RESUMO
This research presents the modification of MOF-199 and ZIF-8 using furfuryl alcohol (FA) as a carbon source to subsequently fix lipase from Pseudomonas cepacia and use these biocatalysts in the transesterification of African palm oil (APO). The need to overcome the disadvantages of free lipases in the biodiesel production process led to the use of metal organic framework (MOF)-type supports because they provide greater thermal stability and separation of the catalytic phase, thus improving the activity and efficiency in relation to the use of free lipase, disadvantages that could not be overcome with the use of other types of catalysts used in transesterification/esterification reactions for the production of biodiesel. The modification of MOFs ZIF-8 and MOF-199 with FA increases the pore volume which allows better immobilization of Pseudomonas cepacia lipase (PCL). The results show that these biocatalysts undergo transesterification with biodiesel yields above 90%. Additionally, studies were carried out on the effect of (1) enzyme loading, 2) enzyme immobilization time, (3) enzyme immobilization temperature, and (4) pH on the % immobilization of the enzyme and the specific activity. The results show that the highest immobilization efficiency for the FA@ZIF-8 support has a value of 91.2% when the load of this support was 3.5 mg/mg and has a specific activity of 142.5 U/g protein. The FA@MOF-199 support presented 80.3% enzyme immobilization and 125% U/g specific activity protein. We established that the specific activity increases in the period from 0.5 to 5.0 h for the systems under investigation. After this time, both the specific activity and the % efficiency of enzyme immobilization decrease. Therefore, 5.0 h (immobilization efficiency of 95 and 85% for FA@MOF-199, respectively) was chosen as the most appropriate time for PCL immobilization. Methods of adding methanol, with three and four steps, were tested, where biodiesel yields greater than 90% were obtained for the biocatalysts synthesized in this work (FA@ZIF-8-PCL and FA@MOF-199-PCL) and above 70% for free PCL, and the maximum yield was reached at a molar ratio between methanol and APO of 4:1 when using the one-step method under the same reaction conditions (as mentioned above). Only the results of FA@ZIF-8-PCL are presented here; however, it should be noted that the results for biocatalyst FA@MOF-199-PCL and lipase-free PCL presented the same behavior. The order of biocatalyst performance was FA@ZIF-8-PCL > FA@MOF-199-PCL > PCL-Free, which demonstrates that the use of FA as a modifier is a novel aspect in the conversion of palm oil into biodiesel components.
RESUMO
This research presents results on the production of biodiesel from the transesterification of acylglycerides present in palm oil, using the biocatalysts ZIF-8-PCL and Gly@ZIF-8-PCL synthesized by immobilization of Pseudomonas Cepacia Lipase as catalytic materials and using pure ZIF-8 and Gly@ZIF-8 (modified ZIF-8) as supports. The Gly@ZIF-8 carbonaceous material was prepared by wet impregnation of ZIF-8 with ethylene glycol as the carbon source, and then thermally modified. The calcination conditions were 900 °C for two hours with a heating rate of 7 °C/min in an inert atmosphere. A textural characterization was performed, and results showed superficial changes of materials at the microporous and mesoporous levels for the Gly@ZIF-8 material. Both the starting materials and biocatalysts were characterized by infrared spectroscopy (FTIR) and Raman spectroscopy. During the transesterification, using the two biocatalysts (ZIF-8-PCL and Gly@ZIF-8-PCL), two supernatant liquids were generated which were characterized by infrared spectroscopy (FTIR), gas chromatography coupled to mass spectrometry (GC-MS), and nuclear magnetic resonance (NMR). The results show that the two routes of synthesis of supports from ZIF-8 will be configured as effective methods for the generation of effective biocatalysts for biodiesel production.