RESUMEN
This study aimed to develop and investigate the synthesis of 2-ethylhexyl oleate catalyzed by Candida antarctica lipase immobilized on magnetic poly(styrene-co-divinylbenzene) (STY-DVB-M) particles in a magnetically stabilized fluidized bed reactor (MSFBR) operated in continuous mode. The physical properties of the copolymer were characterized by Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The glass transition temperature was 85.68 °C, and the onset of thermal degradation occurred at 406.66 °C. Syntheses were performed at 50 °C using a space time of 12 h and a bed porosity of 0.892. Assays were conducted to assess the influence of magnetic field intensity (5 to 15 mT) on reaction yield, ester concentration, and productivity. The highest productivity was 0.850 ± 0.023 mmol g-1 h-1, obtained with a magnetic field intensity of 15 mT. An operational stability test was performed under these conditions, revealing a biocatalyst half-life of 2148 h (179 operation cycles) and a thermal deactivation constant of 3.23 × 10-4 h-1 (R2 = 0.9446). Computational simulations and mathematical modeling were performed using Scilab based on ping-pong bi-bi kinetics and molar balances of reaction species. The model provided consistent results of interstitial velocity and good prediction of reaction yields, with R2 = 0.926. These findings demonstrate that the studied technique can provide improvements in biocatalytic processes, representing a promising strategy for the enzymatic synthesis of 2-ethylhexyl oleate.
Asunto(s)
Enzimas Inmovilizadas , Ácido Oléico , Enzimas Inmovilizadas/química , Reactores Biológicos , Biocatálisis , Lipasa/química , EsterificaciónRESUMEN
In recent years, residual glycerol from biodiesel synthesis made this chemical a cheap, readily available carbon source to bioprocess, which is also a form to reduce costs in the fuel industry. We propose and describe a bioprocess using fluidized and packed-bed continuous bioreactors to convert this residual glycerol into value-added products such as 1,3-propanediol (1,3-PD) and 2,3-butanediol (2,3-BD), largely used in the chemical industry. The bacterium Klebsiella pneumoniae BLh-1, strain isolated by us, was immobilized in the permeable support of polyvinyl alcohol (LentiKats®). After testing different dilution rates (D) for all bioreactor configurations, the best obtained productivities of 1,3-PD was 8.69 g L-1 h-1 at a D = 0.45 h-1 , and 2.99 g L-1 h-1 at a D = 0.30 h-1 for 2,3-BD, both in the packed-bed configuration. In the fluidized-bed reactor, the highest productivity values achieved were 4.48 and 1.16 g L-1 h-1 for 1,3-PD and 2,3-BD, respectively, both at D = 0.33 h-1 . These results show the potential of setting up a bioprocess based on continuous cultures using immobilized K. pneumoniae BLh-1 in PVA matrices in order to efficiently convert the abundant surplus of glycerol into commercially important chemicals such as 1,3-PD and 2,3-BD.
Asunto(s)
Glicerol , Klebsiella pneumoniae , Biocombustibles , Reactores Biológicos , Butileno Glicoles , Glicoles de PropilenoRESUMEN
The present work evaluated the effects of (i) feeding a water contaminated with 80 mg/L PCE to bioreactors seeded with inoculum not acclimated to PCE, (ii) coupling ZVI side filters to bioreactors, and (iii) working in different biological regimes, i.e., simultaneous methanogenic aeration and simultaneous methanogenic-denitrifying regimes, on fluidized bed bioreactor performance. Simultaneous electron acceptors refer to the simultaneous presence of two compounds operating as final electron acceptors in the biological respiratory chain (e.g., use of either O2 or NO3- in combination with a methanogenic environment) in a bioreactor or environmental niche. Four lab-scale, mesophilic, fluidized bed bioreactors (bioreactors) were implemented. Two bioreactors were operated as simultaneous methanogenic-denitrifying (MD) units, whereas the other two were operated in partially aerated methanogenic (PAM) mode. In the first period, all bioreactors received a wastewater with 1 g chemical oxygen demand of methanol per liter (COD-methanol/L). In a second period, all the bioreactors received the wastewater plus 80 mg perchloroethylene (PCE)/L; at the start of period 2, one MD and one PAM were coupled to side sand-zero valent iron filters (ZVI). All bioreactors were inoculated with a microbial consortium not acclimated to PCE. In this work, the performance of the full period 1 and the first 60 days of period 2 is reported and discussed. The COD removal efficiency and the nitrate removal efficiency of the bioreactors essentially did not change between period 1 and period 2, i.e., upon PCE addition. On the contrary, specific methanogenic activity in PAM bioreactors (both with and without coupled ZVI filter) significantly decreased. This was consistent with a sharp fall of methane productivity in those bioreactors in period 2. During period 2, PCE removals in the range 86 to 97 % were generally observed; the highest removal corresponded to PAM bioreactors along with the highest dehalogenation efficiency (94 %). Principal component analysis as well as cluster analysis confirmed the trends mentioned above, i.e., the better performance of PAM over MD, and the unexpected no effect of the ZVI side filters on PCE removal and dehalogenation efficiencies. To the best of our knowledge, this is the first report on the combined treatment ZVI-biological of a water polluted with PCE, where the biological operation relied on simultaneous electron acceptors.