Design and Manufacturing of Catalytic Membrane Reactors by developing new nano-architectured catalytic and selective membrane materials
The aim of DEMCAMER project is to develop innovative multifunctional Catalytic Membrane Reactors (CMR) based on new nano-architectured catalysts and selective membranes materials to improve their performance, cost effectiveness (i.e.; reducing the number of steps) and sustainability (lower environmental impact and use of new raw materials) over four selected chemical processes ((Autothermal Reforming (ATR), Fischer-Tropsch (FTS), Water Gas Shift (WGS), and Oxidative Coupling of Methane (OCM)) for pure hydrogen, liquid hydrocarbons and ethylene production.
The DEMCAMER scheduled workplan will comprise activities related to the whole product chain: i.e. development of materials/components (membranes, supports, seals, catalyst,..) through integration/validation at lab-scale, until development/validation of four pilot scale CMRs prototypes. Additionally, three research lines dealing with: 1) the collection of specifications and requirements, 2) modelling and simulation of the developed materials and processes, and 3) assessment of environmental, health & safety issues -in relation to the new intensified chemical processes- will be carried out..
For a maximum impact on the European industry this research, covering the complete value chain of catalytic membrane reactors, can only be carried out with a multidisciplinary and complementary team having the right expertise, including top level European Research Institutes and Universities (8 RES) working together with representative top industries (4 SME, 5 IND) in different sectors (from raw materials to chemical end-users).
FUNDACION TECNALIA RESEARCH & INNOVATION
Parque Cientifico Y Tecnologico De Bizkaia, Astondo Bidea, Edificio 700
48160 Derio Bizkaia
Higher or Secondary Education Establishments
€ 1 344 034,55
José Luis Viviente (Dr.)
Sort by EU Contribution
VLAAMSE INSTELLING VOOR TECHNOLOGISCH ONDERZOEK N.V.
€ 855 144,50
UNIVERSITA DELLA CALABRIA
€ 750 947,20
TECHNISCHE UNIVERSITEIT EINDHOVEN
€ 663 924,90
AGENCIA ESTATAL CONSEJO SUPERIOR DEINVESTIGACIONES CIENTIFICAS
€ 501 052,50
FRAUNHOFER GESELLSCHAFT ZUR FOERDERUNG DER ANGEWANDTEN FORSCHUNG E.V.
€ 488 302,50
BORESKOV INSTITUTE OF CATALYSIS, SIBERIAN BRANCH OF RUSSIAN ACADEMY OF SCIENCES
€ 252 207,60
INSTITUT NATIONAL DE L ENVIRONNEMENT ET DES RISQUES INERIS
€ 359 802,25
RAUSCHERT KLOSTER VEILSDORF GMBH
€ 246 102
CERAMIC POWDER TECHNOLOGY AS
€ 349 710
HYBRID CATALYSIS BV
€ 327 227
€ 1 160 675,38
ABENGOA BIOENERGIA NUEVAS TECNOLOGIAS SA
€ 72 264
GUASCOR INGENIERIA S.A.
€ 6 889,62
€ 192 180
€ 206 880
TOTAL RESEARCH & TECHNOLOGY FELUY
€ 41 528
TOTAL PETROCHEMICALS FRANCE SA
€ 7 990,84
€ 73 137,16
Grant agreement ID: 262840
1 July 2011
30 June 2015
€ 10 834 742,24
€ 7 900 000
FUNDACION TECNALIA RESEARCH & INNOVATION
Greener and cheaper chemical processes
Grant agreement ID: 262840
1 July 2011
30 June 2015
€ 10 834 742,24
€ 7 900 000
FUNDACION TECNALIA RESEARCH & INNOVATION
Final Report Summary - DEMCAMER (Design and Manufacturing of Catalytic Membrane Reactors by developing new nano-architectured catalytic and selective membrane materials)
DEMCAMER is a 4 years project focussing on the development of novel catalyst materials and membranes for the validation of membrane reactors for four industrially relevant reaction systems, namely Water Gas Shift (WGS), Autothermal reforming of methane (ATR), Oxidative coupling of methane (OCM) and Fischer Tropsch synthesis (FTS).
The project brings together 18 partners covering the whole value chain, ranging from powder producers, to catalyst developers, membrane developers, reactor and system developers, service providers and end users.
New active, stable and selective catalysts have been developed within DEMCAMER for all the reaction system of interest and their production has been scaled up to kg scale (TRL5). At the same time new membranes for gas separation have been developed in the project; in particular, dense supported thin palladium based membranes have been developed for hydrogen separation from reactive mixtures These membranes have been successfully scaled up to TRL4 and used in various lab-scale reactors for WGS (using both packed bed and fluidized bed reactors) and FTS (using packed bed reactors) and in prototype reactors for WGS and FTS. Mixed ionic-electronic conducting membranes in capillary form have been also developed in the project for high temperature oxygen separation from air. These membranes can be used for both ATR and OCM reaction system to increase the efficiency and the yield of the processes. The production of these membranes has been scaled up to TRL3-4. Additionally, zeolite membranes have been developed for water separation and gas separation, although these membranes have not been validated in reactive conditions.
The project also developed adequate sealing techniques to be able to integrate the different membranes in lab-scale and prototype reactors.
Part of the project was devoted to multi-scale modelling of the materials and processes. At particle scale, DFT calculations have been used to evaluate and optimize the amount of active species in the catalysts. At membrane scale, phenomenological model have been used to evaluate and describe the permeation of gases through the membranes. Maxwell-Stefan approaches have been taken to better describe mass transfer limitations occurring in the boundary layer close to the membranes and inside the membrane pores. At reactor scale, both CFD and phenomenological models have been used to evaluate the reactor performances and optimize the operating conditions, while at system scale, flow-sheeting tools have been used to optimize the system performances.
Finally, four prototypes have been designed and constructed for the four reaction systems of interest. Of these prototypes, two based on Pd-based membranes have been successfully operated and the results can be used to validate the models and further develop the reactor design.
Of this large project, many of the milestones, especially on material (catalyst, supports, membranes) have been successfully achieved. Modelling and design milestones and construction of prototypes have been achieved as well. At larger scale the validation of all the processes was not possible for difficulties in membrane stability (especially the oxygen membranes).
Project Context and Objectives:
Process Intensification (PI), which is defined as "any chemical engineering development that leads to a substantially smaller, cleaner, safer and more energy efficient technology", is already the next revolution of the chemical industry. The need for more efficient processes, including further flexible engineering designs and, at the same time, increasing the safety and environmental impact of these processes, is pushing the industry to novel research in this field. The chemistry and related sectors have already recognised the benefits of PI and estimate a potential for energy saving of about 1000 kilo tonnes of oil equivalent (toe) per year using these processes.
The technology of membrane reactor plays an important role in PI and is based on a device combining a membrane based separation and a catalytic chemical reaction in one unit. Every catalytic industrial process can potentially benefit from the introduction of catalytic membranes and membrane reactors instead of the conventional reactors. According to SusChem (European Technology Platform for Sustainable Chemistry, Strategic Research Agenda 2005) more than 80% of the processes in the chemical industry worth approximately €1,500 billion, depend on catalytic technologies, and one the shorter-term (5-10 years) objectives of this Platform is to "integrate reactor-catalyst-separation design: integration and intensification of processes requires the development of new catalytic concepts which break down the current barriers (for example, low flux in catalytic membranes)".
The DEMCAMER project proposes an answer to the paradigm met by the European Chemical Industry: increase the production rate while keeping the same products quality and reducing both production costs and environmental impacts. Through the implementation of a novel process intensification approach consisting on the combination of reaction and separation in a "Catalytic Membrane Reactor" single unit.
The aim of DEMCAMER project was to develop innovative multifunctional Catalytic Membrane Reactors (CMR) based on new nano-architectured catalysts and selective membranes materials to improve their performance, cost effectiveness (i.e.; reducing the number of steps) and sustainability (lower environmental impact and use of new raw materials) over four selected chemical processes ((Autothermal Reforming (ATR), Fischer-Tropsch (FTS), Water Gas Shift (WGS), and Oxidative Coupling of Methane (OCM)) for pure hydrogen, liquid hydrocarbons and ethylene production.
The scientific and technical objectives to achieve this general objective were the following:
1. Development of novel catalyst materials with enhanced properties for improved catalytic conversion of the considered processes:
• A novel class of ATR catalysts based on perovskites generically represented by the formula La1-xSrxCryB’B’’yO3 where B’ and B’’ are selected from Ru, Fe, Mn, Co, Ni
• WGS catalysts based on Pt alloys supported on modified ceria and titania with improved catalytic activity.
