Combining biocatalysts to achieve new phase change materials. Application to non-edible animal fat

"Formerly known as Journal of Molecular Catalysis A: Chemical"The thermal properties of various alkyl threo-9, 10-dihydroxystearates (DHSEs) prepared from non-edible fat were studied. Non-edible animal fat was hydrolyzed in a 93% yield with R. oryzae resting cells. Crude unsaturated fatty acids were recovered from the matter liquor resulting from a crystallization performed to achieve the saturated fatty acids. These unsaturated free fatty acids were epoxidized with 30% H2O2 using immobilized Candida antarctica Lipase-B (CAL-B) as biocatalyst. The epoxy ring was cleaved with hot water in the presence of tert-butanol (t-BuOH). Pure threo-9, 10-dihydroxystearic acid (DHSA) from animal fat was recovered by crystallization (51% yield). Subsequently, DHSA was esterified in alpha-limonene using biocatalysts yielding twelve DHSEs (58-90% yield). Differential scanning calorimetry (DSC) analysis of these esters revealed potential latent heats ranging from 136.83 kJ kg−1 to 234.22 kJ kg−1 and melting temperatures from 52.45 ◦C to 76.88 ◦C. Finally, the compounds with enthalpies above 200 kJ kg−1 were subjected to 100 and 1000 thermal cycles. These experiments showed that these products present good thermal reliability.GREA and DBA are certified agents TECNIO in the category of technology developers from the Government of Catalonia. We thanks to Subproductos Cárnicos Echevarria y Asociados S.L (Cervera, Spain) for supplying the non-edible fat. Moreover, the research leading to these results has received funding from the European Commission Seventh Framework Programme (FP/2007-2013) under grant agreement no PIRSES-GA-2013-610692 (INNOSTORAGE) and from the European Union’s Horizon 2020 research and innovation program under grant agreement no 657466 (INPATH-TES). The authors would like to thank the Catalan Government for the quality accreditation given to their research groups GREA (2014 SGR 123) and Agricultural Biotechnology Research Group (2014 SGR 1296). This work has been partially funded by the Spanish government (CTQ2015-70982-C3-1-R (MINECO/FEDER) and ENE2015-64117-C5-1-R (MINECO/FEDER). Aran Solé would like to thank Ministerio de Economía y Competitividad de España for Grant Juan de la Cierva, FJCI-2015-25741

Non-edible triacylglycerols as feedstock to prepare phase change materials and pressure-sensitive adhesives

Aquest programa de recerca està enfocat en l'aprofitament de triacilglicèrids vegetals i animals d'origen no comestible per preparar productes de valor afegit. Els triacilglicèrids són una font excel•lent per substituir el petroli ja que provenen de diferents fonts renovables i tenen propietats químiques i físiques interessants. No obstant, tot i que són renovables, el seu ús s’ha de discutir. D'una banda, a causa del origen dels triglicèrids, ja que els comestibles competeixen directament amb l'alimentació. Per tant, s'han fet servir dues fonts diferents com són el greix animal no comestible dels escorxadors municipals i un oli vegetal no comestible provinent d'un arbre de cultiu Xinès (Vernicia fordii) anomenat oli de tung. D’altra banda, part de la química involucrada en la preparació de productes "bio-based" té efectes negatius per al medi ambient ja que genera grans quantitats de residus i normalment es fan servir altes temperatures i reactius perillosos. Per superar aquest problema, aquest treball aprofita les condicions suaus i la reusabilitat dels biocatalitzadors com les lipases imobilitzades i les "resting cells". A més, van ser una prioritat els reactius químics no perillosos, les practiques generadores de pocs residus i els reactius barats per tal de completar la transformació del greix animal no comestible i l'oli de tung.Este programa de investigación está enfocado en el aprovechamiento de triacilgliceridos vegetales y animales de origen no comestible para preparar productos con valor añadido. Los triacilgliceridos son una fuente excelente para substituir el petróleo ya que provienen de distintas fuentes renovables y tienen propiedades químicas y físicas interesantes. No obstante, aunque son renovables, su uso tiene que discutirse. Por un lado, debido al origen de los trigliceridos, ya que los comestibles compiten directamente con la alimentación. Por lo tanto, se han usado dos fuentes distintas como son la grasa animal no comestible de los mataderos municipales y un aceite vegetal no comestible proveniente de un árbol de cultivo Chino (Vernicia fordii) llamado aceite de tung. Por el otro lado, parte de la química involucrada en la preparación de productos “bio-based” tiene efectos negativos para el medio ambiente ya que genera grandes cantidades de residuos y normalmente se usan altas temperaturas y reactivos peligrosos. Para superar este problema, este trabajo aprovecha las condiciones suaves y la reusabilidad de los biocatalizadores como las lipasas inmovilizadas y las “resting cells”. Además, fueron una prioridad los reactivos químicos no peligrosos, practicas generadoras de pocos residuos y reactivos baratos para completar la transformación de la grasa animal no comestible y el aceite de tung.The research described in this document is focused on the utilization of vegetable and animal non-edible triacylglycerols to prepare value added products. Triacylglycerols appeared to be an excellent source to substitute petroleum since they come from distinct renewable sources and have various interesting chemical and physical properties. Nevertheless, although they are renewable, their utilization as starting materials to produce chemicals can cause some concerns. On the one hand, edible triacylglycerols compete directly with food and feed. To overpass these concerns, two distinct sources of non-edible triacylglycerols were used such as non-edible animal fat from slaughterhouses and vegetable oil from a Chinese three crop (Vernicia fordii) known as tung oil. On the other hand, some of the chemistal procedures involved in the preparation of bio-based products have negative effects on the environment since high amount of wastes are generated and high temperatures and hazardous reagents are commonly employed. To overcome these issues, the present work takes advantage of the milder conditions and reusability of biocatalyst such as immobilized lipases and resting cells. Additionally, non-hazardous chemicals, low generating waste practices and cheap reagents were a priority to complete the transformation of non-edible animal fat and tung oil

