm3/h (as in the pilot unit experimentally proved in

CoMETHy) to 1,500 Nm3/h or more: increasing or decreasing the number of tubular reactors and

membranes is enough to obtain different plant sizes. An alternative “multi-stage” (or “one”)

configuration has been designed too, suitable for larger scale applications.

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Therefore, CoMETHy technology could be applied in small-medium-large scales and the

reformer used in various operational fields, from an industrial plant to produce large amount of

hydrogen to decentralized small users.

As for the reactor maintenance, in CoMETHy it has been demonstrated the replaceability of

catalysts and membranes in the reactor(s) in less than 4 hours, thus achieving another specific

target set by the FCH JU in the field of hydrogen production.

Socio-economic impact.

The success of CoMETHy process will support the opening of new industrial production lines in

the fields of advanced catalyst systems, hydrogen separation membranes, new reactor and

chemical technologies and new concentrating solar power applications.

The worldwide growth of the “green economy”, with the actual implementation of the FCH JU

plan up to market penetration of developed technologies and the wide application scenarios for

steam reforming, will result in a socio-economic impact: CoMETHy proposes new products and

solutions well aligned with the common strategies on sustainable development, thus supporting

job creation, energy safety and welfare.

5.2 Exploitation of CoMETHy results

The foregrounds generated in CoMETHy potentially pave the way to different exploitation

scenarios, mainly thanks to the inherent innovation proposed by the technology.

In general, the steam reforming technology developed in CoMETHy is considered innovative

compared to the state of the art for different reasons.

First of all, the adoption of a multi-fuel approach, i.e. the possibility to convert either methane

(concentrated or mixed with CO2) or bioethanol in the same reactor, is by itself a new concept.

Moreover, a new solar steam reforming process has been conceived and successfully proved,

featured by the use of molten salts as heat transfer fluid from the CST plant and solar heat

storage medium. Indeed, solar reforming has been studied in previous projects, using solar-

receiver reactors directly heated by the concentrated solar radiation, with full-solar operation

limited to 2,000 hours/year. In CoMETHy, the application of CST molten salts technology with

thermal storage allows to increase the full-solar operation of the reformer to > 4,000 hours/year.

In this way it is possible to maximize the utilization of the solar thermal power.

Furthermore, a new knowledge has been generated in the development of structured

heterogeneous catalysts with enhanced heat transfer properties and reduced pressure drops. Some

advancement has been achieved also in the production of SS-supported Pd-based membranes,

although further research and development is needed to obtain a reliable product.

The exploitable foreground generated in a RTD project like CoMETHy in most cases consists of

a “general advancement of knowledge”, and RTD results are not considered ready for

commercial exploitation, yet. To measure such knowledge advancement, it is convenient to use

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the Technology Readiness Level (TRL). In terms of TRL, CoMETHy has taken a technology

concept initially formulated with basic studies (corresponding to TRL = 2) to demonstration of

the technology in relevant environment (TRL = 6). Demonstration and qualification in a full-

scale operational (industrial) environment (TRL = 7 up to 8) is still needed before commercial

exploitation. Therefore, despite the successful results, this innovative technology is not ready for

market penetration, yet: further work would be needed to further develop and test the knowledge

generated in a follow-up demonstration project (in a real industrial and end-user context) to get

to the market stage.

CoMETHy follow up opportunities, exploitable foreground and the exploitation lines were

widely discussed between project partners during the final project meeting (December 2015).

Some conclusions of this analysis are summarized in the following paragraphs.

Application of developed new materials and components.

Some components studied and developed in CoMETHy, such as structured (open foam)

catalysts, hydrogen separation membranes, integrated membrane reactors, etc., can lead to

potential spin-off for advanced component manufacturing (catalysts, membranes, hydrogen

purification units, reactor assembly, heat recovery units, etc.) and engineering.

This is the case of structured open foam catalysts, developed specifically for low-temperature

steam reforming of methane and/or ethanol. This catalyst is characterized by enhanced heat

transfer, minor pressure drops, and the capability to simultaneously promote steam reforming

and water-gas-shift reactions in the temperature range of 400-550°C. This has been positively

proved in several tests in CoMETHy, so it can be commercially exploited, provided that the

performances are validated over longer times on stream (> 1,000 hours).

Considerable effort has been addressed to palladium based membranes on porous metal supports.

Significant advancement has been achieved, specifically on the porous metal substrate quality

and the deposition of the inter-metallic ceramic barrier layer. Nevertheless, further RTD

activities are required to obtain a reliable product. Therefore, the knowledge generated in

CoMETHy can foster next RTD projects aimed to launch this new product on the market.

Application of CoMETHy reactor concept.

In CoMETHy, two different membrane reformer designs were developed: Integrated Membrane

Reformer (IMR) and non-integrated Multi-Stage Membrane Reformer (MSMR).

The IMR design, also called “closed” reactor, represented a major engineering challenge. It has

been successfully proved up to the pilot scale in a representing unique prototype of this kind,

heated by molten salts up to 550°C. All project partners participated to the development of this

reactor. Before commercial exploitation, it is necessary to validate the performances over longer

operational periods (> 1,000 hours).