• Development of OCM catalysts based on tungsten and promoted with manganese and rare earths and supported on conventional silica carrier.
• FTS: core-shell type bimetallic nano-catalysts based on Ru@Co, Co@Ru and Co@Fe
• Catalyst materials for each type of process obtained by POSS® nanotechnology.
2. To develop new membrane materials with improved separation properties, long durability, and with reduced cost for catalytic reactors designed for gas and water separation (ATR, WGS, OCM and FTS)
• Mixed ion electron conductive (MIEC) membranes (dense nanostructured coatings and hollow fibres) for O2 and H2 separation
• Metal based membranes for H2 production based on Pd-multi alloys and non-Pd alloys over the DOE target for 2015.
• Zeolite membranes based on defect free NaA stabilised sodalite (SOD) and FAU membranes with entrapped catalytic nano-sized particles
3. To understand the fundamental physicochemical mechanisms and the relationship between structure/property/performance and manufacturing process in membranes and catalysts, in order to achieve radical improvements in membrane reactors.
4. To design, model and build up novel more efficient (e.g. reducing the number of steps) membrane reactor configurations based on the new membranes and catalysts supported by simulation.
5. To validate the new membrane reactor configurations, at semi-industrial prototype level, in four selected chemical process (Autothermal Reforming (ATR), Fischer-Tropsch (FTS), Water Gas Shift (WGS), and Oxidative Coupling of Methane (OCM)) for pure hydrogen, liquid hydrocarbons and ethylene production.
6. To improve the cost efficiency of membrane reactors by increasing their performance, decreasing the raw materials consumption and the associated energy losses.
7. To enable the use of new raw materials (i.e.; convert non-reactive raw materials)
8. To assess the health, safety and environmental impact of the four CRM developed processes, a complete LCA of the developed technologies will be performed
The DEMCAMER work plan consisted of activities related to the whole product chain: i.e. development of materials/components (membranes, supports, seals, catalyst...) through integration/validation at lab-scale, until development/validation of four semi-industrial pilot scale CMRs prototypes. Additionally, three research lines dealing with: 1) the collection of specifications and requirements, 2) modelling and simulation of the developed materials and processes, and 3) assessment of environmental, health & safety issues -in relation to the new intensified chemical processes- were also carried out.
For a maximum impact on the European industry this research, covering the complete value chain of catalytic membrane reactors, was carried out with a multidisciplinary and complementary team having the right expertise, including top level European Research Institutes and Universities (8 RES) working together with representative top industries (4 SME and 6 IND) in different sectors (from raw materials to petrochemical end-users).
The DEMCAMER Project has been funded under FP7 Cooperation Specific Programme and Nanotechnologies, Materials and Processes NMP Theme.
4.1.3. Main S&T results/foregrounds
The DEMCAMER project was finalised by end of June 2015. Many progresses have been achieved in all stages of the value chain, from development of the catalysts, membranes, through lab-scale validation, to pilot scale development and testing. Modelling of the technologies also covered a wide range in level of detail from ab-initio calculation for membranes and catalysts, transport in membranes and catalytic membrane reactors simulation to complete process design and simulation. Pilot scale reactors were designed and tested with to different extent for the different processes. Complete assessments of the health, safety and environmental impact of the four CRM have been also addressed. Main S&T results/foregrounds achieved at the end of the project are detailed hereafter.
188.8.131.52. Catalytic Materials
Beneficiaries involved in the development of catalytic materials have designed several catalysts for each process (more than 100 catalyst samples) addressed in the project (ATR, WGS, OCM and FTS). Selection of DEMCAMER catalysts has been completed from catalytic screening tests together with a deep characterization of fresh and used samples in order to know the main structural and surface characteristics of the catalysts developed in DEMCAMER that have strong influence on the catalytic activity and stability. For each catalyst generation the most optimal compositions, in terms of activity and stability, were selected, prepared and supplied for testing at laboratory scale. From durability tests in laboratory reactions, the final optimal composition was selected, with emphasis on the catalyst nanostructure control, as final catalyst generation for scale-up and conformation for testing at pilot scale.
Final catalyst generation developed for each processes showed improved activity, selectivity and stability over catalytic formulations described in the state of the art achieving for all processes, therefore, the initial DEMCAMER objectives. Main results are the following:
The integration of the ATR reactor with membrane requires the use of catalysts with extreme thermal stability (structural/morphological resistances) and high resistance to carbon formation and deactivation by sulphur. Taking into account that ATR catalyst poisoning by sulfur and/or carbon is a structure sensitive reaction, the control of the electronic structure and size of the active metal surfaces has been the strategy followed in the development of innovative ATR catalysts with improved catalytic activity and stability. The ATR catalysts developed in DEMCAMER have been designed following two alternatives: the first, more innovative, based on catalysts with spatially distributed active metal components in a stable structure under reaction conditions and the second, more conventional, based on the modification of supported active metal clusters via the presence of other metals. Within the first alternative a novel class of ATR catalysts based on perovskites generically represented by the formula La1-xSrxCryB’B’’yO3 where B’ and B’’ are selected from Ru, Co, Ni, have been studied in DEMCAMER project. The second class of ATR catalyst was based on more conventional supported catalysts studying different ATR catalysts series varying the nature of active phase (Ni, Ru, Pt, Pd), the support (La2O3, CeO2-ZrO2, CeO2-Gd2O3) and the method of preparation (impregnation, sol-gel,...). Selection of ATR catalysts has been completed from catalytic screening in the ATR reaction of methane at laboratory level together with a deep characterization of fresh and used samples of all catalytic series prepared. The main structural and surface characteristics of the catalysts that have strong influence on the ATR catalytic activity and stability have been identified. From catalytic screening tests, durability tests and characterization of ATR catalysts, the optimal composition and preparation method of catalyst was selected. The final generation of ATR catalysts developed in DEMCAMER was based on Ni-Pd catalysts deposited on optimized ceria based support. The ATR catalyst developed at DEMCAMER showed very high activity/stability in the ATR reaction through: i) the control of synergistic Ni-Pd interaction and ii) optimization of the oxygen storage capacity of the cerium based support. The final generation of ATR catalyst showed activity, selectivity and stability in compliance with the DEMCAMER targets.
The ATR catalyst showed stable performance (methane conversion > 90%, hydrogen yield > 80%) and resistance to deactivation by sulphur and coke during 100 h of operation under reaction feed containing 50 ppm of H2S. Characterization of used catalysts showed excellent resistance to deactivation by carbon formation (no carbonaceous deposits on used catalyst).
The application of WGS catalysts in membrane reactors needs extensive research with the objective to improve catalyst activity, selectivity and stability since the membrane reactor conditions are very different from those encountered in a conventional shift reactor (temperature limit due to membrane stability, low partial pressure of steam and high partial pressure of CO2). In the development of WGS catalysts, innovative WGS catalyst formulations based on ceria and titania-based platinum catalysts have been studied in DEMCAMER project. In order to improve the WGS activity of catalysts two different strategies have been studied: (i) the modification of the electronic structure of the Pt metal surfaces by alloying surface Pt with other atoms and (ii) the modification of ceria and titania supports with basic or acidic dopants to promote redox sites for water dissociation during WGS reaction. Taking into account that the activity of Pt catalysts supported on TiO2 based supports is associated to the formation of Pt-support interfaces producing oxygen vacancies, it is clear that the preparation method of the WGS catalysts must also be controlled selecting methods that promote the formation of interfaces between Pt metal and support surfaces. Conventional preparation method based on controlled impregnation has been applied in order to tune both the Pt-support interactions and the type of Pt surface species (small metal clusters, Pt ions and Pt atoms at a metal cluster edge) present on catalyst surface. Selection of WGS catalysts has been completed from catalytic screening in the WGS reaction at laboratory level together with a deep characterization of fresh and used samples. From catalytic WGS screening tests and physico-chemical characterization data, the optimal composition and preparation method of WGS catalyst was selected. The final generation of WGS catalysts developed in DEMCAMER was based on Pt-Re catalysts deposited on optimized cerium-titanium mixed oxide support. The WGS catalyst developed in DEMCAMER project showed very high WGS activity and stability, showing an important improvement respect to the state-of-the art FeCr HT WGS commercial catalyst .
