A magnetically separable SO 4 /Fe-Al-TiO 2 solid acid catalyst for biodiesel production from waste cooking oil

A novel magnetic SO4/Fe-Al-TiO2 solid acid catalyst was synthesized for biodiesel production via the (trans)esterification of waste cooking oil (WCO). The nanocomposite catalyst was prepared by the sequential functionalisation of commercial rutile/anatase mixed phase TiO2 nanoparticles (NPs) with alumina as a buffer layer, and subsequently hematite to impart magnetic character, prior to sulfation with chlorosulfonic acid to introduce Brønsted acidity. XRD showed that the SO4/Fe-Al-TiO2 catalyst comprised titania (rutile and anatase phases), aluminium sulphate, and hematite nanoparticles, while electron microscopy revealed the layer-by-layer assembly of these components within the SO4/Fe-Al-TiO2 catalyst. FTIR confirmed the presence of surface sulphate groups SO42- and S2O72-/S3O102-, creating a predominantly Brønsted acid catalyst with high acid loading. The catalyst achieved 96 % fatty acid methyl ester (FAME) yield from WCO after 2.5 h of reaction at 90 °C, using 3 wt% of the magnetic catalyst, and a methanol:oil molar ratio of 10:1. SO4/Fe-Al-TiO2 was also effective for feedstocks containing up to 20 wt% of free fatty acid (FFA), and showed excellent stability for WCO (trans)esterification over 10 recycles

Waste to energy: A case study of Madinah city

The concept of energy from waste is getting popular nowadays across the globe, as being capable of producing multi fuels and value-added products from different fractions of municipal solid waste (MSW). The energy recovery technologies under this concept are anaerobic digestion (AD), pyrolysis, transesterification, refuse derived fuel (RDF) and incineration. This concept is very relevant to implementation in countries like Saudi Arabia, who wants to cut their dependence on oil. Moreover, the waste to energy becomes the imperative need of the time because of new governmental policy ‘Vision 2030’ that firmly said to produce renewable energy from indigenous sources of waste, wind and solar and due to given situations of Hajj and Umrah with massive amounts of waste generation in a short period. This study focused on two waste to energy technologies, AD and pyrolysis for food (40% of MSW) and plastic (20% of MSW) waste streams respectively. The energy potential of 1409.63 and 5619.80 TJ can be produced if all of the food and plastic waste of the Madinah city are processed through AD and pyrolysis respectively. This is equivalent to 15.64 and 58.81 MW from biogas and pyrolytic oil respectively or total 74.45 MW of continuous electricity supply in Madinah city throughout the whole year. It has been estimated that the development of AD and pyrolysis technologies will also benefit the economy with net savings of around US $63.51 and US$53.45 million respectively, totaling to an annual benefit of US $116.96 million. Therefore, in Saudi Arabia and particularly in Holiest cities of Makkah and Madinah the benefits of waste to energy are several, including the development of renewable-energy, solving MSW problems, new businesses, and job creation and improving environmental and public health

Spreadability of powders for additive manufacturing: a critical review of metrics and characterisation methods

Powder bed fusion methods of additive manufacturing (AM) require consistent, reproducible, and uniform layers of powder for the reliable production of high-quality parts, where properties of powder are central to achieving this. Among these properties, powder flowability and spreadability play critical roles in determining the quality of these powder layers. While extensive research has been conducted on powder flow and spreading behaviour, and on their characterisation, there is little critical comparison and review of these terms in the context of AM. Such a review is necessary to further develop and enhance our comprehension of spreading dynamics and its relation to powder properties in AM systems. This review paper aims to build a coherent understanding of the correlation between powder characteristics and spreading in powder based additive manufacturing and its impact on manufactured parts. It highlights the current progress in comprehending spreading dynamics, the influence of powder characteristics, environmental conditions, spreading system, and the development of testing tools to assess powder spreadability. Furthermore, the paper critically discusses the challenge of finding appropriate quantitative metrics and recent advances in the use of standardised methods for evaluating powder spreadability