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The MSMR design, also called “open” reactor, has been evaluated to be most suitable for larger

scale applications (> 5,000 Nm3/h hydrogen production). This reactor layout has been designed

but not experimentally proved in CoMETHy.

Application of CoMETHy solar steam reforming process.

After the experimental validation of CoMETHy technology at the pilot scale, different process

schemes have been developed and evaluated from the techno-economical perspective,

considering different scenarios and plant capacity (1,500 and 5,000 Nm3/h hydrogen production).

Moreover, the strategies and best practices to couple the steam reforming plant with the

Concentrating Solar Thermal (CST) plant have been identified, showing the competitiveness of

the developed process with conventional steam reforming routes.

Application of CoMETHy multi-fuel reformer for decentralized hydrogen production.

Besides the possibility to power the steam reforming process by solar energy, other process

schemes have been developed in CoMETHy for distributed hydrogen production.

Based on the solar reforming scheme, mostly suitable for medium-large scale applications (>

1,500 Nm3/h production scale) an “autothermal” process has been developed for smaller scales

(e.g. 750 Nm3/h), for example for refuelling stations. In this case, CoMETHy reformer can be

applied to hydrogen production from natural gas or biogas, using the residual heat value of the

retentate stream to sustain the process. It is noteworthy that this small reformer would be the first

commercial product of this kind in Europe.

Furthermore, a process to convert bioethanol to hydrogen has been developed, with the same

multi-fuelled membrane reformer as above, but with the pre-reformer to convert the diluted

ethanol to methane before feeding the membrane reformer. Considering the multi-fuel feature of

the reformer, this approach allows a full renewable back up of the gas fuel reformer, to “on

demand” allow hydrogen generation.

Possible exploitation burdens and limitations.

In assessing the exploitation potentials of the technology developed, possible burdens should be

also taken into account.

Intellectual Property (IP) issues do not represent a significant limitation to the diffusion of the

developed technology. Clearly, CoMETHy is a product-oriented RTD project with a deep

industrial footprint and a specific know-how was developed in the project. CoMETHy partners

obtained the necessary skills to implement further technical projects. Otherwise, the exploitation

can pass through technology transfer from CoMETHy partners to final users. In any case, the

developed know-how can be transferred to support its wide diffusion.

As far as the technology maturity and readiness is concerned, CoMETHy reactor has been

successfully proved at the pilot scale, but for a limited number of operational hours. In order to

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validate the technology, the process performance over a longer operation time (> 1,000 hours),

would be necessary.

As for the application scenarios, different exploitation cases have been investigated in

CoMETHy and some limitations identified: the wide exploitation of solar reforming is limited to

countries with satisfactory solar radiation intensity for the convenient installation of CSP plants,

i.e. those belonging to the so-called “sun-belt”. Additionally, according to CoMETHy results, the

solar reforming route is applicable for reforming plant scales of 1,500 Nm3/h or more. Although

this minimum solar reforming plant size can still be considered for distributed hydrogen

production, at least 20,000-30,000 m2 area should be available nearby the plant to allocate the

solar collectors. This can represent a limitation for the implementation of the technology in some

cases (e.g. for refuelling stations in urban areas). For more decentralized applications (< 1,500

Nm3/h) the non-solar CoMETHy process can be applied, either for methane, biogas and/or

bioethanol steam reforming. In this last case, the low-temperature steam reforming technology

developed in CoMETHy will compete with alternative small reforming technologies like

compact autothermal reformers.

Future developments.

Considering the technical success of the project and the Technology Readiness Level achieved,

CoMETHy partners agreed to carry out follow-up activities at the demonstration level, as

detailed below.

First, the pilot plant constructed in CoMETHy can be further used, with some adaptations, in

new projects aimed at consolidating results and paving the way for the commercial exploitation

of the technology, for example:

- Plant performance analysis for longer periods (> 1,000 hours).

- Bio-ethanol steam reforming tests.

- Plant integration with CO2 separation membranes and recirculation of the residual H2/CH4

from the retentate to the membrane reactor.

- Support a demonstration project with a preliminary test campaign to test the plant under

specific representative working conditions useful for the design.

Otherwise, new demonstration plants to prove the technology in real industrial or end-user’s

environment can be built.

A first option (for non-solar CoMETHy reformer) is the installation of the methane/biogas steam

reformer in a “biomass-to-hydrogen” context, in the framework of a demonstration project,

possibly directly coupled to a fermentation plant and biogas clean-up unit. In this case, the

reformer would not necessarily be powered by a CSP plant, but the “autothermal” layout is most

likely to be used. Additionally, the membrane reformer can be combined with a dry reformer,

operating at higher temperatures (usually > 650°C) as pre-reformer: CoMETHy membrane

reformer will complete the conversion of bio-methane to pure hydrogen. A small scale

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methane/bioethanol steam reformer (eventually in the multi-fuel configuration) can also be

integrated in a hydrogen refuelling station.

An interesting perspective is the application of the solar steam reforming process to ammonia

plants. Ammonia synthesis plants require large amount of pure hydrogen usually produced by

Natural Gas (NG) steam reforming. A project can be implemented integrating the CoMETHy

solar methane steam reforming technology with an ammonia plant in a “sun belt” region. The

advantage of this approach lays in the replacement of conventional reforming with a solar

reformer (> 40% savings in methane consumption and CO2 emissions during solar operation)

combined with the possibility to use nitrogen as sweep gas in the reactor in order to directly

produce the H2/N2 feed mixture for ammonia synthesis, thus saving the sweeping steam

generation.

