Ion-conducting ceramic membrane reactors for high-temperature applications

Governmental Investment in Low TRL in the United States: Funding Innovative Companies from Concepts to Systems

One stone two birds: Simultaneous realization of partial oxidation of methane to syngas and N2 purification via robust ceramic oxygen-permeable membrane reactors

In this project we will study a novel process concept, i.e., the use of ceramic membrane reactors in upgrading of coal model compounds and coal derived liquids. In general terms, the USC research team is responsible for constructing and operating the membrane reactor apparatus and for testing various inorganic membranes for the upgrading of coal derived asphaltenes and coal model compounds. The USC effort will involve the principal investigator of this project and two graduate research assistants. The ALCOA team is responsible for the preparation of the inorganic membranes, for construction and testing of the ceramic membrane modules, and for measurement of their transport properties. The ALCOA research effort will involve Dr. Paul K. T. Liu, who is the project manager of the ALCOA research team, an engineer and a technician. UNOCAL`s contribution will be limited to overall technical assistance in catalyst preparation and the operation of the laboratory upgrading membrane reactor and for analytical back-up and expertise in oil analysis and materials characterization. UNOCAL is a no-cost contractor but will be involved in all aspects of the project, as deemed appropriate.

In this Chapter the integration of separation and reaction in a membrane reactor is discussed. The use of a membrane reactor based on a silica pervaporation membrane has been studied for esterification reactions. The main purpose of the pervaporation membrane is to remove the water formed during the reaction, so that the equilibrium conversion can be exceeded. A general introduction on membranes is given with emphasis on separation performance and the integration with reactions. Furthermore, an outline of this thesis is presented. * A part of this chapter has been published in Separation and Purification Technology 22-23 (2001) 689-695, “Properties of high flux ceramic pervaporation membranes for dehydration of alcohol/water mixtures” by A.W. Verkerk, P. van Male, M.A.G. Vorstman and J.T.F. Keurentjes 2 Membrane reactors for pervaporation-assisted esterifications In this Chapter the main principles of combining a membrane separation process and an esterification reaction in a membrane reactor are discussed. In such reactions high temperatures and high pressures are often desirable to improve reaction kinetics. This implies that membranes have to be stable at these reaction conditions. Current membrane reactors predominantly use polymeric membranes, which have a limited stability at high temperatures. A promising alternative for these polymer membranes is the use of inorganic membranes. A number of different inorganic microporous membranes are currently available, including zeolite membranes, carbon molecular sieve membranes and silica membranes [Bein, 1996; Drioli and Romano, 2001]. Membrane reactors are being used for various purposes, ranging from controlled addition of reactants [Coronas and Santamaria, 1999], and localization of homogeneous catalysts [Nair et al., 2001], to the selective removal of one of the products. In this thesis the application of a membrane reactor in pervaporation-assisted esterification reactions is studied. The membrane reactor is used to exceed the equilibrium conversion by the selective removal of one of the reaction products. An inorganic membrane is used in combination with a mono-esterification and a di-esterification reaction, where the water produced during the reaction is selectively removed by a supported silica pervaporation membrane. Esterification reactions A class of industrially relevant equilibrium reactions are esterification reactions in which water is one of the products. Esters have various applications, ranging from plasticizers, surface-active agents, flavor and perfume materials, to solvents for the production of various chemicals. The annual production of these esters in the USA exceeded 5·10 tons in the year 1990 [Kirk-Othmer, 1994]. One of the main disadvantages of esterification reactions is that they suffer from a low conversion. In addition to the low conversion, the presence of a possible azeotrope between reactants and products also makes an esterification process more difficult to operate. A simplified reaction equation is given by: R(COOH)n + R(OH)m ! ester + H2O In practice, there are two methods to improve the conversion of equilibrium reactions. In the first approach, a large excess of one of the starting reagents is used. However, this results in a 3 Alcohols + carboxylic acids H2O dist. column relatively inefficient use of reactor space, and an efficient separation is required afterwards. In the second approach, the equilibrium conversion can be exceeded by removing one of the reaction products. For esterification reactions water is the most appropriate component that can be removed. There are a number of ways to remove one of the reaction products. Distillation is an appropriate technique for the removal of water from alcohols (see Figure 2a). However, for these systems the formation of an azeotrope is a potential drawback, which limits the (process) selectivity. Furthermore, in the case of the production of temperature-sensitive products or for biocatalytic conversions, the application of distillation is not feasible as a result of temperature constraints. Membrane separations can be considered a viable alternative for a number of cases. For the removal of water from organic streams, pervaporation seems to be the appropriate membrane technique. The main purpose of the pervaporation membrane is to remove the water from the reaction mixture in order the increase the product yield. In Figure 2b-d the various operation methods are shown. In this thesis the set-up depicted in Figure 2d has been chosen for the pervaporation-assisted reactions. Figure 2a. Conventional set-up for the production of esters.

