Project

BIZEOLCAT – Bifunctional Zeolite based Catalysts and Innovative process for Sustainable Hydrocarbon Transformation

Goal: In the past there have been a number of semi-industrial trials and even commercial processes to obtain on-purpose petrochemical feedstocks from methane and/or propane (more generally, C1-C4 hydrocarbons). However, their commercial success has been limited due to several reasons: from technical drawbacks (low conversions and selectivity) to economics (high capital investment and high operation costs are often obtained). Furthermore there is a need for lowering the carbon footprint of gas and oil industry, i.e. refining industry, contributing to an evolving scenario of sustainable economy in such field. BIZEOLCAT is addressing the use of light alkanes as raw material for specialty chemical industry and not as feedstock for fuels in the current oil refining process, becoming part of this transition.
BIZEOLCAT will aim developing 4 new processes of light alkanes (methane, propane and butane) conversion to olefins (propylene, butadiene) and to aromatics demonstrating higher performance, cost efficiency and environmental sustainability, using innovative methodologies for catalysts preparation and membrane reactor design. A refining company, TUPRAS, will run the pilot unit experiments. Two large companies, CEPSA and PERSTORP, will validate propylene and propylene and benzene, respectively as part of TR5 validation.
sLCA have demonstrated that the expected reduction in the greenhouse emissions related to the manufacturing of propane dehydrogenation developed within the project and also the Aromatization process in comparison to current Oleflex® and benzene production from a reformate plant is far over the target value of 20%.
A joint venture creation is part of BIZEOLCAT exploitation plan.
The BIZEOLCAT consortium comprises 14 partners: 2 technology centres, 2 research institutes, 3 universities, 1 Standardization body, 1 international association and finally 4 large industry and 1 SME from 10 countries (7 EU members, 2 associated countries to H2020, 1 third country).

Date: 1 January 2019 - 31 December 2022

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Project log

Ilaria Perissi
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Olefins are among the most important structural building blocks for a plethora of chemical reaction products, including petrochemicals, biomaterials and pharmaceuticals. However, their chemistry and chemical reactions still offer a wide range of research fields that can be better implemented and understood thanks to molecular modelling tools. In particular, the catalysis over precious metal or metal oxide catalysts has been put forward as an alternative way route to thermal-, steam- and fluid catalytic cracking. Bizeolcat partners from the National Institute of Chemistry (Slovenia) have extensive expertise in Multiscale system modelling as a tool to theoretically understand those processes. In the past decade, kinetic simulations studies have evolved from a rudimentary measurement-complementing approach to a useful engineering environment. By means of simulations, it is possible to predict various experimentally obtained parameters, such as conversion, activity, and selectivity, but it can help to simulate trends, when changing applicative operating conditions, such as temperature or pressure, or even support us in the search for the type of materials, their geometrical properties and phases for better functional performance. On the other side, powerful computers are necessary to process the high number of variables and parameters needed for the simulation and of course that is a world where dynamics are...very fast!
 
Blaz Likozar
added a research item
Olefins are among the most important structural building blocks for a plethora of chemical reaction products, including petrochemicals, biomaterials and pharmaceuticals. An ever-increasing economic demand has urged scientists, engineers and industry to develop novel technical methods for the dehydrogenation of parent alkane molecules. In particular, the catalysis over precious metal or metal oxide catalysts has been put forward as an alternative way route to thermal-, steam- and fluid catalytic cracking (FCC). Multiscale system modeling as a tool to theoretically understand processes has in the past decade period evolved from a rudimentary measurement-complementing approach to a useful engineering environment. Not only can it predict various experimentally obtained parameters, such as conversion, activity, and selectivity, but it can help us to simulate trends, when changing applicative operating conditions, such as surface gas temperature or pressure, or even support us in the search for the type of materials, their geometrical properties and phases for a better functional performance. An overview of the current set state of the art for saturated organic short chain hydrocarbons (ethane, propane and butane) is presented. Studies that combine at least two different dimensional scales, ranging from atomistic-, bridging across mechanistic mesoscale kinetics, towards reactor- or macroscale, are focused on. Insights considering reactivity are compared.
Ilaria Perissi
added an update
C123 , ZEOCAT-3D and  BIZEOLCAT projects funded in 2019 by Horizon 2020 Research and Innovation (RIA)  presented innovative and greener ways to convert alkanes into olefins and aromatics in a joint webinar.
More info:
 
Ilaria Perissi
added an update
To improve light alkanes dehydrogenation and separation, membrane reactors are the way: very selective towards hydrogen and with high flux, coupling mechanical and chemical stability. Membrane Reactors also show Environmental and economic convenience in propylene production in respect with other traditional methodologies.
 
Ilaria Perissi
added an update
Modelling study on multiscale dehydrogenations to investigate the role of surface oxidation on Catofin (propane/butane conversion in olefins) yields.
 