It is possible that CoMETHy reformer prototypes will also find applications integrated in more

complex process schemes. This is the case, for example, of refinery processing where heat is

available for recovery at 500-600°C.

Finally, CoMETHy reformer can be applied to maximize hydrogen recovery from partially

converted syngas streams produced in higher temperature reforming units.

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5.3 Dissemination activities

Dissemination activities undertaken from the beginning and beyond the end of the project

represent a tool to boost exploitation potential and identify new scenarios, perspectives and

stakeholders.

CoMETHy results have been presented in several international journals, conferences and

workshops dealing with chemical reactor engineering, membrane reactors, renewable energy,

hydrogen production, etc.

Two international workshops have been organized in cooperation with other 7FP projects

dealing with palladium membranes and membrane reactors in November 2012 (Italy) and

November 2014 (the Netherlands). The two workshops gathered world players in this field

(Figure 15). Booklets have been produced and distributed after the events.

Figure 15. International workshops organized in November 2012 in Rome and November 2014 in Petten.

In October 2013 a summer school titled “Engineering of membrane reactors for the process

industry” has been organized with several CoMETHy lectures; during the same period, a

CoMETHy session has been organized within the PRES’13 Conference in Rhodes.

Moreover, CoMETHy results have been widely presented in tens of papers published in

international peer reviewed journals and conference proceedings.

Page : 35/43



In Annex 1, all the scientific publications and dissemination activities produced about to the

foreground of the project are listed (also included in Section A” of the Final Report).

It is planned to continue dissemination actions beyond the end of the project in order to promote

the exploitation of the developed technology: dissemination actions planned after the end of the

project will mainly look for the exploitation of results, outlining the potentials of CoMETHy

based applications, with an “end-user” oriented message. Furthermore, the pilot plant operated

during the final project year at the ENEA-Casaccia research center in Rome has been visited by

several groups, and will be available for external visitors to show the developed technology.

The target group comprises potential stakeholders, developers and potential end-users of the

technology developed, who have been identified among those who have already been in contact

with the project, such as participants to dissemination events, components’ producers and

scientific and technological partners internal and external to the project as well as newly

identified final users.

In general, CoMETHy stakeholders, developers and end-users belong to the following focus

areas: renewable energy, hydrogen production, fuel cells, hydrogen refuelling, CSP, solar fuels,

pre-combustion decarbonisation, NG pipeline, catalysis, hydrogen purification, process

intensification, etc. End-users and developers together draw the picture of a potential production

chain, getting the innovation to the market/to a further development step.

Page : 36/43



ANNEX 1: List of CoMETHy publications

Peer Reviewed Publications

- “Hydrogen production through catalytic low-temperature bio-ethanol steam reforming”. Clean Technologies and

Environmental Policy. Vol. 14/Issue 5, 973-987. Published by UNISA & Processi Innovativi in October 2012.

- “A Tunnel Model for Activated Hydrogen Dissociation on Metal Surfaces”. Journal of Physical Chemistry C.

Vol. 117/Issue 15, 7475-7486. Published by Technion in April 2013.

- “On the activity of bimetallic catalysts for ethanol steam reforming”. International Journal of Hydrogen Energy.

Vol. 38/Issue 16, 6633-6645. Published by UNISA & Processi Innovativi in May 2013.

- “Predicting CH4 Dissociation Kinetics on Metals: Trends, Sticking Coefficients, H Tunnelling, and Kinetic

Isotope Effect”. Journal of Physical Chemistry C. Vol. 117/Issue 44, 22811-22826. Published by Technion in

November 2013.

- “CeO2-supported Pt/Ni catalyst for the renewable and clean H2 production via ethanol steam reforming”.

Applied Catalysis B: Environmental. Vol. 145, 73-84. Published by UNISA & Processi Innovativi in February

2014.

- “State-of-the-art catalysts for CH4 steam reforming at low temperature”. International Journal of Hydrogen

Energy. Vol. 39/Issue 5, 1979-1997. Published by AUTH & ENEA in February 2014.

- “Enhancement of pure hydrogen production through the use of a membrane reactor”. International Journal of

Hydrogen Energy. Vol. 39/Issue 9, 4749-4760. Published by CERTH in March 2014.

- “Modelling H2 transport through a Pd or Pd/Ag membrane, and its inhibition by co-adsorbates, from first

principles”. Journal of Membranes Science. Vol. 466, 58-69. Published by Technion in September 2014.

- “Effective approximations for concentration-polarization in Pd-membrane separators”. Chemical Engineering

Journal. Vol. 260, 835-845. Published by Technion in January 2015.

- “On-site pure hydrogen production by methane steam reforming in high flux membrane reactor: Experimental

validation, model predictions and membrane inhibition”. Chemical Engineering Journal. Vol. 262, 862-874.

Published by Technion in February 2015.

- “Methane steam reforming at low temperature: Effect of light alkanes’ presence on coke formation”. Catalysis

Today. Vol. 242, 119-128. Published by AUTH in March 2015.

