Investigating Pervaporation for In Situ Acetone Removal as Process Intensification Tool in ω-Transaminase Catalyzed Chiral Amine Synthesis.

Hydrophobic pervaporation (PV), allowing for the separation of an organic component from an aqueous stream, was investigated for in situ acetone removal from a transamination reaction. A poly(dimethylsiloxane) membrane was applied in a coupled enzymatic process at 5 L scale. Among the four components, there was no loss of donor and product amines through PV which was highly desirable. However, in addition to removal of acetone, there was also an unwanted loss of acetophenone (substrate ketone) because of PV. The coupled enzyme-PV process resulted in 13% more product formation compared to the control process (where no PV was applied) after 9 h. Results from a qualitative simulation study (based on partial vapor pressures and a vapor-liquid equilibrium of the feed solution) indicated that PV might have an advantage over direct distillation strategy for selective removal of acetone from the reaction medium. © 2018 American Institute of Chemical Engineers Biotechnol. Prog., 35: e2731, 2019.

Pectin oligosaccharides from sugar beet pulp: molecular characterization and potential prebiotic activity.

Pectin oligosaccharides (POS) have been indicated as a new class of potential prebiotic compounds, which can be produced from pectin-rich food byproducts. In the present study, different technological means of POS production were explored to produce tailor-made POS mixtures starting from sugar beet pulp. The overall POS production process consisted of two steps: the extraction of pectin and the hydrolysis of pectin to tailored POS by combined hydrolysis/fractionation approaches. Different extraction as well as hydrolysis and fractionation methodologies were applied. The obtained POS were characterized for their total galacturonic acid content and, at a deeper level, using a HILIC-ESI/MS methodology, for the POS structure and composition. The composition of POS fractions was studied as a function of the technology used to obtain them. Finally, the potential prebiotic properties of the POS mixtures obtained were thoroughly explored by several in vitro experiments aimed at detecting lactic acid bacteria (LAB) stimulation by POS fractions. Several fractions were very efficient in stimulation, in a species-dependent manner. The overall best fractions were in general those rich in arabinans having a low degree of polymerization, obtained from the enzymatic extraction of biomass and subsequent fractionation with low-medium molecular weight cut-off. Quite interestingly, no POS fraction was able to stimulate pathogenic E. coli strains. The data reported here clearly indicate the possibility to obtain diverse fractions with different prebiotic properties starting from the same biomass, and outline clear potential for POS obtained from sugar beet pulp with the appropriate technology to act as prebiotic compounds.

Biobutanol production from C5/C6 carbohydrates integrated with pervaporation: experimental results and conceptual plant design.

In this study, a simulated lignocellulosic hydrolyzate was used in a continuous two-stage fermentor setup for production of acetone, butanol and ethanol. An organophilic pervaporation unit was coupled to the second fermentor. The dilution rate in the first fermentor was kept constant at 0.109 h(-1), while the dilution rate in the second fermentor was gradually decreased from 0.056 to 0.020 h(-1). Glucose was completely consumed, while 61% of the xylose was consumed at the lowest dilution rate, leading to an overall solvent productivity of 0.65 g L(-1) h(-1) and a high concentration of 185 g kg(-1) solvents in the permeate in the last fermentation zone during 192 h. Based on the experimental results, a process integrated with organophilic pervaporation was conceptually designed and compared with a base-case. Chemcad simulations indicate an energy reduction of ~50% when organophilic pervaporation is used. This study also demonstrates significant reductions in process flows and energy consumption by the use of organophilic pervaporation as in situ product recovery technology.

Integrated bioprocess for long-term continuous cultivation of Clostridium acetobutylicum coupled to pervaporation with PDMS composite membranes.

A continuous cultivation of Clostridium acetobutylicum ATCC 824 is described using a two-stage design to mimic the two phases of batch culture growth of the organism. A hydrophobic pervaporation unit was coupled to the second fermentor containing the highest solvent titers. This in situ product recovery technology efficiently decreased butanol toxicity in the fermentor while the permeate was enriched to 57-195 g L(-1) total solvents depending on the solvent concentrations in the fermentor. By the alleviation of product inhibition, the glucose concentration could be increased from 60 to 126 g L(-1) while the productivity increased concomitantly from 0.13 to 0.30 g L(-1)h(-1). The continuous fermentation was conducted for 1172 h during which the pervaporation was coupled to the second fermentor for 475 h with an average flux of 367 g m(-2)h(-1). The energy consumption was calculated for a 2 wt.% n-butanol fermentation broth and compared with the conventional process.

