Catalytic conversion of alcohol-waste vegetable oil mixtures over aluminosilicate catalysts

Abstract

Thermochemical catalytic conversion of ethanol-waste cooking oil (eth-WCO) mixtures was studied over synthesised aluminosilicate catalysts HZSM-5, FeHZSM-5 and NiHZSM-5. The thermochemical reactions were carried out at temperatures of 400° and 450°C at a fixed weight hourly space velocity of 2.5 h-1 in a fixed bed reactor system. Successful conversion of the eth-WCO mixtures was carried out over the synthesised catalyst systems and in order to fully understand the influence of the catalysts, several techniques were used to characterise the synthesised materials which include XRD, SEM, EDS, BET techniques. Results of the catalyst characterisation showed that highly crystalline solid material had been formed as evidenced by the high relative crystallinity in comparison with the commercial HZSM-5 catalyst at 2θ peak values of 7°- 9° and 23°- 24°. The introduction of metals decreased the intensity of the peaks leading to lower values of relative crystallinity of 88% and 90% for FeHZSM-5 and NiHZSM-5, respectively. However this was even slightly higher than the commercial sample which had a value of 86% with respect to HZSM-5 synthesised catalyst taken as reference material. There was no significant change in XRD patterns due to the introduction of metal. Elemental analysis done with energy dispersive spectroscopy showed the presence of the metal promoters (Fe, Ni) and the Si/Al ratio obtained from this technique was 38 compared to the target ratio of 50 set out initially in the synthesis. From the SEM micrographs the morphology of the crystals could be described as regular agglomerated sheet like material. Surface area analysis showed that highly microporous crystals had been synthesised with lower external surface area values ranging from 57.23 m2/g - 100.82 m2/g compared to the microporous surface area values ranging from 195.96 m2/g to 212.51 m2/g.

For all catalyst employed in this study high conversions were observed with values of over 93 %, almost total conversion was achieved for some samples with values as high as 99.6 % with FeHZSM-5 catalysts. Despite the high level of conversion the extent of deoxygenation varied with lower values recorded for FeHZSM-5 (25%WCO) at 400°C and NiHZSM-5

(75%WCO) at 450°C with oxygenated hydrocarbons of 19.5% and 19.33% respectively. The organic liquid product yield comprised mostly of aromatic hydrocarbon (toluene, p-xylene and naphthalene) decreased with the introduction of metal promoters with NiHZSM-5 producing higher yields than FeHZSM-5. For the pure waste cooking oil (WCO) feedstock the parent catalyst HZSM-5 had a liquid yield of 50% followed by NiHZSM-5 with 44% and lastly FeHZSM-5 had 40% at 400°C which may be seen to follow the pattern of loss of relative crystallinity. An increase in operating temperature to 450°C lowered the quantity of organic liquid product obtained in the same manner with the HZSM-5 parent catalyst still having the highest yield of 38% followed by Ni-HZSM-5 with 36% and Fe-HZSM-5 having a value of 30% for pure waste cooking oil feedstock which may be attributed to thermally induced secondary cracking reactions. For all catalyst systems with an increase in the content of waste cooking oil from 25% to 100% in the feed mixture there was a linearly increasing trend of the liquid product yield. HZSM-5 catalyst increased from 14% to 50% while FeHZSM-5 increased from 16% to 40% and NiHZSM-5 increased from 12% to 44% at a temperature setting of 400°C with lower values observed at 450°C.Results obtained in this study show the potential of producing aromatics for fuel and chemical use with highly microporous zeolite from waste material such as waste cooking oil forming part of the feedstock.