- “H Tunnelling Effects on Sequential Dissociation of Methane over Ni(111) and the Overall Rate of Methane

Reforming”. Journal of Physical Chemistry C. Vol. 119/Issue 17, 9260-9273. Published by Technion in April

2015.

- “Directing selectivity of ethanol steam reforming in membrane reactors”. International Journal of Hydrogen

Energy. Vol. 40/Issue 17, 5837-5848. Published by University La Sapienza, UNISA & Technion in May 2015.

- “Multi-fuelled Solar Steam Reforming for Pure Hydrogen Production Using Solar Salts as Heat Transfer Fluid”.

Energy Procedia. Vol. 69, 1750-1758. Published by all partners in May 2015.

- “Can the permeance of a Pd-based membrane be predicted from first principles?”. Current Opinion in Chemical

Engineering. Vol. 9, 27-33. Published by Technion in August 2015.

- “Pure hydrogen production in a membrane reformer: Demonstration, macro-scale and atomic scale modelling”.

Chemical Engineering Journal. Vol. 278, 363-373. Published by Technion in October 2015.

- “Ethanol steam reforming over bimetallic coated ceramic foams: Effect of reactor configuration and catalytic

support”. International Journal of Hydrogen Energy. Vol. 40/Issue 37, 12650-12662. Published by UNISA &

Fraunhofer IKTS in October 2015.

Page : 37/43



- “Design concepts of a scaled-down autothermal membrane reformer for on board hydrogen production”.

Chemical Engineering Journal. Vol. 282, 123-136. Published by Technion in December 2015.

- “Approximate models of concentration-polarization in Pd-membrane separators. Fast numerical analysis”.

Journal of Membranes Science. Vol. 500, 136-150. Published by Technion in February 2016.

- “Catalyst development for steam reforming of methane and model biogas at low temperature”. Applied Catalysis

B: Environmental. Vol. 181, 34-46. Published by AUTH & ENEA in February 2016.

- “Transport-permeation regimes in an annular membrane separator for hydrogen purification”. Journal of

Membranes Science. Vol. 503, 199-211. Published by University La Sapienza & ENEA in April 2016.

- “Optimization of an experimental membrane reactor for low-temperature methane steam reforming”. Clean

Technologies and Environmental Policy. 1-11- Published by CERTH in May 2015.

Article/Section in an edited book or book series

- “Hydrogen Production by Solar Steam Reforming as a Fuel Decarbonization Route”. Book title: “CO2: A

Valuable Source of Carbon”. Pages 109-122. Springer London. Published by ENEA in 2013.

- “Membrane technologies for solar-hydrogen production”. Book title: “Membranes for Clean and Renewable

Power Applications”. Pages 325-346. Elsevier. Published by ENEA in 2014.

- “Coke-Resistant Catalysts for Methane Steam Reforming in the Presence of Higher Hydrocarbons”. Book title:

“Progress in Clean Energy, Volume 2”. Pages 469-480. Elsevier. Published by AUTH in 2015.

- “Criteria for palladium membrane reactor design: architecture, thermal effects and autothermal design”. Book

title: “Palladium Membrane Technology for Hydrogen Production, Carbon Capture and Other Applications:

Principles, Energy Production and Other Applications”. Elsevier. Pages 167-189. Published by Technion in

2015.

- “The use of electroless plating as a deposition technology in the fabrication of palladium-based membranes”.

Book title: “Palladium Membrane Technology for Hydrogen Production, Carbon Capture and Other

Applications: Principles, Energy Production and Other Applications”. Elsevier. Pages 43-67. Published by ECN

in 2015.

- “Palladium membranes in solar steam reforming”. Book title: “Palladium Membrane Technology for Hydrogen

Production, Carbon Capture and Other Applications: Principles, Energy Production and Other Applications”.

Elsevier. Pages 43-67. Published by ENEA in 2015.

Papers in Proceedings of Conferences/Workshops

- “Catalytic Activity and Selectivity of CeO2 supported Pt-Ni and Pt-Co catalysts for Bio-ethanol Steam

Reforming”. Proceedings of EFC11 - Rome, 14-16 December 2011. Published by UNISA & Processi Innovativi

in December 2011.

- “Hydrogen production for fuel cells applications through CeO2-supported bimetallic catalysts in bio-ethanol

steam reforming reaction”. Fuel Cells 2012: Science & Technology - A Grove Fuel Cell Event. Published by

UNISA & Processi Innovativi in April 2012.

- “Development of a multi-fuelled low-temperature steam reformer for hydrogen production”. Proceedings of the

5th World Hydrogen Technologies Convention (WHTC 2013). Published by ENEA in September 2013.

- “Time-on-stream stability of new catalysts for low-temperature steam reforming of biogas”. Chemical

Engineering Transactions. Published by ENEA, UNISA & AUTH in September 2013.

- “Low temperature methane steam reforming: Catalytic activity and coke deposition study”. Chemical

Engineering Transactions. Published by AUTH & ENEA in September 2013.

Page : 38/43



- “Steam Reforming of Ethanol to H2 over Bimetallic Catalysts: Crucial Roles of CeO2, Steam-to-Carbon Ratio

and Space Velocity”. Chemical Engineering Transactions. Published by UNISA & Processi Innovativi in

September 2013.