The integration of the OCM reactor with mixed ionic-electronic conducting membranes (MIECM) requires a good match between oxygen permeation rate through membrane and the OCM reaction rate on catalyst. The La-Sr/CaO and Mn-Na2WO4/SiO2 type catalysts were shown to be among the most suitable for OCM reaction, and therefore they have been used as base formulations to be optimized after a systematic synthesis, physicochemical and catalytic characterization studies in DEMCAMER project. The OCM catalysts developed in DEMCAMER have been designed following two strategies to improve OCM activity/selectivity/stability: (i) optimization of formulations and oxide contacts by application of different preparation methods and (ii) addition of dopants (Mn and rare earths) and promoters (S, P, Cl) to increase the selectivity to ethylene. At the first stage of the investigation, the optimal support type and value of metal content for Mn-Na2WO4/SiO2 OCM catalysts were established. Further, the modification of Mn-Na-W/SiO2 material by different promoters as structural and electronic modifying agents was performed. From these results, Mn-La- modified-Mn-Na2WO4/SiO2 OCM catalysts was selected as more perspective composition. The optimization of preparation techniques (incipient wetness impregnation, mixture slurry method), conditions of impregnation (temperature of impregnating solution), temperature of catalyst calcination (800oC, 850oC, 900oC, 1000oC) and pretreatment conditions of Mn-Na2WO4/SiO2 catalyst before OCM reaction (700 C O2/He; 800 C O2/He; 800 C He) were also optimized. The optimal OCM catalyst derived from DEMCAMER project provide high activity/selectivity (CH4 conversion=55%, C2 yield=22%) close to the best results in the state-of-the-art through i) optimal active phase exposition and ii) surface phase stability at high temperature.
The use of membrane reactors for FT reactions is an attractive option because this approach allows to control the heat of the reaction and to enhance the selectivity to long-chain hydrocarbons. Several concepts such as distributed hydrogen feed, water removal and forced-through flow membrane have been assessed using different reactor configurations. FTS membrane reactors require the integration of novel catalysts with higher catalytic performances that that of state-of-the-art Co-based catalysts in terms of C5+ productivity. To achieve this objective, several generations of FTS catalyst based on Ru-type have been prepared, characterized and tested for the FTS reactor in DEMCAMER project. The strategies followed in DEMCAMER project to improve activity/selectivity of FTS catalysts were: (i) the synthesis of core-shell ruthenium-containing bimetallic nanostructured catalysts of the type Ru@Co, Ru@Fe and Ru@Ni, (ii) the use of TiO2 as support to control the exposition and interaction of Ru active sites and, (iii) the addition of promoters (B) to increase the stability and selectivity to C5+. The first generation of FTS catalysts consisted in Al2O3 supported bimetallic particles M/Ru (M=Fe, Co or Ni) with core@shell (M@Ru) like structures. Based upon foreground knowledge other generation of FTS catalysts were also developed based upon B-doped Ru/TiO2. From catalytic screening FTS tests, durability tests and characterization of catalysts, the optimal composition and preparation method of FTS catalyst was selected. We succeed in preparing Co@Ru and Ru/TiO2 catalysts with very high FTS performances with initial and steady-state CH2 production rates of ca. 180 and 120 molCH2/h/at-grRu, respectively. In addition we found that the presence of B in B-Ru/TiO2 prevents catalyst deactivation by suppressing the formation of carbon deposits during the FTS reaction. The catalyst formulation B-Ru/TiO2 was selected as final generation catalyst achieving over this catalyst high values of activity, selectivity and stability in compliance with the DEMCAMER targets. It should be mentioned that hydrocarbon productivity with the final FTS catalyst formulation was higher than that reported for the benchmark Co-based and also identified in the industrial requirements for the intensification of targeted FTS reaction.
The B-Ru/TiO2 FTS catalyst developed in DEMCAMER project achieves a CO conversion above 60% maintained for up to 80 h on stream.
Beneficiaries involved in membranes have developed and supplied the membranes for the ATR, WGS, OCM and FTS lab-scale catalytic membrane reactors and pilot prototypes. The first part of the work has been devoted to the development of the materials for the Mixed Ion-Electron Conducting membranes, zeolite membranes, metallic supports and interdiffusion layers and selection of improved materials for the target application. Afterward, a selection has been made for the most promising ceramic and metallic porous supports as well as the interdiffussion barrier layers and of the improved membrane materials. Finally, the different membranes MIEC, metal based membranes for H2 separation and zeolite membranes for FTS were developed. Best membranes were selected for the pilot scale reactor after testing at lab-scale. Main results end of the project are detailed hereafter.
Screening production of feedstock perovskite powders for the development of hollow fibers for O2 and H2 permeation has been carried out. Protocols for large-scale production of the selected perovskite material have been set up. MIEC hollow fibers were developed by spinning and phase inversion methods. Following the lab-scale permeation tests O2 MIEC membranes have been selected for the prototype. For ATR and OCM more than 80 MIEC membranes in lengths of 10 cm and more than 40 in lengths of 5 cm have been produced and made available. However, when sealed did not have sufficient mechanical integrity to withstand mechanical stresses during the integration in the reactor prototype assemblies.
In addition MgO porous supports have been also developed. They could be used as supports for the development of MIEC supported membranes.
Metal based membranes for H2 production
Both metal based and ceramic based porous supports (Al2O3, TiO2, Mullite) have been developed in the frame of the DEMCAMER project.
To increase the mechanical properties of the ceramic Al2O3 porous supports thicker walls porous supports has been developed. Showing that improved properties of the 1 channel porous supports when increasing the wall from 1.5 to 3 mm (1-ch. tube OD 10 mm / ID 7 mm and 1-ch. tube OD 10 mm / ID 4 mm) could be achieved.
Pd-Ag membranes supported onto Al2O3 porous ceramic support have been developed by simultaneous electroless plating showing H2 permeances (>2.6 x 10-6 mol m-2 s-1 Pa-1) and selectivities (H2/N2 > 10,000) over the DEMCAMER target. Besides the membranes for the lab-scale tests, 33 membranes of 22-23 cm long (OD 10 mm – ID 7 mm) have been delivered for the WGS prototype. In addition, 5 Pd-Ag membranes of 15 cm long (OD 10 mm – ID 7 mm) with higher Ag content have been developed by a two-step process: simultaneous electroless plating of Pd-Ag and direct Ag deposition by PVD. These membranes have been delivered for testing the FTS H2 distributed feeding concept at small pilot scale.
Zeolite membranes were made as a thin layer of NaA, MFI and S-SOD inside of porous ceramic α-Al2O3 tubes (prepared by RKV) by a stepwise synthesis for water separation in FTS-CMR. Alongside this a carbon (C) membrane was developed and tested for this purpose. By end of the project, S-SOD did have low water selectivity because of a high defect rate and NaA was non stable in the test conditions. However, MFI and Carbon membranes show water separation properties suitable to be used for testing the water separation concept in FTS.
184.108.40.206. Lab-scale reactors
The beneficiaries involved on lab scale testing have designed, developed, construct and test different membrane reactors for the four reaction systems considered in DEMCAMER. The first part of the work has been devoted to the integration of catalyst and membranes in the new reactors. Particular attention has been paid to the selection of adequate sealing techniques that allow integration of the membranes without losing the membrane selectivity. Important was also the scalability of the sealing technique used. The most important results were related to the sealing of Pd-based membranes. Starting from very simple glass sealing we develop a system based on Swagelok/graphite that was scaled up to easily integrate tens of membranes in a single prototype. The latest results showed that this sealing could be used in WGS conditions achieving high purity of H2 (with lower than 20 ppm CO). As for the oxygen membranes both gold/ceramic and reactive air brazing (based on silver/copper) have been successfully demonstrated. An important lesson learned during DEMCAMER is to check the compatibility of the catalyst material with the membranes. We developed a protocol to test the membranes and catalyst very early in the phase of development and avoid problems with interaction between the two.
In the following few highlights are reported for the four reaction systems.
Lab scale WGS
The WGS packed bed membrane reactors were designed and built for hosting Pd-based membranes produced in the DEMCAMER project as well commercial ones. These membrane reactors were used in by considering three different combinations of membrane and catalyst:
a) Pd-Ag supported membrane + catalyst developed in the DEMCAMER project.
b) Pd-Ag supported membrane developed in DEMCAMER + commercial catalyst.
c) Pd-Ag commercial membrane + catalyst developed in DEMCAMER.
