Immobilization-Stabilization of β-Glucosidase for Implementation of Intensified Hydrolysis of Cellobiose in Continuous Flow Reactors

Cellulose saccharification to glucose is an operation of paramount importance in the bioenergy sector and the chemical and food industries, while glucose is a critical platform chemical in the integrated biorefinery. Among the cellulose degrading enzymes, β-glucosidases are responsible for cellobiose hydrolysis, the final step in cellulose saccharification, which is usually the critical bottleneck for the whole cellulose saccharification process. The design of very active and stable β-glucosidase-based biocatalysts is a key strategy to implement an efficient saccharification process. Enzyme immobilization and reaction engineering are two fundamental tools for its understanding and implementation. Here, we have designed an immobilized-stabilized solid-supported β−glucosidase based on the glyoxyl immobilization chemistry applied in porous solid particles. The biocatalyst was stable at operational temperature and highly active, which allowed us to implement 25 °C as working temperature with a catalyst productivity of 109 mmol/min/gsupport. Cellobiose degradation was implemented in discontinuous stirred tank reactors, following which a simplified kinetic model was applied to assess the process limitations due to substrate and product inhibition. Finally, the reactive process was driven in a continuous flow fixed-bed reactor, achieving reaction intensification under mild operation conditions, reaching full cellobiose conversion of 34 g/L in a reaction time span of 20 min.

13 Electrochemistry in Laboratory Flow Systems

Organic electrosynthesis in flow reactors is an area of increasing interest, with efficient mass transport and high electrode area to reactor volume present in many flow electrolysis cell designs facilitating higher rates of production with high selectivity. The controlled reaction environment available in flow cells also offers opportunities to develop new electrochemical processes. In this chapter, various types of electrochemical flow cells are reviewed in the context of laboratory synthesis, paying particular attention to how the different reactor environments impact upon the electrochemical processes, and the factors responsible for good cell performance. Coverage includes well-established plane-parallel-plate designs, reactors with small interelectrode gaps, extended-channel electrolysis cells, and highly sophisticated designs with rapidly rotating electrodes to enhance mass transport. In each case, illustrative electrosyntheses are presented.

Mechanical Stability Is Key for Large-Scale Implementation of Photocatalytic Surface-Attached Film Technologies in Water Treatment

Replacement of classical tertiary water treatment by chemical-free sunlight-driven photocatalytic units has been often proposed. Photocatalysts are required to be cost-effective, inert, chemically stable, reusable, and easy to separate and also that they are mechanically stable. The effect of mechanical stress on a photoactive TiO2 layer, and on its effectivity for degradation of phenol as a model pollutant, has been studied during photocatalytic water treatment using NUV–vis light. Sol–gel (SG) and liquid phase deposition (LPD) methods have been used to coat spherical glass beads with the photocatalyst (TiO2). Physicochemical characterization of coated glass beads has been performed by N2 adsorption–desorption isotherms, SEM, EDXS, and AFM. Phenol photocatalyzed degradation was carried out both in stirred batch and flow reactors irradiated with a medium-pressure Hg-vapor lamp (λ > 350 nm). Phenol concentration was determined by HPLC, and its photoproducts were identified using HPLC/MS. In the stirred batch reactor, all LPD-coated glass beads displayed higher catalytic activity than SG-coated ones, which increased with calcination temperature, 700°C being the most efficient temperature. Preliminary etching of the glass beads surface yielded dissimilar results; whereas, phenol photodegradation with SG-coated etched glass beads is twice faster than with unetched SG ones, the rate reduces to one-third using LPD etched instead of unetched LPD glass beads. Phenol photodegradation using LPD is similar both in stirred batch and flow reactors, despite the latter uses a lower catalyst load. LPD-etched catalyst was recovered and reused in the stirred batch reactor; its activity reduced sharply after the first use, and it also lost activity in successive runs, ca. 10% of activity after each “use and recover” cycle. In the flow reactor, activity loss after the first experiment and recycling (ca. 30%) was much larger than in the following runs, where the activity remained rather constant through several cycles. LPD is more adequate than SG for TiO2 immobilization onto glass beads, and their calcination at 700°C leads to relatively strong and reactive photocatalytic films. Still, TiO2-coated glass beads exhibited very low photoactivity compared to TiO2-P25 nanoparticles, though their separation is much easier and almost costless. The durability of the catalytic layer increases when using a flow reactor, with the pollutant solution flowing in a laminar regime through the photocatalyst bed. In this way, the abrasion of the photocatalytic surface is largely reduced and its photoactivity is better maintained.