- “Modelling and Simulation of a Membrane Reactor for the Low Temperature Methane Steam Reforming”.

Chemical Engineering Transactions. Published by CERTH in September 2013.

- “Development of a Solar-powered, Fuel-flexible Compact Steam Reformer: the CoMETHy Project”. Chemical

Engineering Transactions. Published by ENEA in September 2013.

- “Complete methane conversion to pure hydrogen at low temperature using a membrane reactor”. PanHellenic

Symposium of Catalysis. Published by CERTH in October 2014.

- “High Thermal Conductivity Structured Bimetallic Catalysts for Low Temperature Ethanol Steam Reforming”.

Proceedings 2nd

International Congress on Energy Efficiency and Energy Related Materials (ENEFM2014).

Published by UNISA in November 2014.

- “How does radial convection influence the performance of membrane module for gas separation?”. Chemical

Engineering Transactions. Published by University La Sapienza & ENEA in May 2015.

- “Optimization of a membrane reactor for methane steam reforming at low temperatures”. PanHellenic Scientific

Conference in Chemical Engineering. Published by CERTH in June 2015.

- “Optimization of a Membrane Reactor for Low Temperature Methane Steam Reforming”. Chemical Engineering

Transactions. Published by CERTH in October 2015.

- “Hydrogen Production via steam reforming of a “model” bioethanol: study of coke formation over Pt-Ni/CeO2-

ZrO2”. Proceedings of EFC2015. Published by UNISA in December 2015.

Thesis & dissertations

- “Steam reforming di etanolo a bassa temperature su catalizzatori bimetallici supportati”. Thesis by D. Pisano,

UNISA. September 2012.

- “Analisi di proprietà termiche di schiume ceramiche a cella aperta”. Thesis by M.C. Quilli, University Campus

Bio Medico. February 2013.

- “Trasporto di calore in schiume solide ceramiche in carburo di silicio”. Thesis by F. Patrizio, University Campus

Bio Medico. May 2013.

- “Process Intensification by Simultaneous Reactor and Catalyst Optimization: Scaled Down Reformer”. Thesis by

Hadas Abir, Technion. August 2013.

- “Analisi sperimentale delle prestazioni di polveri catalitiche a base di Ni, Pt, Rh per lo Steam Reforming a basse

temperature”. Thesis by W. Montanari, University Campus Bio Medico. October 2013.

- “Analisi sperimentale delle prestazioni di un catalizzatore a base di Ni depositato su schiume solide in SiC per lo

steam reforming a basse temperature”. Thesis by F. De Cesaris, University Campus Bio Medico. October 2013.

- “Catalizzatori strutturati per la produzione di H2 via Steam Reforming di Etanolo”. Thesis by C. Ruocco,

UNISA. February 2014.

- “Sustainable hydrogen production by low-temperature thermochemical processes”. Thesis by M.A. Murmura,

University La Sapienza. January 2015.

- “Produzione di idrogeno mediante Steam Reforming di Bio-Etanolo a Bassa Temperatura”. Thesis by L. Bassi,

UNISA. March 2015.

- “Innovation in Hydrogen Production by Low Temperature Bio-ethanol Catalytic Steam Reforming”. Thesis by

F. Castaldo, UNISA. April 2015.

Page : 39/43



- “Pd Membrane Technologies for Scaled-down Pure H2 Generation: Process Design, Experimental Verification

and DFT-based kinetics”. Thesis by M. Patrascu, Technion. September 2015.

Patent applications

- Method and system for the production of hydrogen, European Patent (by Processi Innovativi), Application n.

EP12159998.9, Application Date: 16 March 2012.

Other dissemination activities

Website

- Publication of CoMETHy project website www.comethy.enea.it, 30 June 2012, Rome (Italy).

Flyers and booklets

- Flyer titled “Development of High Temperature Reactors” distributed at Fairs, conferences and IKTS-Website

by Fraunhofer IKTS in 2013.

- Flyer titled “Ceramic Foams for Chemical and Thermal Processes” distributed at Fairs, conferences and IKTS-

Website by Fraunhofer IKTS in 2013.

- Booklet about the outcome of the “International Joint Workshop on Palladium Membrane Technology Scale Up”

distributed by ENEA in February 2013.

- Flyer materials prepared for the FCH JU by ENEA with CoMETHy project information in March 2013.

- Flyer materials prepared for the FCH JU by ENEA with CoMETHy project information in April 2013.

- CoMETHy calendars with project pictures, description and results, distributed at the end of the project in

December 2015.

Organization of International Workshops

- Organization of the “International Joint Workshop on Palladium Membrane Technology Scale-up”, 12-14

November 2012, Rome (Italy).

- Organization of a special session titled “CoMETHy” in the “PRES’13 Conference – 16th

Conference of Process

Integration, Modelling and Optimisation for Energy Saving and Pollution Reduction”, 30 September 2013,

Rhodes (Greece).

- Organization of seminars and poster presentations around CoMETHy topics within the summer school

“Engineering of Membrane Reactors for the Process Industry”, 3-6 October 2013, Sarteano (Italy).

