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A Spanish university has developed a 3D-printed heterogeneous monolithic catalyst with polymeric support allowing the acceleration of catalytic reactions in an optimal way at moderate temperatures, being especially suitable in preferential oxidation of carbon monoxide in hydrogen rich gases. Catalyst manufacturing companies interested in the commercial exploitation of this technology via patent licensing or technical cooperation agreements are sought.
Catalysts used in heterogeneous catalysis consist of an inert support on which a phase with catalytic activity (active phase) is deposited.
The most relevant supports are monoliths with cellular structure (honeycomb), which are characterized because they are easily manipulated to install or replace them, do not generate preferential paths in the fluid, are robust, have a great resistance to friction wear, have low pressure drops and great characteristics of heat and mass transference. These supports are used in a wide range of applications, among them, the preferential oxidation of carbon monoxide in hydrogen rich gases (CO-PROX). The CO-PROX is necessary for proper development of polymer-electrolyte membrane fuel cell.
The use of honeycomb monoliths in heterogeneous catalysis is limited both by the technology available for their manufacture and by the techniques available to support the active phases. The use of polymeric materials to manufacture catalyst supports is simple and economic; however, they have low thermal stability compared to ceramics. In addition, it is difficult to support active phases in polymeric substrates.
In order to overcome limitations described above, a Spanish research group has developed a new heterogeneous catalyst comprising a polymeric support formed by a set of channels on which the active phase is deposited homogeneously.
This polymeric support is monolithic with any geometry, and its main function is to disperse, stabilise and provide great mechanical properties to the active phase. In addition, it has a cellular structure and it is formed by a plurality of channels and surfaces that they may be smooth or have irregularities in their walls. These irregularities are full of active phase and facilitate the homogeneous distribution along the channel walls of the monolith, thus increasing its useful working surface.
The procedure to obtain this novel heterogeneous catalyst comprises the following steps:
1. 3D printing to give monolithic form to the thermostable polymeric resin catalytic support.
2. Immersion coating with a suspension comprising the active phase(s).
3. Rotate the product horizontally and dry it under dynamic conditions to ensure that the active phase continues distributed evenly.
4. Heat treatment in an inert atmosphere to remove volatile substances from the substrate and strengthen the bond between the active phase and the substrate.
5. Heat treatment in an oxidising atmosphere to improve the accessibility of the reagents to the active phases present on the channels.
Since the monolithic support is a polymeric resin that is photosensitive to ultraviolet light and stable up to 300ºC, it can be used in those catalytic applications occurring at a temperature lower than the degradation of the polymer, i.e. below 300ºC, for example, in CO-PROX. Then, this technology finds its application in the chemical and energy industrial sectors.
The university is mainly looking for manufacturers of catalysts interested in acquiring this technology for its commercial exploitation through license agreement. The company should be responsible for the development of the industrial prototype, the validation of the technology, its installation and its introduction into the market. The university will be ready to provide technical assistance in each step, if required.
However, the university would be also interested in establishing technical cooperation agreements to further develop the laboratory-scale prototype, to find new applications or to adapt it to the company’s needs. The goal of this type of cooperation would be increasing the technology readiness level for a future commercial exploitation of the patent. The university would offer its support based on their know-how; while, the partner sought would provide its expertise to help improve this invention. The university would offer this partner a preferential option to acquire this technology in exclusivity.
The main advantages of this novel polymeric catalyst are listed below:
• The presence of slits with prismatic geometry in the channels of the polymeric monolith facilitates the homogeneous distribution of the active phase.
• The homogeneity of the coating inside the channels prevents excess active phase in some and deficit in others, thus ensuring catalytic efficiency of the catalyst.
• It presents conversion and selectivity profiles similar to the current powder catalysts without supporting.
• It has been shown to have great catalytic activity for prolonged reaction times and, therefore, it is more robust than powder catalysts.
• It is more resistant to friction wear than current catalysts.
• It has low pressure drops.
• It has really great heat and mass transfer characteristics.
While, the most innovative aspects of this technology are:
• By using 3D printing it is possible to design and manufacture monolithic supports with complex geometries that allow to improve their performance.
• Polymeric resin monoliths have been designed and manufactured by 3D printing for using as catalyst supports in heterogeneous catalysis (Figure 3).
• A homogeneous coating of the monolith channels is obtained with an adequate distribution of the active phases.
• A single impregnation step is sufficient to cover homogeneously the surface of the monolith channels.
• A strong anchorage of the powder catalyst to the channels of the monolith is achieved thanks to the heat treatment in an inert atmosphere after impregnation, as well as an additional heat treatment in an oxidising atmosphere.
Catalytic activity tests have been successfully performed at laboratory level (Technology readiness level: 4-5) for the reaction of preferential oxidation of carbon monoxide in hydrogen rich gases (CO-PROX).
It can be concluded that the general behaviour of these novel catalysts is similar to the unsupported commercial powder catalysts, presenting qualitatively very similar conversion and selectivity profiles.
Furthermore, after 10 hours of reaction, both the conversion (95%) and the selectivity (90%) remain stable, thus demonstrating their great catalytic activity for prolonged reaction times (Figure 4).
Spanish patent applied for but not yet granted.
- Type of partner sought: Industry.
- Specific area of activity of the partner: chemical sector; energy sector; catalyst manufacturer.
- Task to be performed:
* In the license agreement: to buy a license for the technology, to further develop it to the industrial scale and to introduce it into the market.
* In the technical cooperation agreement: to provide their expertise in order to collaborate with the scientists on further development and improvements of the technology. The company should identify technical requirements and/or market and client’s needs in order to carry out further technical development so that the market readiness will be increased and the technology could be commercially exploited.