Ilaria Perissi
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Ilaria Perissi
added a research item
Propane (C 3 H 8) and butane (C 4 H 10) are short straight-chain alkane molecules that are difficult to convert catalytically. Analogous to propane, butane can be dehydrogenated to butenes (also known as butylenes) or butadiene, which are used industrially as raw materials when synthesizing various chemicals (plastics, rubbers, etc.). In this study, we present results of detailed first-principles-based multiscale modelling of butane dehydrogen-ation, consisting of three size-and timescales. The reaction is modelled over Cr 2 O 3 (0001) chromium oxide, which is commonly used in the industrial setting. A complete 108-step reaction pathway of butane (C 4 H 10) dehydrogenation was studied, yielding 1-butene (CH 2 CHCH 2 CH 3) and 2-butene (CH 3 CHCHCH 3), 1-butyne (CHCCH 2 CH 3) and 2-butyne (CH 3 CCCH 3), butadiene (CH 2 CHCHCH 2), butenyne (CH 2 CHCCH), and ultimately butadiyne (CHCCCH). We include cracking and coking reactions (yielding C 1 , C 2 , and C 3 hydrocarbons) in the model to provide a thorough description of catalyst deactivation as a function of the temperature and time. Density functional theory calculations with the Hubbard U model were used to study the reaction on the atomistic scale, resulting in the complete energetics and first-principles kinetic parameters for the dehydrogenation reaction. They were cast in a kinetic model using mean-field microkinetics and kinetic Monte Carlo simulations. The former was used to obtain gas equilibrium conditions in the steady-state regime, which were fed in the latter to provide accurate surface kinetics. A full reactor simulation was used to account for the macroscopic properties of the catalytic particles: their loading, specific surface area, and density and reactor parameters: size, design, and feed gas flow. With this approach, we obtained first-principles estimates of the catalytic conversion, selectivity to products, and time dependence of the catalyst activity, which can be paralleled to experimental data. We show that 2-butene is the most abundant product of dehydrogenation, with selectivity above 90% and turnover frequency above 10 −3 s −1 at T = 900 K. Butane conversion is below 5% at such low temperature, but rises above 40% at T > 1100 K. Activity starts to drop after ∼6 h because of surface poisoning with carbon. We conclude that the dehydrogenation of butane is a viable alternative to conventional olefin production processes.
T.A. Peters
added a research item
We report on the effect of butane and butylene on hydrogen permeation through thin state-of-the-art Pd-Ag alloy membranes. A wide range of operating conditions, such as temperature (200-450 • C) and H 2 /butylene (or butane) ratio (0.5-3), on the flux-reducing tendency were investigated. In addition, the behavior of membrane performance during prolonged exposure to butylene was evaluated. In the presence of butane, the flux-reducing tendency was found to be limited up to the maximum temperature investigated, 450 • C. Compared to butane, the flux-reducing tendency in the presence of butylene was severe. At 400 • C and 20% butylene, the flux decreases by~85% after 3 h of exposure but depends on temperature and the H 2 /butylene ratio. In terms of operating temperature, an optimal performance was found at 250-300 • C with respect to obtaining the highest absolute hydrogen flux in the presence of butylene. At lower temperatures, the competitive adsorption of butylene over hydrogen accounts for a large initial flux penalty.
Blaz Likozar
added a research item
As the global demand for propene (propylene) is increasing, classic commercial production processes are becoming unable to keep up. Non-oxidative dehydrogenation, although hitherto underutilised industrially, has been put forward as a viable and green alternative, which is already used in a few commercial processes. In this work, we present detailed first-principles calculations of this reaction over a chromium oxide catalyst, which is the cornerstone of the Catofin® process. A complete reaction pathway for the dehydrogenation of propane to propene and ultimately to propyne (methylacetylene) was considered. Cracking, which can yield C1 and C2 hydrocarbons, and the deactivation of the catalyst because of coking were also included and modelled. We used density functional theory calculations with the Hubbard model to study the structure of the involved intermediates, their adsorption and their interconversion to explain how chromium oxide catalysts facilitate this reaction and which processes cause their deactivation. We showed that the interaction of the hydrocarbons and molecular hydrogen with the catalytic surface is rather weak, resulting in low surface coverages, but increasing with multiple bonds present in hydrocarbons. Having constructed the potential energy surface with all the intermediates and the transition states linking them, we proposed a kinetic model for the reaction. Kinetic Monte Carlo simulations were performed at experimentally relevant temperatures (700–1000 °C), pressures (up to 10 bar) and inlet mixture compositions to study the kinetics of the reaction and discover the rate determining steps. As the reaction is highly endothermic, considerable conversions only occur at high temperatures. The accumulation of propene and propyne in the reaction mixture adversely affects the reaction rate and selectivity. Higher pressures increase the reaction rate but also increase the rate of coke formation, which poisons the catalyst. Deactivation of the catalyst has a strong temperature dependence and is caused by the accumulation of C∗and CH3CC∗on the surface, which are hard to remove even with hydrogen.
Ilaria Perissi
added an update
Download the presentation at the project website: www.bizeolcat.eu(Results>Presentations).
The BiZeolCat partner from TU/e (www.tue.nl) held a presentation within the conference session “Novel Reactors” concerning the employment of the membrane reactor technology in improving the yield of dehydrogenation and aromatization processes.
Indeed, direct dehydrogenation and aromatization processes require high operating temperatures (550-600 °C) and low pressures (0.5-2 bar) to reach a quite high yield of conversion. Nevertheless, existing industrial processes are characterized by very low performance, mainly due to the presence in the reaction chamber of coproducts that deactivate the catalysts.
An optimization possibility is represented by the membrane reactor technology, which deals with the combination of reaction and separation in a single reactor unit: here, the dehydrogenation reactions are performed continuously removing hydrogen as a by-product. This allows for both shifting the thermodynamic equilibrium towards the desired products and for lowering the catalyst deactivation rate, resulting in a less energy-intensive process than the traditional ones. Within the BiZeolCat the TU/e is designing a fluidized bed membrane reactor, with Palladium-based membranes, interconnected with a unit for the catalyst regeneration, used to be the main source of heat for the reaction itself. The features of this new reactor substantially contribute to the achievement of all the sustainability objectives of the BiZeolCat project.
 