- Organization of the “Joint Workshop on Scale-up of Pd Membrane Technology – From Fundamental

Understanding to Pilot Demonstration”, 20-21 November 2014, Petten (the Netherlands).

Organization of technical tours

- Guided visits to CoMETHy pilot plant built at ENEA-Casaccia research center organized for several visitors and

groups in 2015.

http://www.comethy.enea.it/

Page : 40/43



Presentations at workshops, conferences and other events

- Oral presentation by ENEA titled “Attività ENEA nel campo della produzione di idrogeno” at the scientific

event “Le Celle a Combustibile e l’Idrogeno in Italia – Stato dell’Arte e Sviluppi Futuri”, 13 December 2011,

Rome (Italy).

- Poster presentation by UNISA titled “Hydrogen production for fuel cells applications through CeO2-supported

bimetallic catalysts in bio-ethanol steam reforming reaction” at the Conference “Fuel Cells 2012, Science and

Technology”, 11 April 2012, Berlin (Germany).

- Oral presentation by ENEA titled “Solar Steam Reforming of Natural Gas for Hydrogen Production” at scientific

workshop “CO2: valuable source of carbon”, 16 April 2012, Rome (Italy).

- Oral presentation by CERTH titled “Compact Multifuel Multifuel-Energy To Hydrogen Converter” at scientific

workshop “Hydrogen Energy for Life Conference”, 24 May 2012, Thessaloniki (Greece).

- Oral presentation by ENEA titled “Development of a multi-fuelled low-temperature steam reformer for hydrogen

production” at the “World Hydrogen Energy Conference, WHEC 2012”, 3 June 2012, Toronto (Canada).

- Oral presentation by UNISA titled “Renewable and clean hydrogen production through catalytic steam

reforming of from biomass-derived ethanol” at the Conference “CAT4BIO, Advances in Catalysis for Biomass

Valorization”, 8 July 2012, Thessaloniki (Greece).

- Poster presentation by UNISA titled “Bio-ethanol steam reforming reaction over bimetallic ceria-supported

catalysts” at the “15th

Conference Process Integration, Modelling and Optimisation for Energy Saving and

Pollution Reduction”, 25 August 2012, Prague (Czech Republic).

- Oral presentation by UNISA titled “Cerium oxide-supported catalysts for ethanol steam reforming reaction” at

the “8th

International Conference on f-Elements”, 26 August 2012, Udine (Italy).

- Oral presentation by ENEA titled “CoMETHy project” at the IEA/SolarPACES International Expert Group

Meeting “Solar Fuels”, 11 September 2012, Marrakech (Morocco).

- Poster presentation by ENEA titled “Development of a solar powered steam reformer for hydrogen production

using molten salts as solar heat carriers” at the “SolarPaces Conference 2012”, 11 September 2012, Marrakech

(Morocco).

- Oral presentation by UNISA titled “Sistemi bimetallici supportati per la produzione di idrogeno da bioetanolo”

at the "GRICU 2012 Conference", 16 September 2012, Montesilvano (Italy).

- Oral presentation by AUTH titled “Hydrogen production via low temperature steam reforming in the presence of

Ni and Rh catalysts” at the “HYDECON Scientific Workshop”, 17 October 2012, Thessaloniki (Greece).

- Oral presentation by UNISA titled “Investigation on the kinetic behaviour of bio-ethanol steam reforming over

bimetallic catalysts supported on cerium oxide” at the “IX International Conference Mechanisms of Catalytic

Reactions”, 22 October 2012, St. Petersburg (Russia).

- Oral presentation by AUTH titled “Hydrogen production via low temperature steam reforming in the presence of

Ni and Rh catalysts” at the “12th

Panhellenic Catalysis Symposium”, 25 October 2012, Chaina (Greece).

- Oral presentation by ECN titled “The use of electroless plating as a deposition technology in the fabrication of

palladium-based membranes” at the scientific workshop “Pd Membrane Technology Scale-up Workshop”, 12


- Oral presentation by GKN titled “Multi-layer design of sintered metal support structures for Pd-membranes” at

the scientific workshop “Pd Membrane Technology Scale-up Workshop”, 12 November 2012, Rome (Italy).

- Oral presentation by Technion titled “Criteria for Membrane Reactor Design: Thermal Effects, Autothermal

Design and Radial Gradients” at the scientific workshop “Pd Membrane Technology Scale-up Workshop”, 12


Page : 41/43



- Oral presentation by ENEA titled “Introduction to CoMETHy : Compact Multifuel-Energy To Hydrogen

converter” at the scientific workshop “Pd Membrane Technology Scale-up Workshop”, 12 November 2012,

Rome (Italy).

- Oral presentation by ENEA titled “Membranes in Solar Steam reforming” at the scientific workshop “Pd

Membrane Technology Scale-up Workshop”, 14 November 2012, Rome (Italy).

- Oral presentation by ENEA titled “CoMETHy Compact Multifuel-Energy To Hydrogen converter (FP7 - FCH

JU - 279075)” at the FCH JU Review Days 2012, 28 November 2012, Bruxelles (Belgium).

- Oral presentation by ENEA titled “Progetto CoMETHy – Compact Multifuel-Energy To Hydrogen converter” at

the scientific event “Energia e idrogeno: L’esperienza italiana nel programma europeo Idrogeno e celle a

combustibile”, 13 December 2012, Milan (Italy).