The combination of catalyst developed in DEMCAMER with thin (thickness 3.6 micron) Pd-based membrane resulted in a significant drop (98%) in membrane permeance, probably owing to interactions between membrane and catalysts. To overcome this drawback, a commercial catalyst was used with another membrane developed in DEMCAMER with the same characteristics of the previous mentioned and it was not observed any significant drop in performance. In addition, the combination between a Pd-Ag commercial membrane (100 micron thick) and the DEMCAMER catalyst did not show any drop in the membrane permeance. The membrane permeation properties were evaluated both with and without a catalytic bed, before and after reaction experiments. The measurements were carried out up to 6 bar at 360 and 400°C. No influence of catalyst presence and thermal cycles on membrane permeation properties was observed for the whole experimental run which lasted more than 2100 hours. The MR performance, also compared with simulation model developed in WP8 with a satisfactory agreement, resulted among the best in literature in terms of both CO conversion and hydrogen recovery (96% CO conversion and 84% H2 recovery @ 400 °C, 4 bar and a gas hourly space velocity of 2500 h-1. In parallel, concentration polarization measurements were also performed on the same reactor, confirming a polarization of ca 25% as mean value, occurring in the reactor.
In addition, very extensive validation tests of fluidized bed membrane reactors have been achieved in the project. We tested both commercial and DEMCAMER membranes for both single tube and multi-tube configurations and with different catalysts. Lately we integrated 5 Pd-based membranes in the reactor and operated continuously for up to 800 h. The results reported show that even in fluidization conditions the system is able to achieve flux and selectivities well above the DEMCAMER targets.
Best results show CO levels in the permeate side at levels of 5-7 ppm, which means that the produced hydrogen (recovered up to 60% in these tests) could be directly used in fuel cells. Additionally the catalyst does not react with nor stick to the membrane surface. These results fully demonstrate the WGS reactor concept.
Lab Scale OCM
A setup for OCM was built and the reactor demonstrated at lab scale. During the course of this final work on lab scale OCM CMRs the BCFZ hollow fibres used in different configurations often showed fractures along their length, most frequently in the sealing/contact zone. It is suspected that the main cause for this happening was the difference in thermal expansion coefficients (TEC) between the various components. Two types of catalyst materials obtained have been investigated for integration into the lab-scale OCM-CMR reactors 2wt.%Mn1.6wt.%Na3.1wt.%W/SiO2 and 2wt%Mn 1.6wt%Na 3.1wt%W 2wt%La/SiO2 (the latter being the third and final catalyst generation produced in DEMCAMER).
Lab scale ATR
Based on the permeation results on membrane sealing and experimental permeation tests at high temperature, first a few membranes have been tested for long term testing.
The best results have been obtained with a BSFZ membrane, with high fluxes and good stability for more than 1000 hr. It can be seen that after a fist activation period of around 50 hr (due to adjustments in the lattice structure of the MIEC) the membrane flux remain very stable even after repeated cooling down and heating up of the system.
Based on these promising results, a new membrane reactor for real validation has been designed and built. The reactor can accommodate 4 MIEC membranes with diameter of up to 4 mm and 10 cm length, and two porous membranes for steam addition.
Unfortunately, the new batches of membranes received were of a lower quality compared with the original ones. Most of these membranes just broke while applying the first layer of the sealing.
Lab Scale FTS
The evaluation of the PBMR H2-distributed feeding concept was also tested with Pd-Ag membranes developed in DEMCAMER. These membranes consist of a Pd and Ag layer (few microns) deposited at the outer layer of a ceramic tube. Both membranes have a length of Pd-Ag layer of 6 cm prepared over alumina tube with OD and ID of 10 and 7 mm. The FT catalyst used in all experiments with PBMR was the “final generation” FTS catalyst Ru-1B-Ti.
The most successful approach resulted when poor H2 syngas (H2/CO=1) was flown to the reaction chamber (inner side of the membrane) and the H2 needed to reach the right FTS stoichiometry (H2/CO=2) was admitted (and properly distributed) into the reaction chamber through the Pd-based membranes by flowing H2/He at the outer side of the membrane. Under the optimum reaction conditions (280 ºC), CO conversion recorded with the H2-distributed feeding PBMR concept for FTS with (H2/CO=1)inner is lower than that obtained in a conventional PBR feed with H2/CO =2 (37.9 vs 50.7 %) but significantly higher than that obtained in a conventional PBR feed with H2/CO =1 (14.1 %). Remarkably, product selectivity is positively affected by the “more adequate” H2-distribution attained in the PBMR and the selectivity towards the targeted high-molecular hydrocarbons increases by a factor of 4. In addition, a significant decrease of CH4 production (from 60 to 15%) is also observed (when compared to PBR at 280ºC). Under the studied experimental conditions membranes tend to deactivate after a few hours on stream (probably due to the formation of waxes) but their performance can be recovered by in situ thermal treatments under inert atmosphere.
220.127.116.11. Pilot scale prototypes
Pilot scale prototypes have been designed and assembled for each of the four industrial processes in DEMCAMER.
The autothermal reforming membrane reactor (ATR-MR) uses MIEC membranes to feed oxygen into the catalytic bed for reforming reaction. Oxygen is distributed along the reactor bed which reduces the temperature peaks compared to pre-mix feed. The reactor holds up to 80 membranes for oxygen feed. The reactor includes an auxiliary burner which is used for start-up and can also be used during operation to reach maximum production capacity of 5 Nm3/h of hydrogen in syngas. Compared to conventional ATR the system in DEMCAMER does not require the supply of pure oxygen, which for small scale plants becomes economically unfeasible considering cryogenic separation of air.
Following the construction of the ATR prototype the factory acceptance tests have been carried out (including HAZOP: Hazard and Operability). In parallel, a test protocol for the Autothermal Reformer Membrane (ATR-MR) prototype was defined. The FAT showed leakage from each bundle equipped with membranes. Due to failure of overall installed membranes, it was not possible provide the oxygen required for the autothermal operating condition. The system, therefore, has been operated and tested as a natural gas steam reformer. During the testing (ca. one week) the system was stable and allowed produce up to 3.3 Nm3 of H2 per Nm3 of NG feed. The novel developed catalyst exhibited good activity and stability: test results showed almost complete conversion (>99 %) and hydrogen productivity higher than 90%.
At the current point in time the DEMCAMER technology applied to the ATR reaction has failed to deliver results beyond the laboratory scale. Significant improvements would have to be made on the robustness of the MIEC membranes before any industrial application under safe conditions could be imagined.
The pilot prototype is designed for producing 5 Nm3/h grade 3.0 pure hydrogen in a water gas shift membrane reactor. The reactor separates hydrogen in-situ right where it is produced by means of WGS reaction. The complete setup includes the steam methane reformer which feeds the membrane reactor with real syngas rather than simulated gas from cylinders. Such setup allowed to evaluate the integration and definition of controls under realistic conditions.
Following the construction of the WGS prototype the factory acceptance tests have been carried out (including HAZOP: Hazard and Operability). In parallel, a test protocol for the Water Gas Shift Membrane Reactor (WGS-MR) prototype was defined.
The testing and validation of the WGS-MR prototype has been performed afterwards. The upgrading, by WGS reaction, of a syngas mixture in a membrane reactor integrated downstream a reformer has been proved on pilot scale. The results showed as the integration of the Pd-based membrane tubes allowed up to 20% of hydrogen recovery using only 63 % of the design membrane area. The hydrogen purity grade is of 2.5.
The system, tested for ca. 1000 hours at several operating conditions showed stable performance. During the testing time, an increasing trend of membrane performance has been overall observed. From the initial value, less than 10%, a maximum H2 recovery of 20% has been observed. The increase in WGS feed temperature promoted the H2 permeation.
The oxidative coupling of methane membrane reactor (OCM-MR) employs MIEC membranes just as the ATR reactor, and just as in such case the use of membranes avoids the use of expensive cryogenic separation for production of oxygen. The match between the temperatures for OCM reaction and permeation of oxygen between 800-900 °C is crucial for this concept. The system holds up to 20 MIEC membranes for oxygen separation.
Following the construction of the OCM prototype in WP6 the factory acceptance tests have been carried out (including HAZOP: Hazard and Operability). The FAT showed leakage from each bundle equipped with membranes. In parallel, a test protocol for the oxidative coupling of methane membrane reactor (OCM-MR) prototype was defined. Due to failure of overall installed membranes, it was not possible to test and validate the OCM-MR prototype.
At the current point in time the DEMCAMER technology applied to the OCM reaction has failed to deliver results beyond the laboratory scale. Significant improvements would have to be made on the robustness of the MIEC membranes before any industrial application under safe conditions could be imagined.