Biodiesel production from used cooking oil using a novel surface functionalised TiO2 nano-catalyst

A novel, efficient and recyclable mesoporous TiO2/PrSO3H solid acid nano-catalyst was synthesised by the post-synthetic grafting of propyl sulfonic acid groups onto a mixed phase of a TiO2 support. The synthesised nano-catalyst was characterised using FTIR, SEM, TEM, XPS, N2 adsorption–desorption isotherms, XRD, DSC, TGA, and CHNS analysis. The percentage of loading for propyl sulfonic acid on the TiO2 support was calculated using CHNS analysis and TGA. The catalytic performance of TiO2/PrSO3H on the production of the fatty acid methyl esters (FAME) via simultaneous esterification and transesterification reactions from used cooking oil (UCO) has been studied. The effects of different process parameters showed that 98.3% of FAME can be obtained after 9 hrs of reaction time with 1:15 molar ratio of oil to methanol, 60 °C reaction temperature and 4.5 wt% catalyst loading. It was also found that the one-pot post-surface functionalisation strategy with hydrophilic functional groups (-SO3H) enhanced the acid strengths of the nano-catalyst providing more acid sites for the reactants, and improving the accessibility of methanol to the triglycerides (TG)/free fatty acids (FFAs) by increasing the pore volumes/sizes of the nano-catalyst. The solid acid nano-catalyst was re-used in four consecutive runs without significant loss of catalytic efficiency. Finally, the synthesised biodiesel fuel satisfied ASTM and EN standards

Functionalization of metallic powder for performance enhancement

The oxidation state and surface properties of powder particles play a major role in the final properties of powder manufactured components. In the present study, the coating of a non-stainless low alloy (SA508 Grade 3) steel powder was explored to protect it from progressive oxidation while also studying the effects on powder flowability and electrical charging. The protective coating was applied by magnetron sputtering of chromium. The surface chemistries of both as-received and Cr coated powders were studied using X-ray photo electron spectroscopy (XPS). Accelerated oxidation tests were carried out on both uncoated and Cr coated powders to study the effects of coating on oxidation resistance. Hard X-ray photoelectron spectroscopy (HAXPES) analysis was used to measure oxygen pick up near the surface, showing significant reductions for the case of the Cr coated powder. The conductivity of the powder was found to increase with Cr coating. The flowability of the powder was characterised by the tapped density, the angle of repose (AOR) and a powder rheometer, and it was found to improve with a Cr coating, which can be attributed to reduced tribo-electrical charging and reduced cohesivity of the powder particles

Synthesis of Ti(SO4)O solid acid nano-catalyst and its application for biodiesel production from used cooking oil

A novel solid acid nano-catalyst [Ti(SO4)O] was synthesised and used for the simultaneous esterification and transesterification of free fatty acids in used cooking oil (UCO) to produce biodiesel. The synthesised nano-catalyst was fully characterized by different analytical techniques. The XPS results clearly confirmed that the bidentate sulphate coordinated to the Ti4+ metal in the nano-catalyst product. Obtained d-spacing values from the experimental data of XRD peaks and the SAED pattern of produced nano-catalyst agreed well with the d-spacing values from the JCPDS-ICDD card numbers 04-011-4951 for titanium sulphate oxide or titanium oxysulfate crystal structures.This confirms the sulphate groups were within the crystalline structure rather than on the surface of titania nanoparticles, which has not been previously reported. It has been demonstrated 97.1% yield for the fatty acid methyl ester can be achieved usign the synthetised catalyst under a reaction time of 3 h, catalyst to UCO ration of 1.5 wt% and methanol to UCO ratio of 9:1 at 75 °C reaction temperature. The nano-catalyst showed a good catalytic activity for the feedstock containing ≤6 wt% free fatty acid. Furthermore, the catalytic activity and re-usability of the Ti(SO4)O for the esterification/transesterification of UCO were investigated. XRD results confirmed that the amount of View the MathML source species in the solid acid nano-catalyst slowly decreased with re-use after 8 cycles under optimised conditions, which is higher than the reusability of other functionalised titania reported in the literature. Finally, the biodiesel prodcued from this process satisfied the ASTM and European Norm standards