- Oral presentation by AUTH titled “Low temperature methane reforming over Ni and Rh catalysts supported on

lanthana modified ceria-zirconia” at the “10th

Natural Gas Conversion Symposium”, 2 March 2013, Doha

(Quatar).

- Oral presentation by AUTH titled “A study on the activity of Ni and Rh based catalysts on the low temperature

methane reforming” at the “8th

Panhellenic Scientific Conference of Chemical Engineering”, 23 May 2013,

Athens (Greece).

- Oral presentation by CERTH titled “Enhancement of Pure Hydrogen Production Through the Use of a

Membrane Reactor” at the “11th

International on catalysis in Membrane Reactors”, 7 July 2013, Porto (Portugal).

- Oral presentation by ENEA titled “Characterization of new developed catalyst for natural gas and biogas steam

reforming reaction” at the “International Congress of Energy and Environment engineering and Managemen”, 17

July 2013, Lisbon (Portugal).

- Poster presentation by ENEA titled “CoMETHy project” at the IEA – SolarPACES 27th

Annual Meeting Task II

“Solar Chemistry Research”, 16 September 2013, Las Vegas (USA).

- Poster presentation by ENEA titled “Development of a multi-fuelled low-temperature steam reformer for

hydrogen production” at the “5th

World Hydrogen Technologies Convention, WHTC 2013”, 25 September 2013,

Shanghai (China).

- Oral presentation by ENEA titled “Development of a Solar-powered, Fuel-flexible Compact Steam Reformer:

the CoMETHy Project” at the “PRES’13 Conference – 16th

Conference of Process Integration, Modelling and

Optimisation for Energy Saving and Pollution Reduction”, 30 September 2013, Rhodes (Greece).

- Oral presentation by ENEA titled “Time-on-stream stability of new catalysts for low-temperature steam

reforming of biogas” at the “PRES’13 Conference – 16th

Conference of Process Integration, Modelling and


- Oral presentation by AUTH titled “Low temperature methane steam reforming: Catalytic activity and coke

deposition study” at the “PRES’13 Conference – 16th Conference of Process Integration, Modelling and


- Oral presentation by UNISA titled “Steam Reforming of Ethanol to H2 over Bimetallic Catalysts: Crucial Roles

of CeO2, Steam-to-Carbon Ratio and Space Velocity” at the “PRES’13 Conference – 16th

Conference of Process

Integration, Modelling and Optimisation for Energy Saving and Pollution Reduction”, 30 September 2013,

Rhodes (Greece).

- Oral presentation by CERTH titled “Modelling and Simulation of a Membrane Reactor for the Low Temperature

Methane Steam Reforming” at the “PRES’13 Conference – 16th

Conference of Process Integration, Modelling

and Optimisation for Energy Saving and Pollution Reduction”, 30 September 2013, Rhodes (Greece).

- Lecture by Processi Innovativi titled “Compact Multifuel Energy To Hydrogen conversion (CoMETHy)”

(dealing with ethanol reforming) at the Summer School “Engineering of Membrane Reactors for the Process

Industry”, 4 October 2013, Sarteano (Italy).

Page : 42/43



- Lecture by Processi Innovativi titled “Compact Multifuel Energy To Hydrogen conversion (CoMETHy)”

(dealing with the reactor) at the Summer School “Engineering of Membrane Reactors for the Process Industry”,

4 October 2013, Sarteano (Italy).

- Lecture by ENEA titled “Methane Reformer Powered with Solar Heat” at the Summer School “Engineering of

Membrane Reactors for the Process Industry”, 4 October 2013, Sarteano (Italy).

- Lecture by Technion titled “Criteria for Membrane Reactor Design” at the Summer School “Engineering of

Membrane Reactors for the Process Industry”, 4 October 2013, Sarteano (Italy).

- Lecture by UNISA titled “Structured catalyst and support for membrane reactors” at the Summer School

“Engineering of Membrane Reactors for the Process Industry”, 4 October 2013, Sarteano (Italy).

- Oral and poster presentations by ENEA titled “CoMETHy Compact Multifuel-Energy To Hydrogen converter

(FP7 - FCH JU - 279075)” at the “FCH JU Review Days 2013”, 11 November 2013, Bruxelles (Belgium).

- Oral presentation by Fraunhofer IKTS titled “Catalytic activated foams at the IKTS booth” at the “Hannover Fair

2014”, 7 April 2014, Hannover (Germany).

- Oral presentation by GKN titled “Porous metal/ceramic composite structures Material for ultra-filtration and H2

separation membrane” at the “Materials Forum, Hannover Fair 2014”, 8 April 2014, Hannover (Germany).

- Oral presentation by AUTH titled “Coke resistant catalysts for methane steam reforming in the presence of

higher hydrocarbons” at the “International Conference on Clean Energy, ICCE-2014”, 8 June 2014, Istanbul

(Turkey).

- Poster presentation by AUTH titled “Low temperature steam methane reforming over Ni and Rh catalysts

supported on La/CeO2-ZrO2: the active role of CeO2 in methane activation” at the scientific workshop titled

“Fundamentals and applications of cerium dioxide in catalysis”, 11 July 2014, Udine (Italy).