The pilot scale prototype for Fischer Tropsch in a membrane reactor was build and assembled into a test setup. Two concepts were evaluated in the project: (i) the use of water separation membranes for removal of water from the products which enhances the FTS reaction; (ii) the use of hydrogen permeation membranes for controlled distribution of the H2/CO ratio along the reactor. The pilot scale system used concept (ii) with 5 Pd-based hydrogen permeating membranes.
Following the construction of the FTS small prototype the factory acceptance tests have been carried out (including HAZOP: Hazard and Operability). In parallel, a test protocol for the FTS membrane reactor (FTS-MR) prototype was defined.
The testing of the FTS-MR prototype has been performed afterwards. According to the results the FTSMR prototype cannot be validated to obtain hydrocarbons higher than C5. The mainly products obtained were water, methane and CO2. This means that the reaction had progressed to the production of methane.
At the current point in time the DEMCAMER technology applied to the FTS reaction has failed to deliver results beyond the laboratory scale. The interest of the revised concept of controlled hydrogen addition has not been proven. Significant improvements should be made to validate a pilot scale both the water separation concept as well as the hydrogen distributed feeding concept for FTS.
The systems are controlled with PLC. The level of automation and integration vary from manual operation to complete automation. With the complete automation of the systems a test plan can loaded in the program allowing an automated schedule of tests. Most of the units included SCADA interface which allow the user to fully operate and monitor the system remotely.
18.104.22.168. Modelling and simulation
The activities modelling and simulation mainly concerned the modelling of the behaviour of membranes and catalysts, the transport in membranes as well as the simulation of catalytic membrane reactors (MR) for the four processes studied in the project: ATR, WGS, OCM, and FTS. Main progress towards objectives and significant results are detailed hereafter.
Ab initio calculation for membranes and catalysts
The aim was to develop an ab-initio investigations free from fitting and adjustable parameters for zeolite and metallic membranes, as well as for catalyst particles to be used in WGS, ATR, OCM and FTS.
- A computational procedure allowing the selection of zeolites on the basis of their ideal separation factor in a broad range of temperatures and different initial conditions was developed. It provided good results for analysing and optimizing crystalline nano-porous materials such as heterogeneous FAU zeolites adapt to Water Gas Shift gases purification via membrane processes.
- Ab-initio investigation on the H2 trapping as function of the composition of V-based alloys was carried out in this Task. An atomic cluster approach was used to estimate the most favourable arrangements of the hydrogen atoms in the considered alloys and the H2 trapping energies.
- Ab initio calculations for the core-shell Ru-Co nanoparticles were carried out with VASP software, chosen for its high computational efficiency and chemical reliability. DFT results pointed to a preferential core-shell formation on the Ru-Co system than in the Ru-Fe. Comparing the pure metals reactivity, the most active towards CO adsorption resulted the Ru (0001) surface that holds the CO molecule in a hole configuration, favouring its dissociation mechanism as a starting point of the FTS. Energetic and structural parameters results for the bimetallic surfaces were estimated.
- The possible structures of selected catalysts for ATR by using a combination of DFT and Hartree-Fock were identified.
- Ab-initio calculations were used to clarify the mechanism of OCM by tungsten center at silica possible structures of such center by building a cluster model of the α-cristobalite (111) surface.
Transport in membranes
The transport of gases through the various types of membranes developed in the project was also analysed:
- The transport in the MIEC membranes was modelled by a set of equations selected on the basis of the experimental permeation results obtained as a function of temperature and sweep gas flow rate. The expression for the description of the permeation through the membrane is available and the parameters for different membranes were determined. This expression (based on Xu’Thompson’s model) was used in the modelling of ATR and OCM.
- Hydrogen transport in the Pd-based supported membranes was modelled identifying the elementary steps of the permeation process. It allowed evaluating the hydrogen profiles along the membrane layers and in the gas phase layers adjacent to the supported membrane and to calculate quantitatively the influence of each step on the whole permeation process. The effects of both concentration gradient/polarization and inhibition on hydrogen permeation were correctly evaluated and used for MR simulation performance. The simulation results showed also to what extent these phenomena could affect the performance of the Water-Gas Shift reactor, thus providing useful information for prototype developed pilot-scale.
- The transport of light gases like H2, CH4, CO2 and N2 in zeolites membranes was investigated with a Maxwell-Stefan multicomponent approach, coupled to the Knudsen mechanism when required. The modelling and simulation analysis of the mass transport of multicomponent vapour/gas mixtures through defected zeolite layers was performed for different geometrics and operating conditions, among which a particular importance was paid to the influence of defect degree and defect size (i.e. defect mean pore diameter). The selectivity moderately decreases with increasing feed pressure and water vapour content and dramatically decreases with increasing defect size and degree were the main results. Therefore, just a small increment of defects over the zeolite surface determines a strong drop of the membrane performances in terms of separation factors owing to the presence of zones in which surface diffusion is replaced by the Knudsen mechanism and viscous flow. This analysis was of specific interest in FTS modelling and simulation, confirming the necessity of defect free zeolite membranes for this making attractive the FTS in an MR.
Simulation of the CMRs
The membrane reactors were simulated for the four processes of interest aiming to analyse their performance as function of the various operating parameters and the various configuration of the reactor.
- Methane partial oxidation reaction system at high GHSV for a LaCrRuO3 catalyst developed in WP3 was investigated in Fluidized bed MR. The kinetics of the new catalyst was studied and incorporated in the ATR model. The reactor was modelled and a sensitivity analysis was also carried out. The model was used to refine the ASPEN calculations.
- WGS reaction was investigated in fluidized bed MR and packed bed MR. In the first case, a typical 1D two-phase phenomenological model was developed and used for description of the experimental data of permeation and reaction at lab scale and for the design of the reactor for the pilot.
- The model for the simulation of the performance of a fixed bed MR was integrated with the information on the rate determining steps of the permeations and was used to analyse the performance of an MR for WGS reaction equipped of a Pd-based membrane having the characteristics of the membranes developed in the framework of WP4. The model took into account the concentration polarization phenomena occurring during reaction. After comparison with experimental results at lab scale it was used for the design of the packed bed MR at pilot scale.
- 1D numerical simulation model was defined to study and better understanding the OCM reaction in MIEC-MRs. The reactor was simulated and the results compared with different reactor configurations. The distributive feeding shows superior performances in terms of selectivity and yields compared with other reactor types. Additionally the air separation (which is a major cost in OCM plants) is integrated in the reactor achieving a double beneficial effect of the final economic performance of the reactor/system. This model was used for the MR design at pilot scale.
- 1D numerical simulation model to study the FTS catalytic MR was defined and validated for porous membranes, after incorporating the kinetics for the FTS catalysts obtained experimentally. Only the H2 feed concept was simulated so far because is the only concept that was proven at lab scale. This model was used for the MR design at pilot scale.
Process design and simulation
The simulations of the transport of membranes and lab-scale CMR were used as input in the design and simulation of the four processes of interest.
- A 1D model was coupled with ASPEN to evaluate the effect of the reactor size and design on the ATR process efficiency.
The results show that the reforming efficiency is approaching 70% (the equivalent reforming efficiency is about 76-77%) which is slightly lower than the system operated with fired tubular reforming as presented in (Martínez et al., 2013). However, this configuration was designed for small-medium scale applications and therefore the operating conditions, such as the steam production and the turbomachines are not as efficient as in the case of large scale H2 plant. The combination of the ATR-MR with HER allows recovering efficiently the heat of the syngas and reducing the heat duty for the reforming; however the cost of the entire system must be verified.
- A new process integrated with WGS-MR was designed where H2 separation and purification (PSA) is no longer required since more than 90% of H2 produced is directly recovered in the permeate stream with a purity of 99.99%. Two scenarios were investigated; they being vacuum or sweep gas on permeate. In both cases the effect of concentration gradients on the packed bed MR performance was taken into account. The hydrogen production and CO conversion of both configurations exceeded the targets set in the specifications. The “vacuum” configuration resulted the most promising in terms of both CO conversion and hydrogen recovery; therefore, it was selected by HYGEAR to implement the simulations of the pilot. Various options for retentate post processing were investigated all resulting in a reduction of the extra natural gas required by the burner. Overall, the integrated system showed positive assets in terms of CO conversion and pure hydrogen production as well as of raw material exploitation and energy consumption.