05/00704 Distribution of aboveground biomass in corn stover

Recently the development of alternative feed stocks for fuels and chemicals has received growing interest to reduce greenhouse gas (GHG) emissions from a variety of sources. One large source of GHG emissions is long haul transportation of people and goods by ground, sea, and air. For the foreseeable future, long haul transportation will continue to depend on infrastructure compatible hydrocarbon fuels. The use of fuels synthesized from alternative renewable feed stocks such as biomass is one way to reduce the GHG emissions from these modes of transportation. Processes currently being commercialized to convert biomass into fuels and chemicals rely on high energy reactions that require catalysts and/or hydrogen. These restraints require centralized processes and result in high conversion cost. In order for biomass based fuel and chemicals to have a significant market penetration they need to compete economically with petroleum based streams, thus finding ways to reduce the cost of the biomass conversion is essential. As part of a project to produce infrastructure compatible fuel and chemicals Ceramatec is developing an electrochemical process, adapted from the Kolbe electrolysis. This process converts fatty acids from a biomass origin into long chain hydrocarbons, which can be further converted into lubricants and fuel using existing infrastructure. The conventional Kolbe electrolysis has been investigated since 1849 when Kolbe applied it to the synthesis of different hydrocarbons. The reaction pathway is generally considered to follow a mechanism in which a one electron oxidation at an electrode surface generates a radical and CO2. The radical can then undergo homo- or hetero- coupling with other radicals generated at the surface of the electrode.[1] While it has been extensively studied, the Kolbe electrolysis has never been widely commercialized because of low efficiency and yield caused by the high over potentials and reactivity of the electrolyte that are conventionally used. To circumvent these shortcomings, Ceramatec’s decarboxylation process uses a two compartment electrochemical reactor, where the compartments are separated by a ceramic membrane.[2] The separation afforded by the membrane (NaSelect®) is such that Na-ions are exclusively (>99% efficiency) transferred between the compartments, allowing different electrolytes to be used for the anolyte and catholyte. This affords: 1) the anolyte to be customized for the electrolysis of interest, and 2) the catholyte to be designed to have high conductivity and a low reduction potential. The latter helps reduce the overall cell potential, improving the energy efficiency of the process. The use of this membrane requires the anolyte to contain sodium salts of carboxylic acids, thus the anodic reaction can be represented generically by the reaction below. 2RCO2Na → R-R + 2CO2 + 2e -+ 2Na+ The Na-ions that are produced in the anolyte are then transferred across the membrane to the cathode compartment, where the corresponding reduction reaction occurs, as shown below using water as an example. 2H2O + 2e- +2Na+ → 2NaOH + H2 The sodium hydroxide produced in the cathode compartment can be used to saponify the fatty acid feed stock, making it a closed loop system for sodium. Also, the use of the two compartment reactor causes the distance between the anode and cathode to be separated into three regions: 1) the distance between the anode and the membrane, 2) the membrane thickness, and 3) the distance between the membrane and the cathode. This separation decreases the length of diffusion through the anolyte, permitting the anolyte conductivity to be sacrificed for improved oxidative stability. We have used these benefits to optimize the decarboxylation process, obtaining saturated hydrocarbons with yields and electrical efficiency over 80% while maintaining a low power consumption of 1.8 kWh/L ($0.18/L). These oxygen free hydrocarbons are produced using a modular process without the use of hydrogen. This process has also been scaled up in a self-contained portable pilot unit designed to produce over 1 L/day of saturated hydrocarbons from a tubular electrochemical reactor. The pilot unit is being used to address scale-up issues at a modular level and obtain data that is needed to help determine the economic feasibility of the process on an industrial scale. The results of this reactor optimization and scale-up will be discussed. Also, results using the membrane reactor to produce different high value chemicals will be shared. Acknowledgement This material is based upon research supported by the National Institute of Food and Agriculture, U.S. Department of Agriculture, under Agreement No. 2012-10008-20263.