Biodiesel production from used cooking oil using novel solid acid catalysts

Damage to the environment as a consequence of exploration, production, imminent depletion, use of fossil fuels and concerns over climate change (increasing lifecycle greenhouse gas emissions), has increased the need for a more eco-friendly, renewable and sustainable source of energy. The level of biodiesel production has been increasing over the last twenty years, reflecting a rapid rise in demand due to its availability, renewability, lower gas emissions, non-toxicity, and its biodegradability. The impact of CO2 emissions on climate change, worldwide industrialisation, countries not having oilfields and need for a strategic and alternative source of energy have also driven an ever increasing demand. Biodiesel is mainly produced in industry by the transesterification process of triglycerides with low molecular weight alcohols using homogenous acid or base catalysts. However, the biodiesel industry faces some significant challenges; (i) high cost of biodiesel feedstock and (ii) the cost of biodiesel processing, including separation, purification and the neutralisation of by-products. These issues can be resolved with catalysts that are highly tolerant to moisture and free fatty acid (FFA) in feedstock oils. Solid acid catalysts have shown promise as catalysts in the simultaneous esterification and transesterification to overcome these issues. Here, lab-scale biodiesel production from simultaneous esterification and transesterification of used cooking oil (UCO) over different developed novel solid acid catalysts has been investigated. The synthesised catalysts, including TiO2/PrSO3H, Ti(SO4)O and SO_4^(2-)/Fe-Al-TiO2, were characterised via XRD, SEM, TEM, TEM-EDS, EDS-mapping, FT-IR, DRIFT-pyridine, TPD-MS with n-propylamine, TGA/FT-IR, CHNS analysis, DSC, TGA, N2 porosimetry, VSM and XPS. The effect of different process parameters on the fatty acid methyl ester (FAME) yield over different catalysts was also studied, including the effect of reaction temperature, mole ratio of methanol to UCO, time of esterification/transesterification, and amount of catalyst to UCO loading in order to achieve the optimum process conditions to obtain the highest FAME yield. Furthermore, a significant aim was to design a highly active, low cost, stable, easy recoverable, FFA tolerant and highly re-usable solid acid catalyst for biodiesel fuel production. It was found that SO_4^(2-)/Fe-Al-TiO2 performs well under optimum conditions of 2.5 h of reaction time, 3 wt% of synthesised magnetic catalyst to UCO ratio, 10:1 methanol to UCO mole ratio and 90 oC reaction temperature for simulations esterification and transesterification processes. A massive improvement in catalytic stability, easy recovery (using external magnetic field), high tolerance to FFA and water have been achieved via the introduction of alumina and iron oxides to the catalyst support. The synthesised biodiesels from UCO over different solid acid catalyst processes were analysed in accordance to ASTM D6475 and EN14214 standard methods to determine characteristic fuel properties such as kinematic viscosity, density, flash point, FAME content, LAME content, and acid number

A core-shell SO4/Mg-Al-Fe3O4 catalyst for biodiesel production

Catalytic transesterification of triglycerides and esterification of free fatty acids underpins sustainable biodiesel production, wherein efficient heterogeneous catalysts are sought to replace mineral acids. A robust, magnetic core-shell SO4/Mg-Al-Fe3O4 catalyst was synthesised by stepwise co-precipitation, encapsulation, and surface functionalisation. The resulting magnetically-separable catalyst has a surface area of 123 m2 g-1, uniform 6.5 nm mesopores, and a high total acid site loading of 2.35 mmol g-1. Optimum conditions for the (trans)esterification of waste cooking oil (WCO) over the sulfated solid acid catalyst were 95 °C, a methanol:WCO molar ratio of 9:1, and 300 min reaction to achieve 98.5 % FAME yield. Esterification of oleic acid to methyl oleate resulted in an 88 % yield after 150 min under the same reaction conditions. The magnetic solid acid catalyst exhibited good thermal and chemical stability and enabled facile catalyst separation post-reaction and the production of high quality biodiesel