- A new process FTS carried out in an MR. The results show that the best conditions for operating the FTS-MR system with the Ru-B/TiO2 catalyst are 280ºC, 10 bar, H2/CO =2 and 7.500 mL(H2+CO)/gcat·h. The results obtained in the tests show that the use of packed bed MR for the H2 distributed feeding concept results in an increase of both the selectivity and CO conversion. With respect to the economic evaluation of the system, the minimum selling price of FTS diesel obtaining with the DEMCAMER technology was calculated and compared to conventional technologies prices. The simulation process had been done according to lab data, which means that in order to carry out scaling up; a big effort has to be done. This scaling-up effort had not been considered in the economic evaluation. The minimum selling price obtaining for the diesel was 0.9 €/L, similar price to the price of biodiesel.
- The plant performance reflecting the effect of using MR technology for the OCM process was investigated. The model was used to size some of the subcomponents, to aid the optimisation of the system and to help the explanation the measurements when the reactor is tested. A parameter study was performed with the optimized output set for C2 production and yield. Results show that the optimal operating conditions are at 870°C and O2/C feed ratio ~ 0.3. The model and optimization was also useful for the definition of the test plan in WP7.
Pilot scale modelling
Pilot scale models of the processes were extended from the preliminary version. When having results from pilot scale tests it was possible to validate and improve the models.
Control strategies for the pilot systems were developed. The first phase of the control definitions was through specification of Input/Output control and monitoring variables. The final definitions of the control strategies were expanded with the control logics as implemented in the PLCs. The ATR, OCM and WGS systems used local control with PLC and remote SCADA interface. The controls allow the systems to perform a predefined set of testing conditions following a test plan without the need of an operator. The FTS system used manual controls owing to the contained scale of the unit and reduced duration of the test plan.
22.214.171.124. LCA and safety issues
Comparison of CMR technologies to reference technologies from a life-cycle, safety and socio-economic perspective was performed. The socio-economic analysis focused more specifically on three configurations of hydrogen production, i.e. ATR process and WGS at large scale and small scale, in comparison with reference cases. The socio-economic analysis includes traditional economic indicators that aggregated monetary and non-monetary values on investment indicators. Based on time series analysis, main inputs included market prices such as natural gas, electricity, labour, water, catalysts and membranes were forecasted. As a result, an operational net present value (NPV) was estimated for each of the CMR and reference configurations. The socio-economic analysis integrated also ‘non-monetary costs and benefits’ and focused on environmental and health issues, including the LCA results. An “environmental net present value” (En-NPV) was then estimated for the different configurations. A sensitivity analysis has been performed. It concentrated on three aspects: the impact of a decrease of electricity price, the variation of carbon price assumptions – which is a sensitive parameter with regard to the En-NPV – and the extension of the CMR membrane lifespan from 1 year to 2 years and to 5 years – which impacted significantly the operational cash flow and the profitability in all configurations.
The following points can be outlined from the various assessments:
- In the case of the ATR process, the CMR process represented lower environmental impacts compared to reference technology for water withdrawal, due to the lower amount of steam needed, but appear less interesting for GHG emissions, due to a higher amount of natural gas feedstock, and higher electricity consumption. The impact of infrastructures on human health is also higher for the CMR technologies, due to the use of palladium for the catalyst. From a safety point of view, CMR and reference do not present significantly different risk levels, although toxicity hazard potential was higher for CMR technology in case of leaks located at the outlet of the reactor. However, it can be stated that a future CMR process with CO-shift in one step and no assistance of the ATR reactor with a burner, may be slightly safer than SMR process, provided that issues related to the current weak membranes are solved. With regards to socio-economic aspects, net present value (NPV) - configurations studied with membrane lifespan of 1 and 2 years and configurations based on an ATR process had lower NPV than, the reference case. Considering the environmental net present value (Env-NPV) - configurations studied with membrane lifespan of 1 and 2 years and configurations based on an ATR process have lower Env-NPV than the reference case. In the context of a low CO2 price assumption, performances of these two configurations can be considered as comparable.
- For the WGS, a small scale and a large scale process were considered.
o At large scale, the CMR technologies showed an interesting alternative for the GHG emissions, and for the impact on resources depletion. However, since the electricity consumption is higher for both CMR technologies, the water withdrawal, the impact on human health and the impact on ecosystem quality remain lower for the conventional WGS large scale technology. In addition to the higher electricity consumption of the CMR technologies, the infrastructures represent higher impact on human health due to the use of Palladium for the membranes. The large scale WGS CMR configuration with a membrane lifespan of 5 years showed a higher NPV than reference configuration. The Env-NPV of the large scale WGS CMR configuration with a membrane lifespan of 5 years is lower than the one calculated for the reference case. In the context of a low CO2 price assumption, performances of these two configurations can be considered as comparable.
o At small scale, the CMR technology represented equivalent or slightly higher impacts on climate change and on resource depletion, but as for the WGS large scale, the CMR technology showed much higher water withdrawal, impact on human health and impact on ecosystem quality. In fact, while the amount of natural gas consumed and the amount of steam is lower for the CMR technology, the electricity needed for the process is much higher than for the conventional technology. As far as the large scale technology is concerned, the infrastructures represented higher impact on human health due to the use of palladium for the membranes. The operational cost of the CMR technology does not compensate environmental costs. The comparison highlights the need of potential improvements for a membrane lifespan of 5 years.
Among configurations studied, the large scale system showed better socio-economic performance than the smaller ones (269 tonnes/year natural gas input instead of systems with an input within a range of 16-20 tonnes/year). Also, the importance of membrane lifespan for the overall performance of processes using CMR was underlined. The safety benefits were significant for CMR WGS technology compared to traditional WGS configuration, mainly because of the removal of hydrogen from the main stream. At both small and large scales, CMR WGS configurations are safer than the traditional WGS reference process.
- The only processes for which the CMR solution represents lower impacts for all the environmental indicators are the OCM process (for which the yield of the processes is exactly the same but with lower electricity and compressed air consumption) and the FTS process, showed a higher yield and higher selectivity of heavy hydrocarbons than the reference process. From a safety perspective, the OCM was compared to methanol-to-olefin process as no conventional OCM exists and it appeared that conventional process was safer than CMR technology. However, the MTO process is much more mature than OCM prototypes. For FTS process, the CMR technology presented a higher thermal runaway risk at large scale compared to reference technology. However, consequences of hazardous events look lower for CMR than reference, mainly because CMR technology operates at much lower pressure compared to its corresponding reference technology.
The results on the CMR technologies showed mixed trends compared to conventional technologies. The results could be better, worst or comparable from a sustainable point of view depending on the indicator considered (global perspective taking into account socio-economic aspects, safety and life cycle assessment). The conclusions that were drawn needed to take into account the following points:
- Work performed showed that there are various important aspects to be considered when comparing systems. First of all, the amount of feedstock is a crucial parameter to decrease the impacts of the process, in particular for the GHG emissions and the impact on resources depletion. However, it is necessary to also consider the heat and electricity consumption needed for the process, since an increase of one of those two parameters could offset the impact reduction obtained from a reduction of feedstock amount, and even reverse the conclusions. The electricity consumption is also one of the main contributors to the total water withdrawal, together with the steam consumption. Finally, a last parameter to be taken into account is the use of palladium for the infrastructures (catalyst and membrane), since it represents a large contributor to the impact on human health.
- The actual safety level of the final plants will of course depend on the implemented safety barriers. If efficient and reliable solutions can be implemented to immediately stop the flow in case of ruptured membranes (e.g. specific system developed by Hygear partner) and that membrane mechanical resistance is improved, provided that the CMR configuration does not create potential runaway concern at large scale, the overall safety level of the new CMR reactors should be either similar to the conventional technologies or even better compared to reference processes.
- Concerning the SEA, a number of recommendations for future improvements of CMR hydrogen production units were provided:
o Decarbonisation and overall environmental improvement by electricity: electricity consumption is a critical trigger for process improvement; it is noted electricity consumption is a key parameter in the variation of the DEMCAMER environmental net present value. A decrease of electricity consumption would significantly decrease the operating costs and – under the hypothesis of the actual energy mix in Europe – decrease significantly environmental impacts through decrease of climate change and air quality impacts.
o Taking into account climate change impacts: for the small scale ATR (CMR) case and the large scale WGS (CMR) case the inclusion of a carbon capture system may significantly improve the environmental impact of the technology and then, the social benefit of the technology – compared to reference technology;
Depending upon the scenarios and considered factors, the CMR technologies may be more interesting in some aspects and less in others compared to the reference technologies. The provided elements will help stakeholders to guide potential future deployment of CMR technologies by taking into account the deployment perspectives, the corrective measures and by being risk-informed.