Fatty acid eutectic mixtures and derivatives from non-edible animal fat as phase change materials

A set of compounds from non-edible fat waste was prepared and their thermal behavior was studied. The fat was hydrolyzed and crystallized in a simple and robust process to yield palmitic acid-stearic acid (PA-SA) mixtures. The PA-SA mass ratios determined by GC-FID (gas chromatography-flame ionization detection) were similar to those reported for eutectic mixtures of PCMs (phase change materials). DSC (differential scanning calorimetry) results indicated that the melting and solidification temperatures were around 55 °C and 52 °C and the latent heat of the crystallized fractions measured was around 180 kJ kg−1. The thermal cycling reliability of the eutectic mixtures was also tested during 1000 melting/freezing cycles. The loss in melting and solidification enthalpies was below 14% in all mixtures showing a promising behavior for PCM applications. Additionally, the unsaturated fatty acids were recovered and transformed to threo-9,10-dihydroxystearic acid (DHSA) and some of their inorganic salts, which were analyzed by FT-IR (Fourier transform-infrared spectroscopy) and tested for the first time using the DSC technique.GREA and DBA are certified agents TECNIO in the category of technology developers from the Government of Catalonia. We thanks to Subproductos Cárnicos Echevarria y Asociados S.L (Cervera, Spain) for supplying the non-edible fat. Moreover, the research leading to these results has received funding from the European Commission Seventh Framework Programme (FP/2007–2013) under grant agreement no. PIRSES-GA-2013-610692 (INNOSTORAGE) and from the European Union's Horizon 2020 research and innovation program under grant agreement no. 657466 (INPATH-TES). The authors would like to thank the Catalan Government for the quality accreditation given to their research groups GREA (2014 SGR 123), Agricultural Biotechnology Research Group (2014 SGR 1296) and DIOPMA (2014 SGR 1543). This work has been partially funded by the Spanish government (CTQ2015-70982-C3-1-R (MINECO/FEDER), ENE2015-64117-C5-1-R (MINECO/FEDER) and ENE2015-64117-C5-2-R (MINECO/FEDER)). Dr Camila Barreneche would like to thank Ministerio de Economia y Competitividad de España for her grant Juan de la Cierva FJCI-2014-22886. Aran Solé would like to thank Ministerio de Economía y Competitividad de España for Grant Juan de la Cierva, FJCI-2015-25741

Fatty acid eutectic mixtures and derivatives from non-edible animal fat as phase change materials

A set of compounds from non-edible fat waste was prepared and their thermal behavior was studied. The fat was hydrolyzed and crystallized in a simple and robust process to yield palmitic acid-stearic acid (PA-SA) mixtures. The PA-SA mass ratios determined by GC-FID (gas chromatography-flame ionization detection) were similar to those reported for eutectic mixtures of PCMs (phase change materials). DSC (differential scanning calorimetry) results indicated that the melting and solidification temperatures were around 55 °C and 52 °C and the latent heat of the crystallized fractions measured was around 180 kJ kg−1. The thermal cycling reliability of the eutectic mixtures was also tested during 1000 melting/freezing cycles. The loss in melting and solidification enthalpies was below 14% in all mixtures showing a promising behavior for PCM applications. Additionally, the unsaturated fatty acids were recovered and transformed to threo-9,10-dihydroxystearic acid (DHSA) and some of their inorganic salts, which were analyzed by FT-IR (Fourier transform-infrared spectroscopy) and tested for the first time using the DSC technique