Sustainable production of aromatics, especially benzene, toluene and xylenes (BTX), is essential considering their broad applications and the current global transition away from crude oil utilization. Aromatization of lower olefins, particularly ethene and propene, offers great potential if they are derived from more circular alternative carbon feedstocks such as biomass and waste plastics. This work aims to identify the preferred olefin feed, ethene or propene, for BTX production in a fixed-bed reactor. A commercial H-ZSM-5 (Si/Al = 23) catalyst was used as a reference catalyst, as well as a Ga-ZSM-5 catalyst, prepared by Ga ion-exchange of the H-ZSM-5 catalyst. At 773 K, 1 bar, 45 vol % olefin, 6.75 h−1, propene aromatization over the Ga-ZSM-5 catalyst exhibited higher BTX selectivity of 55 % and resulted in slower catalyst deactivation compared to ethene aromatization.
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Catalytic pyrolysis of crude glycerol over a shaped H-ZSM-5 zeolite catalyst with (partial) recycling of the product oil was studied with the incentive to improve benzene, toluene, and xylene (BTX) yields. Recycling of the polycyclic aromatic hydrocarbon (PAH) fraction, after separation from BTX by distillation and co-feeding with the crude glycerol feed, was shown to have a positive effect on the BTX yield. Further improvements were achieved by hydrogenation of the PAH fraction using a Ru/C catalyst and hydrogen gas prior to co-pyrolysis, and BTX yields up to 16 wt% on feed were obtained. The concept was also shown to be beneficial to other biomass feeds such as e.g., Kraft lignin, cellulose, and Jatropha oil.
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Bio-aromatics (benzene, toluene, xylenes, BTX) were prepared by the catalytic pyrolysis of six different black liquors using both in situ and ex situ approaches. A wide range of catalysts was screened and conditions were optimized in microscale reactors. Up to 7 wt % of BTX, based on the organic fraction of the black liquors, was obtained for both the in situ and ex situ pyrolysis ( T = 500-600 °C) using a Ga-modified H-ZSM-5 catalyst. The in situ catalytic pyrolysis of black liquors from hardwood paper mills afforded slightly higher yields of aromatics/BTX than softwood black liquors, a trend that could be confirmed by the results obtained in the ex situ catalytic pyrolysis. An almost full deoxygenation of the lignin and carbohydrate fraction was achieved and both organic fractions were converted to a broad range of (substituted) aromatics. The zeolite catalyst used was remarkably stable and even after 100 experiments in batch mode with intermittent oxidative catalyst regeneration, the yields and selectivity toward BTX remained similar. The ex situ pyrolysis of black liquor has potential for large-scale implementation in a paper mill without disturbing the paper production process.
MULTIFILE
This conference paper deals with various organizations and pilot initiatives regarding the theme of sustainability.
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This report focuses on the feasibility of the power-to-ammonia concept. Power-to-ammonia uses produced excess renewable electricity to electrolyze water, and then to react the obtained hydrogen with nitrogen, which is obtained through air separation, to produce ammonia. This process may be used as a “balancing load” to consume excess electricity on the grid and maintain grid stability. The product, ammonia, plays the role of a chemical storage option for excess renewable energy. This excess energy in the form of ammonia can be stored for long periods of time using mature technologies and an existing global infrastructure, and can further be used either as a fuel or a chemical commodity. Ammonia has a higher energy density than hydrogen; it is easier to store and transport than hydrogen, and it is much easier to liquefy than methane, and offers an energy chain with low carbon emissions.The objective of this study is to analyze technical, institutional and economic aspects of power-to-ammonia and the usage of ammonia as a flexible energy carrier.
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Wind and solar power generation will continue to grow in the energy supply of the future, but its inherent variability (intermittency) requires appropriate energy systems for storing and using power. Storage of possibly temporary excess of power as methane from hydrogen gas and carbon dioxide is a promising option. With electrolysis hydrogen gas can be generated from (renewable) power. The combination of such hydrogen with carbon dioxide results in the energy carrier methane that can be handled well and may may serve as carbon feedstock of the future. Biogas from biomass delivers both methane and carbon dioxide. Anaerobic microorganisms can make additional methane from hydrogen and carbon dioxide in a biomethanation process that compares favourably with its chemical counterpart. Biomethanation for renewable power storage and use makes appropriate use of the existing infrastructure and knowledge base for natural gas. Addition of hydrogen to a dedicated biogas reactor after fermentation optimizes the biomethanation conditions and gives maximum flexibility. The low water solubility of hydrogen gas limits the methane production rate. The use of hollow fibers, nano-bubbles or better-tailored methane-forming microorganisms may overcome this bottleneck. Analyses of patent applications on biomethanation suggest a lot of freedom to operate. Assessment of biomethanation for economic feasibility and environmental value is extremely challenging and will require future data and experiences. Currently biomethanation is not yet economically feasible, but this may be different in the energy systems of the near future.
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Paper sludge contains papermaking mineral additives and fibers, which could be reused or recycled, thus enhancing the circularity. One of the promising technologies is the fast pyrolysis of paper sludge, which is capable of recovering > 99 wt.% of the fine minerals in the paper sludge and also affording a bio-liquid. The fine minerals (e.g., ‘circular’ CaCO3) can be reused as filler in consumer products thereby reducing the required primary resources. However, the bio-liquid has a lower quality compared to fossil fuels, and only a limited application, e.g., for heat generation, has been applied. This could be significantly improved by catalytic upgrading of the fast pyrolysis vapor, known as an ex-situ catalytic pyrolysis approach. We have recently found that a high-quality bio-oil (mainly ‘bio-based’ paraffins and low-molecular-weight aromatics, carbon yield of 21%, and HHV of 41.1 MJ kg-1) was produced (Chem. Eng. J., 420 (2021), 129714). Nevertheless, catalyst deactivation occurred after a few hours’ of reaction. As such, catalyst stability and regenerability are of research interest and also of high relevance for industrial implementation. This project aims to study the potential of the add-on catalytic upgrading step to the industrial fast pyrolysis of paper sludge process. One important performance metric for sustainable catalysis in the industry is the level of catalyst consumption (kgcat tprod-1) for catalytic pyrolysis of paper sludge. Another important research topic is to establish the correlation between yield and selectivity of the bio-chemicals and the catalyst characteristics. For this, different types of catalysts (e.g., FCC-type E-Cat) will be tested and several reaction-regeneration cycles will be performed. These studies will determine under which conditions catalytic fast pyrolysis of paper sludge is technically and economically viable.