Technology Readiness Levels at 40: A Study of State-of-the-Art Use, Challenges, and Opportunities

Studies of the Methane Steam Reforming Reaction at High Pressure in a Ceramic Membrane Reactor

Limitations and potentials of oxygen transport dense and porous ceramic membranes for oxidation reactions

Progress on Porous Ceramic Membrane Reactors for Heterogeneous Catalysis over Ultrafine and Nano-sized Catalysts

Ion-conducting ceramic membranes for renewable energy technologies

An experimental and theoretical investigation of a catalytic membrane reactor for the oxidative dehydrogenation of methanol

The IPCEI program at GF includes innovation along all technology readiness levels (TRLs). One example for very low TRL is the Reconficurable FET based on Schottky Barriers, close to 22FDX-processing. It enables camouflaging circuits for security applications, by e.g. providing NAND or NOR type cells, that can not be identified by reverse engineering. Another example is the development of a mmWave-variant of 22FDX allowing for operation frequencies typically in the 28-80 GHz regime, but also ranging up to 140 GHz. Characterisation of devices up to 3-4 times the operational frequency, a prerequisite for operation of the devices at these frequencies and showcases in the GHz regime for auto-Radar, 5 G and imaging radar are shown. These are just two examples, how the energy efficient 22FDX-technology at GF is enrichened by specialized variants and applications-specific- features.

The urgently needed phasing out of fossil resources requires that we should critically assess for which applications (virgin) carbon-based materials are essential and in which cases it is possible to dematerialise. Nevertheless, it is anticipated that a large fraction of the functionalities that are currently supplied by carbon-based materials will remain essential in the decades to come. Therefore, a transition to new high performance materials and products made from non-fossil renewable feedstock needs to be realized. In the past decade, various studies have pointed out that this transition can be realised by the utilisation of three particular alternative sources, exclusively. These are biomass, recycled materials and carbon dioxide (CO2). Out of these three pathways, the development of processes for the conversion of CO2 into polymers that can be used for plastics is lagging behind. This lag can largely be explained by the technical challenges that still exist for sourcing and subsequent conversion of CO2. As a result, the currently available technologies are not yet cost-effective. Nevertheless, driven by the increasing demand for fossil-free resources and increasing levels of CO2 taxation, a wide range of new chemical and microbial conversion technologies have been developed in the past decade, some of which are currently being investigated at an industrial level. This study identifies and assesses the most relevant sources and conversion routes for CO2-based materials from a technical perspective. A specific focus is placed on the conversion of CO2 into polymers that can be used in packaging, building and textile applications. The present study identifies specific CO2-to-product pathways and the five parameters that determine the technical, economic and ecologic feasibility of these routes, those being: • The CO2 content of the polymer, i.e., the fraction of carbon that originates from CO2 • The energy required for the conversion process(es) • The technical feasibility and yield of the conversion process which is reflected in the technology readiness level (TRL) number • The oxidation state of the carbon within the target polymer • The lifetime of a product that determines the potential of CO2 capture and storage. Based on the performed assessment, the electrochemical conversion of CO2 can be considered one of the most promising routes. Furthermore, all ‘CO2-to-product’ routes score low on the energy required. Currently, most CO2 conversion processes have a low TRL, which is not surprising given the relative new research area. Although multiple polymers (polyethylene, polypropylene and polyglycolic acid) score excellent on the CO2 content in the polymer, only applications in building and construction have a high CO2 capture potential due to their long lifespan. Fast moving consumer goods, like clothing and food packaging, have a short lifespan, and although these materials are partially recycled, there are inherent recycling losses. Overall, these products are considered to be a less effective carbon sink and as such, using CO2 as feedstock will have a lower impact for these applications. Finally, it is concluded that the economic potential of each of the identified CO2 conversion methods heavily relies on whether the technology can mature quickly and significantly, and on the extent to which they can be coupled to excess renewable energy streams in the future. Additionally, a heavy driver in the economics of these solutions will depend on the taxation of the carbon offset that is mitigated by a specific route and whether the potential for long term carbon capture will be taken into account for such taxation.

Abstract. In recent years, there has been a growing interest in recyclable and eco-friendly materials, driven by the need to develop components with complex geometries, variable thicknesses, and large dimensions, particularly in sectors such as building and automotive. Eco-Sustainable Sandwich Panels (ESSP), which combine lightweight cores with thermoplastic natural fiber-based composites, offer a promising solution to these demands by providing a balance between mechanical performance and sustainability. Despite their potential, ESSPs remain underexplored, with limited knowledge regarding the key factors necessary for their manufacturing. The low Technology Readiness Level (TRL) of these materials, along with challenges in ensuring reliable performance, particularly in terms of adhesion between skins and cores, hinders their broader industrial adoption. This study investigates the forming of Eco-sustainable Sandwich Panels (ESSP) consisting of an aluminum honeycomb core and skins made from flax fiber prepreg with a polypropylene matrix, manufactured by hot press molding. The aim is to evaluate the influence of process parameters on the adhesion between skins and core, which is critical for the mechanical performance of the panel. For this purpose, preliminary numerical analyses and destructive testing were made, and the results provide valuable insights for optimizing the production process of eco-sustainable sandwich panels and their potential industrial applications.