Ilaria Perissi
added an update
The Bizeolcat’s partners from the Kemijski Inštitut - National Institute of Chemistry have recently calculated the entire reaction network for the propane dehydrogenation over chromium oxide catalysts. The DFT+U approach was used to account for the strong correlation of Cr and Cr2O3 (0001) surface was selected as the most stable one. The entire reaction network consists of 15 elementary reactions, which are shown in Figure 1.
The calculated reaction potential surface is in Figure 2. Kinetic modelling using kinetic Monte Carlo has also been performed. Using these data, we show that the reaction proceeds through the intermediates CH3CH2CH3, CH3CHCH3, CH3CHCH2 and does not proceed to propyne at normal operating conditions (850 K, 1.5 atm, non-oxidative). Hydrogen is formed as a side-product.
 
Ilaria Perissi
added an update
@BiZeolCat aims to develop new catalysts, based on Moderinite Framework Inverted (MFI) zeolites, that are characterised by a high density of anchoring points for the grafting of active metals (except chromium due its toxicity) to improve the sustainability of the following light alkanes reactions:
•Propane dehydrogenation in propylene (PDH)
•Butane and butenes mixtures oxidative dehydrogenation (BODH)
•Butane and butenes mixtures non-oxidative dehydrogenation (BDH)
•Alkane (C1 to C4) aromatization
Three series of different MFI zeolites’ based supports will be developed and used:
Series 1. Commercial MFI samples treated to increase the number of anchoring sites
Series 2. MFI topology synthesized with Si/Al ratio 1:100 and crystal size around 1-3 microns
Series 3. MFI topology with stacked nanosheet morphology (2-4 unit cells thickness) and Si/Al ratio around 1 and 50
Glad to show preliminary results for series 1 and 2.
Upper figure, series 1 -Commercial modified ;
Lower figures series 2 synthesized @UniverisyofOslo
 
Blaz Likozar
added a project goal
In the past there have been a number of semi-industrial trials and even commercial processes to obtain on-purpose petrochemical feedstocks from methane and/or propane (more generally, C1-C4 hydrocarbons). However, their commercial success has been limited due to several reasons: from technical drawbacks (low conversions and selectivity) to economics (high capital investment and high operation costs are often obtained). Furthermore there is a need for lowering the carbon footprint of gas and oil industry, i.e. refining industry, contributing to an evolving scenario of sustainable economy in such field. BIZEOLCAT is addressing the use of light alkanes as raw material for specialty chemical industry and not as feedstock for fuels in the current oil refining process, becoming part of this transition.
BIZEOLCAT will aim developing 4 new processes of light alkanes (methane, propane and butane) conversion to olefins (propylene, butadiene) and to aromatics demonstrating higher performance, cost efficiency and environmental sustainability, using innovative methodologies for catalysts preparation and membrane reactor design. A refining company, TUPRAS, will run the pilot unit experiments. Two large companies, CEPSA and PERSTORP, will validate propylene and propylene and benzene, respectively as part of TR5 validation.
sLCA have demonstrated that the expected reduction in the greenhouse emissions related to the manufacturing of propane dehydrogenation developed within the project and also the Aromatization process in comparison to current Oleflex® and benzene production from a reformate plant is far over the target value of 20%.
A joint venture creation is part of BIZEOLCAT exploitation plan.
The BIZEOLCAT consortium comprises 14 partners: 2 technology centres, 2 research institutes, 3 universities, 1 Standardization body, 1 international association and finally 4 large industry and 1 SME from 10 countries (7 EU members, 2 associated countries to H2020, 1 third country).