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.
DOCUMENT
Pyrolysis liquids from lignocellulosic biomass have the potential to be used as a feed for aromatics such as benzene, toluene, and xylenes (BTX) using catalytic upgrading with zeolites. We here report an experimental study on the conversion of various pyrolysis oil fractions to determine the most suitable one for BTX synthesis. For this purpose, the pyrolysis liquid was fractionated using several extraction/distillation steps to give four fractions with different chemical compositions. The fractions were analyzed in detail using nuclear magnetic resonance spectroscopy, elemental analysis, gas chromatography-mass spectroscopy, thermogravimetric analysis, Karl-Fischer titration, and gel permeation chromatography. Catalytic pyrolysis experiments were carried out using a tandem microreactor with H-ZSM-5 (23) as the catalyst. The highest BTX yield of 24% (on a carbon and dry basis) was obtained using the fractions enriched in phenolics, whereas all others gave far lower yields (4.4-9%, on a carbon and dry basis). Correlations were established between the chemical composition of the feed fraction and the BTX yield. These findings support the concept of a pyrolysis biorefinery, where the pyrolysis liquid is separated into well-defined fractions before further dedicated catalytic conversions to biobased chemicals and biofuels using tailored catalysts.
DOCUMENT
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
Plastic products are currently been critically reviewed due to the growing awareness on the related problems, such as the “plastic soup”. EU has introduced a ban for a number of single-use consumer products and fossil-based polymers coming in force in 2021. The list of banned products are expected to be extended, for example for single-use, non-compostable plastics in horticulture and agriculture. Therefore, it is crucial to develop sustainable, biodegradable alternatives. A significant amount of research has been performed on biobased polymers. However, plastics are made from a polymer mixed with other materials, additives, which are essential for the plastics production and performance. Development of biodegradable solutions for these additives is lacking, but is urgently needed. Biocarbon (Biochar), is a high-carbon, fine-grained residue that is produced through pyrolysis processes. This natural product is currently used to produce energy, but the recent research indicate that it has a great potential in enhancing biopolymer properties. The biocarbon-biopolymer composite could provide a much needed fully biodegradable solution. This would be especially interesting in agricultural and horticultural applications, since biocarbon has been found to be effective at retaining water and water-soluble nutrients and to increase micro-organism activity in soil. Biocarbon-biocomposite may also be used for other markets, where biodegradability is essential, including packaging and disposable consumer articles. The BioADD consortium consists of 9 industrial partners, a branch organization and 3 research partners. The partner companies form a complementary team, including biomass providers, pyrolysis technology manufacturers and companies producing products to the relevant markets of horticulture, agriculture and packaging. For each of the companies the successful result from the project will lead to concrete business opportunities. The support of Avans, University of Groningen and Eindhoven University of Technology is essential in developing the know-how and the first product development making the innovation possible.
Buildings are responsible for approximately 40% of energy consumption and 36% of carbon dioxide (CO2) emissions in the EU, and the largest energy consumer in Europe (https://ec.europa.eu/energy). Recent research shows that more than 2/3 of all CO2 is emitted during the building process whereas less than 1/3 is emitted during use. Cement is the source of about 8% of the world's CO2 emissions and innovation to create a distributive change in building practices is urgently needed, according to Chatham House report (Lehne et al 2018). Therefore new sustainable materials must be developed to replace concrete and fossil based building materials. Lightweight biobased biocomposites are good candidates for claddings and many other non-bearing building structures. Biocarbon, also commonly known as Biochar, is a high-carbon, fine-grained solid that is produced through pyrolysis processes and currently mainly used for energy. Recently biocarbon has also gained attention for its potential value with in industrial applications such as composites (Giorcellia et al, 2018; Piri et.al, 2018). Addition of biocarbon in the biocomposites is likely to increase the UV-resistance and fire resistance of the materials and decrease hydrophilic nature of composites. Using biocarbon in polymer composites is also interesting because of its relatively low specific weight that will result to lighter composite materials. In this Building Light project the SMEs Torrgas and NPSP will collaborate with and Avans/CoE BBE in a feasibility study on the use of biocarbon in a NPSP biocomposite. The physicochemical properties and moisture absorption of the composites with biocarbon filler will be compared to the biocomposite obtained with the currently used calcium carbonate filler. These novel biocarbon-biocomposites are anticipated to have higher stability and lighter weight, hence resulting to a new, exciting building materials that will create new business opportunities for both of the SME partners.
The ENCHANT project aims to clarify the differences between circular Calcium Carbonate (CCC) and grounded Calcium Carbonate (GCC), in order to expand the applications of the circular alternative CCC in the paint and coating industry. CCC is produced by pyrolysis from paper waste in an innovative process developed by the company Alucha Works B.V., and it can be applied again as filler or binder in consumer products (e.g. plastics, rubbers, paints and coatings) in a cost-effective manner. Products containing CCC have a higher content of circular resources, which minimizes their carbon footprint, and reduces the exploitation of primary resources. Performances of CCC in oil-based paints, however, is not optimal, due to a larger oil adsorption as compared to GCC. A physical and chemical characterization of CCC and GCC samples, including competitive oil-water adsorption measurements, would help Alucha to formulate a solution to match the properties of CCC and GCC, either adjusting the recycling process or applying a surface modification treatment to CCC. This would enable Alucha to expand the market for CCC, making oil-based formulation products more circular.