4.1.4. Potential impact
Traditionally, Europe has been dominant in chemicals production, a position which has weakened in the past few years. Recognising the industry’s strategic importance, China and India have made successful efforts to build up large and increasingly sophisticated production facilities.
According to the European Chemical Industry Council (CEFIC), in 2012, with 556.6 billion € sales, the EU chemical industry has lost its first place in the ranking to Asia (1726 € billion), mainly due to the rise of China and India. This represents a decline in global market share from 30.5% in 2002 (€290 million) to 17.8% in 2012. Consequently, the EU’s share of global chemicals production is decreasing in several segments. Europe’s competitive position is at risk for his lack in competitiveness. The research and implementation of Process Intensification, such as catalytic membrane reactors, can help to increase the competitiveness of the EU Chemical Industry.
It is well understood that the reactor is the heart of any chemical process (which also influence size and costs of downstream separation processes), and therefore most of the chemical industry would benefit from the implementation of membrane reactors in their processes, integrating reaction and separation steps in one unit, reducing the energy costs and the environmental impact (lower by-products). An EU study indicates that the potential energy saving across the chemical sector using “Intensified Reactors” is about 11 PJ/year . These benefits could also be extended to other sectors, including glass and metals . On the other hand, by the integration of Reaction and Separation into one step will reduce the needs of materials down to a 40% compared to standard processes .
Hydrogen has been mainly used in the last 100 years as chemical product for different industrial applications (ammonia synthesis, methanol production, petroleum refining, etc.), with an annual production of about 55 million tons, increasing by approximately 6% per year. It is important to underline that most of the produced hydrogen (about 85%) is consumed where generated, while the remaining 15% is commercialized.
Almost a 50% of the global production for hydrogen is currently generated via steam methane reforming, therefore coming from natural gas with a 70-80% efficiency. About 30% of the hydrogen produced comes from oil/naphtha reforming from refinery/chemical industrial off-gases, 18% from coal gasification, 3.9% from water electrolysis and only a 0.1% from other sources. Above 95-97% of hydrogen today is produced from fossil fuels using high-temperature chemical reactions that convert hydrocarbons to a synthetic gas, which is then processed to make hydrogen. The conversion of natural gas into hydrogen takes place in catalytic reactors (reformers), in centralized locations with a typical hydrogen production rate of more than 10.000 Nm3/h. In this way of supplying hydrogen to the customers, two thirds of the energy content of hydrogen produced is wasted as compression energy and the required transportation energy. On-site hydrogen generation systems are intended to overcome these drawbacks.
One promising new concept proposed in DEMCAMER is the hydrogen membrane reformer, which combines the advantages of the reforming reaction with the separation of hydrogen. The DEMCAMER is basically a membrane-assisted reformer that circumvents the equilibrium limitations of traditional systems by selective removal of hydrogen. As such it allows higher yields at much lower temperatures than conventional systems and thus it reduces energy requirement practically to the theoretical minimum while also resulting in cost savings. Furthermore, this approach is directly answering to the increasing industrial demand in hydrogen (fertilizer industry, food processing, semiconductor industry, glass manufacturing, metal treatment, etc.), at pressure ranges of less than 10 bar with continuous hydrogen flows between 5 Nm3/h and 250 Nm3/h.
Another aspect of on-site hydrogen production is supporting the development of a hydrogen infrastructure and thus the transition of hydrogen into the market. A hydrogen infrastructure is required for the refilling of hydrogen-propelled vehicles as cars (both internal combustion and fuel cells), busses and fuel cell driven bicycles. The hydrogen produced by the on-site hydrogen generation systems is offered in the required hydrogen quality for the production process and at required product pressure (less than 10 bar).
Liquid Hydrocarbons production
Currently, the largest part of our energy used (electric power generation, heating, and transportation) is based on fossil fuels. In the last decade alternative and renewable energy resources became increasingly important for several reasons, mainly to combat greenhouse emissions, but also to ensure security of supply and a lower increase of costs for energy by reducing fuel import dependency. Sustainability in energy supplies may require new concepts with respect to feedstock, production and the final products. Improvements in overall efficiency of the technical process are necessary as these will directly lead to lower emissions of CO2, besides NOx and unburned hydrocarbons, thus contributing to a more environmental friendly energy production.
For the transport sector, several activities are ongoing leading to the operation of cars and trucks with natural or biogas, ethanol or biodiesel and to the development of fuel flexible and hybrid cars. A key for the success of these concepts is the availability of certified fuels to convince the consumer of buying these products, as to be seen in the introduction of E5 in Europe and E10 to gasoline in Germany. The road transportation sector is also becoming part of the efforts finding alternatives to fuels from fossil sources. The gasoline and diesel from crude-oil have been the only road fuel worldwide available since decades. The total consumption of transport fuel is about 30.4 million barrels per day.
Today, road fuels constitute about 55.5 percent of the global oil consumption and they are responsible for about 25% of the overall CO2 emissions worlwide . Besides, global population is growing and demand for mobility is increasing and a further increase of the road traffic is foreseen. The number of vehicles on the road is expected to double to more than two billion by 2050. If fuel consumption and hence CO2 emissions will continue to grow at the same rate, in 2050, the CO2 emissions would be almost 5 times higher than today.
Substitution of oil therefore needs to start as soon as possible and increase rapidly to compensate for declining oil production, expected to reach a peak within this decade. Climate protection and security of energy supply therefore both lead to the requirement of building up an oil-free and largely CO2-free energy supply to transport on the time horizon of 2050. The current energy policy agreed by the European Commision included a renewable energy roadmap proposing, among other measures, a binding 20% target for the overall share of renewable energy by 2020.
Decarbonising transport is a core theme of the EU 2020 strategy and of the common transport policy. The long-term perspective for transport in Europe has been laid out in the Commission Communication on the Future of Transport of 2009. The long-term objective of the European Union on CO2 emissions is an overall reduction of 80-95% by 2050. Production costs of biofuels vary widely across processes and geographical regions. The main differences in biofuel production costs are due to feedstock prices, the process energy used, and the prices received for by-products from the production process. Thus costs can be highly variable dependent on the various combinations used in each country. Cost estimates for 2nd-generation biofuels show significant differences depending on plant complexity and biomass conversion efficiency. Important factors include annual full-load hours of plant operation, feedstock costs and capital requirements. Accordingly, biofuel plants with a higher biomass-to-biofuel production ratio are typically able to accept higher biomass supply costs compared to less efficient plants. IEA confirms that the overall costs for synthetic fuel production from biomass (BtL technology) were about 1 €/L in 2010, with projected a reduction of 10-15% in these costs by 2015 and 20% by 2030.
Conventional GTL technology utilized by Shell and Sasol is only economic for plants producing 30,000 barrels per day or more. There are only five of these plants in the world, 3 operated by Shell and 2 by Sasol and only about 6% of the world’s known gas fields are large enough to sustain GTL plants of that size. In contrast, smaller scale GTL plants are designed to be economic at 1,500 b/d to 15,000 b/d, requiring only 15,000-150,000 million BTUs of gas per day as feedstock. Distributed GTL could unlock up to 50% of the remaining fields that conventional GTL cannot economically exploit. Shell recently announced the cancellation of their 140,000 b/d Gulf Coast GTL project due to cost considerations and market uncertainty over the long-term spread between gas and diesel prices. Shell’s plant would not have come online until the mid-2020’s which highlights the challenges in investing billions in a facility whose business model is based on arbitraging the long-term spread between gas and petroleum prices that are notoriously hard to predict.
The EIA estimates very challenging economic prospects for large-scale GTL projects. According to the EIA, GTL plants are more economic when configured to sell waxes and lubricating products because the chemicals market is much smaller than the fuel market. F-T waxes are used to produce candles, paints, coatings, resins, plastic, synthetic rubber, tires and other products. The EIA’s analysis suggests GTL developers should maximize wax production.
The membrane Fischer-Tropsch reactor addressed in DEMCAMER project could allow deployment to practically any region of the globe to make use of market gas reserves. Membrane based Fischer-Tropsch process focuses on the production routes of liquid fuels (Gas to Liquid, GTL) from Fischer-Tropsch synthesis (FTS) which is an ideal alternative to existing FTS process, which maximizes the gasoline output, minimizing the obtained paraffinic waxes and increasing the overall process efficiency.