- Oral presentation by ENEA titled “CoMETHy project” at the IEA – SolarPACES 28th


“Solar Chemistry Research”, 15 September 2014, Beijing (China).

- Oral presentation by ENEA titled “Multi-fuelled Solar Steam Reforming for pure Hydrogen Production using

Solar Salts as Heat Transfer Fluid” at the “SolarPACES 2014 Conference”, 19 September 2014, Beijing (China).

- Poster presentation by AUTH titled “Επίδραση των Προσμίξεων του Φυσικού Αερίου κατά την

Ατμοαναμόρφωση σε Χαμηλή Θερμοκρασία Παρουσία Καταλυτών Ni και Rh” at a scientific event, 16 October

2014, Palios Agios Athanasios Pellas (Greece).

- Poster presentation by ENEA titled “CoMETHy Compact Multifuel-Energy To Hydrogen converter (FP7 - FCH

JU - 279075)” at the “FCH JU Review Days 2014”, 10 November 2014, Bruxelles (Belgium).

- Oral presentation by Processi Innovativi titled “Optimization of porous metal support for Pd deposition” at the

“Joint Workshop on Scale-up of Pd Membrane Technology – From Fundamental Understanding to Pilot

Demonstration”, 20 November 2014, Petten (the Netherlands).

- Oral presentation by ENEA titled “Introduction to CoMETHy – Compact Multifuel-Energy To Hydrogen

converter” at the “Joint Workshop on Scale-up of Pd Membrane Technology – From Fundamental

Understanding to Pilot Demonstration”, 20 November 2014, Petten (the Netherlands).

- Oral presentation by Technion titled “Reactor modelling, simulation and operating parameters optimization” at

the “Joint Workshop on Scale-up of Pd Membrane Technology – From Fundamental Understanding to Pilot


- Oral presentation by Technion titled “Reactor modelling, simulation and operating parameters optimization” at

the “Joint Workshop on Scale-up of Pd Membrane Technology – From Fundamental Understanding to Pilot


Page : 43/43



- Oral presentation by Processi Innovativi titled “Solar assisted reforming and CCS in novel process schemes for

H2 production-techno economic assessment” at the “Joint Workshop on Scale-up of Pd Membrane Technology

– From Fundamental Understanding to Pilot Demonstration”, 21 November 2014, Petten (the Netherlands).

- Oral presentation by Processi Innovativi titled “Integrated membrane reactor testing and modelling” at the “Joint

Workshop on Scale-up of Pd Membrane Technology – From Fundamental Understanding to Pilot


- Oral presentation by ENEA titled “A new catalyst formulation for hydrogen production from biogas at low

temperature (the CoMETHy project)” at the “Energy & Materials Research Conference”, 25 February 2015,

Madrid (Spain).

- Lecture by ENEA titled “Molten Salts as Heat Transfer Fluids for Chemical Reactors” at the “SFERA II project

Training course for CSP professionals” 17 March 2015, Rome (Italy).

- Oral presentation by Fraunhofer IKTS titled “Catalytic activated foams at the IKTS booth” at the “Hannover Fair

2015”, 13 April 2015, Hannover (Germany).

- Oral presentation by ENEA titled “Solar Steam Reforming for Hydrogen Production using Solar Salts as Heat

Transfer Fluid” at the “23rd

SC meeting”, 27 May 2015, Wuhan (China).

- Oral presentation by AUTH titled “ΠΑΡΑΓΩΓΗ ΥΔΡΟΓΟΝΟΥ ΜΕΣΩ ΑΤΜΟΑΝΑΜΟΡΦΩΣΗΣ

ΜΕΘΑΝΙΟΥ ΣΕ ΧΑΜΗΛΗ ΘΕΡΜΟΚΡΑΣΙΑ ΠΑΡΟΥΣΙΑ ΚΑΤΑΛΥΤΩΝ Ni ΚΑΙ Rh” at a scientific event, 4

June 2015, Patra (Greece).

- Oral presentation by Fraunhofer IKTS titled “Catalytic activated foams at the IKTS booth” at the exhibition

“Achema Fair 2015”, 15 June 2015, Frankfurt (Germany).

- Oral presentation by ENEA titled “CoMETHy” at the “12th

International Conference on Catalysis in Membrane

Reactors (ICCMR12)”, 23 June 2015, Szczecin (Poland).

- Oral presentation by AUTH titled “Mechanistic implications on low temperature steam reforming of methane

over Ni/La/CeO2-ZrO2” at the “EuropaCat XII” Conference, 30 August 2015, Kazan (Russia).

- Poster presentation by ENEA titled “Solar steam reforming for hydrogen production using molten salts as solar

heat carriers” at the “WHTC 2015” Conference, 11 October 2015, Sydney (Australia).

- Oral presentation by ENEA titled “CoMETHy project” at the IEA – SolarPACES 29th


“Solar Chemistry Research”, 12 October 2015, Cape Town (South Africa).

- Oral presentation by ENEA titled “Development, demonstration and evaluation of a membrane reactor for solar

steam reforming using molten salts as heat transfer fluid” at the “SolarPACES 2015” Conference, 17 October

2015, Cape Town (South Africa).

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