The technology targeted in DEMCAMER project allows processing the mentioned Energy sources helping to reduce the environmental impact of gas flaring and municipal solid wastes and biomass wastes accumulation, producing motor fuels and energy efficiently (syngas could be derived from dry, steam, partial oxidation and autothermal reforming processes using natural gas, coal or biomass). The membrane FTS prototype in the DEMCAMER was targeting to improve the current state of the art F-T reactors by increasing the conversion achieved in the reactor, by suppressing the overreaction and by increasing the gas-liquid interface.
Ethylene, the simplest of olefins, is by far the most important raw material in the petrochemical industry. Direct applications include, among others, the three polyethylene plastics HDPE, LLDPE, and LDPE as well as petrochemical intermediates, which are in turn mainly used for the production of plastics. Other syntheses lead to the production of solvents, cosmetics, pneumatics, paints, packaging, etc. Global ethylene production capacity on January of 2013 was over 143 million tonnes per year (Mtpy) and is predicted to be growing with the annual rate of 3% until 2020. Detailed information about the recorded and predicted trends of ethylene production worldwide is available in several reports and reviews which suggest a dynamic and distributed market of this product all around the world. Around 30% of the total ethylene production is delivered by Asia-pacific region and the rest is produced mainly in North America, West Europe and Middle East.
Europe accounts today for nearly 20% of the global ethylene industry and it remains one of the largest markets for its derivatives, but it’s suffering a constant decline in capacity and consumption: last year the trend of falling ethylene production continued, driven not only by weak domestic demand but also lower cost imports. Europe's ethylene industry is largely based on disadvantaged naphtha feedstock, causing domestic producers to lose out to their peers in the US and the Middle East, whose crackers primarily use ethane. Moreover, the (Western) European petrochemicals industry is caught between the crisis in its markets (including the auto industry) and its higher material procurement costs.
As a result, ethylene, crucial for the whole plastics industry, was 1,5 times as expensive in Europe as in the United States in 2012. In order to address this negative trend, the EU industry is currently restructuring in order to achieve long-term survival: local producers are attempting to shift to lighter feedstocks to improve their cost position, however this is not an easy task as hurdles such as infrastructure, geographic location, co-product requirements and supply contracts could limit flexibility. Consequently, the difficult conditions have led to ethylene plant closures of over two million tons, with demand having fallen by around 3Mln tons.
The DEMCAMER project intended to concretely contribute to the improvement of the above-mentioned condition of the EU industry, by making a viable a more economic and efficient route for ethylene production, thus promising to re-establish the European position globally.
Benefits of producing Ethylene from natural gas
With an oil-to-gas price stably over 3 (even in these days of low oil price), it becomes more and more attractive to convert methane to higher hydrocarbons (including C2) that are conventionally produced by cracking of oil (fractions). Additionally, a large amount of natural gas is annually wasted as it is produced in remote areas where its conversion with conventional systems or its transportation is uneconomical. Worldwide many anti-flaring regulations are introduced. This market is expected to grow between 2020-2030 and no economic solutions are available. Many current developments still work on centralized solutions, combining many sources of associated gas into one stream with high CAPEX costs.
The sum of these factors clearly shows the high potential of the use of methane for ethylene production as a highly promising and concrete alternative for the EU process industry.
DEMCAMER project must offer a series of benefits in order to commercialize its products. The following table describes how DEMCAMER globally could contribute towards economic impacts:
Associated community societal objectives
Employment: Under the risk that the EU chemical industry could become soon a net importer of chemicals, SusChem outlined strategic R&D strategies aimed to help this sector in maintaining a large global share. DEMCAMER will contribute herewith by providing decisive step-changes in the bulk chemical industry that will not only safeguard its global market position and employment but also enable it to enter new markets and create new workplaces.
Quality of life & Health:
- Production cost savings of ~ 50% in 1st stage products will reach downstream suppliers of daily commodity goods (e.g. petrochemical, plastics) in the short-medium term.
- Smaller and more compact CMRs, with lower hazardous inventories, will lead to safer and more comfortable working conditions.
- Innovations in water membranes will positively impact the water treatment sector.
- More efficient use of raw material resources and minimization of by-products formation (less wastes) due to the high selectivity and conversion rates.
- CO2 capture/storage is an essential factor for fossil fuels to be part of the sustainable energy scenario, but is associated with high costs (capture ~70-80% of total costs). One primary EU objective is to decrease the capture costs from 50-60 to 20-30 €/t CO2. DEMCAMER will contribute by developing reactors with intrinsic CO2 capture, thus reducing the needs for downstream steps. These factors will allow a reduction in the global energy consumption of at least 7%.
- Fostering of green transportation and energy supply technologies due to lower H2 prices.
Actions were undertaken to create awareness of the DEMCAMER project, its objectives and anticipated and achieved results. These actions were carried on, continued through the whole project duration and are in progress after the project end as well. In addition, to the specific ones listed later on, they include
i) Publications in scientific journals. Overall DEMCAMER has already published more than 32 articles in peer-reviewed journals and there are still request for further publications. A detailed list is reported in Section A.
ii) Major international and national conferences attended by DEMCAMER participants and both poster and oral presentations given, as appropriate. Conferences attended in particular included regular events conducted in the frame of the above mentioned target groups and conferences organised or sponsored by organisations such as the “World Hydrogen Energy Conference” sponsored by the ”International Association for Hydrogen Energy IAHE” (http://www.iahe.org). Also, industry fairs as ACHEMA (Germany)) etc., have been attended by DEMCAMER participants. Important international conferences as e.g. the World Hydrogen Energy Conferences (2012 in Toronto, Canada) or the World Hydrogen Technology Conventions (2011 in Glasgow, Scotland) were also attended. Specific conferences related to the membrane reactors (i.e. International Conference on Catalysis in Membrane Reactors. Overall the consortium has contributed in more than 119 oral or poster presentation. A detailed list is reported in Section A.
iii) Six monthly newsletters on the project activities and dissemination. 8 newsletters have been released.
iv) Non-confidential presentations. 4 non-confidential presentations have been released.
v) Brochure and poster presenting the projects (including posters for main scientific and pilot pics).
vi) Information letter sent to platforms and national and international organizations to improve the visibility and the awareness of the project.
vii) Contacting other consortia working on projects related to the same R&D field for identifying common interests and joint activities.
viii) The training, dissemination and/or exploitation workshops. The following public workshops have been organised by DEMCAMER or jointly with other EC projects:
• The one day internal Exploitation Strategy Seminar day before the M6 meeting in Mol (Belgium).
• The scientific-oriented training workshop for PhD students and young researchers at Eindhoven, on January the 30th, 2013. The workshop has been organised by the two projects on membrane reactors granted by FP7 - Theme NMP: DEMCAMER and CARENA.
• The technology oriented workshop has been organised with other EC funded projects that share similar technological challenges. CARENA, CoMETHy and ReforCELL. The two-day workshop was held at the Energy Research Centre of the Netherlands ECN, Petten, The Netherlands on 20th-21st of November 2014. The workshop brought together more than 70 participants from 17 countries with a broad participation of industrial stakeholders besides representatives of research institutions and universities.
• The final dissemination and exploitation event which took place in Szezcin (Poland), on 22nd and 25th June 2015, as specific event during the International Conference on Catalysis in Membrane Reactors.
ix) Thesis: Five PhD thesis have been carried out in the frame of the DEMCAMER projects as well as ten MSc thesis.
x) Public website. A public website was available around month 4th. The website has been regularly updated with the latest news as well as the different public documents released by the consortium (i.e. public presentations, newsletters,...).
List of Websites:
Project public website with further information of the about the project and consortium and main contacts details are detailed hereafter:
Coordinator: Dr. José Luis Viviente
Scientific responsible: Associate Prof. Fausto Gallucci
Dissemination manager: Prof. Enrico Drioli
Exploitation manager: Dr. Leonardo Roses
Grant agreement ID: 262840
1 July 2011
30 June 2015
€ 10 834 742,24
€ 7 900 000
FUNDACION TECNALIA RESEARCH & INNOVATION
Deliverables not available
Grant agreement ID: 262840
1 July 2011
30 June 2015
€ 10 834 742,24
€ 7 900 000
FUNDACION TECNALIA RESEARCH & INNOVATION
Grant agreement ID: 262840
1 July 2011
30 June 2015
€ 10 834 742,24
€ 7 900 000
FUNDACION TECNALIA RESEARCH & INNOVATION