Solvent-resistant nanofiltration for product purification and catalyst recovery in click chemistry reactions.

The quickly developing field of "click" chemistry would undoubtedly benefit from the availability of an easy and efficient technology for product purification to reduce the potential health risks associated with the presence of copper in the final product. Therefore, solvent-resistant nanofiltration (SRNF) membranes have been developed to selectively separate "clicked" polymers from the copper catalyst and solvent. By using these solvent-stable cross-linked polyimide membranes in diafiltration, up to 98 % of the initially present copper could be removed through the membrane together with the DMF solvent, the polymer product being almost completely retained. This paper also presents the first SRNF application in which the catalyst permeates through the membrane and the reaction product is retained.

Probing the molecular level of polyimide-based solvent resistant nanofiltration membranes with positron annihilation spectroscopy.

Positron annihilation spectroscopy (PAS) has been performed to link fundamental polymer properties to membrane performance, more specifically for polyimide (PI)-based solvent-resistant nanofiltration membranes. Laboratory-made membranes with well-known properties were applied first to define proper pretreatment conditions for the membrane to allow PAS-analysis and to allow more correct linking of PAS results to membrane properties. This knowledge was then applied to probe the structure of commercial PI-based Starmem membranes.

Compositional optimization of polyimide-based SEPPI membranes using a genetic algorithm and high-throughput techniques.

Asymmetric, nanosized zeolite-filled solvent resistant nanofiltration (SRNF) membranes, prepared from emulsified polyimide (PI) solutions via the earlier reported solidification of emulsified polymer solutions via phase inversion (SEPPI) method, were optimized for their performance in the separation of rose bengal (RB) from 2-propanol (IPA). All membranes were prepared and tested in a parallellized, miniaturized, and automated manner using laboratory-developed high-throughput experimentation techniques. Nine different synthesis parameters related to the composition of the casting solutions were thus optimized. In a first, "conventional" approach, a preliminary systematic screening was carried out, in which only four constituents were used, that is, Matrimid PI, NMP as solvent, THF as volatile cosolvent, and an NMP-based zeolite precursor sol as emulsifying agent. A combinatorial strategy, based on a genetic algorithm and a self-adaptive evolutionary strategy, was then applied to optimize the SRNF performance of PI-based SEPPI membranes. This directed approach allowed the screening of an extended, 9-dimensional parameter space, comprising two extra solvents, the two corresponding nanosized zeolite suspensions, as well as another cosolvent. Coupling with high-throughput techniques allowed the preparation of three generations of casting solutions, 176 compositions in total, resulting in 125 testable membranes. With IPA permeances up to 3.3 L.m(-2) h(-1) bar(-1) and RB rejections around 98%, the combinatorially optimized membranes scored significantly better with respect to fluxes and selectivities than the best membranes obtained in the systematic screening. The best SEPPI membranes also showed much higher IPA permeances than two commercial SRNF membranes at similar or slightly lower RB rejections.

Evaporative light scattering detector: toward a general molecular weight cutoff characterization of nanofiltration membranes.

An evaporative light scattering detector (ELSD) coupled with HPLC was used for the first time to characterize membranes. Polydispersed PEG-200, 600, and 1000 were selected as probe molecules to study the dependence of membrane retention on molecular weight via a gradient eluted HPLC separation coupled to ELSD detection. The results show that HPLC/ELSD is a really general and powerful technique to study the nanofiltration (NF) process since it does not require any special properties for the solutes (chromospheres or fluorophores) and possesses the required sensitivity. Especially in solvent resistant NF (SRNF), where a wide range of organic solvents is used, the ELSD detector was not affected by the interaction between solvent and solutes, which is a critical issue compared to other more common detectors.

Solvent resistant nanofiltration: separating on a molecular level.

Over the past decade, solvent resistant nanofiltration (SRNF) has gained a lot of attention, as it is a promising energy- and waste-efficient unit process to separate mixtures down to a molecular level. This critical review focuses on all aspects related to this new burgeoning technology, occasionally also including literature obtained on aqueous applications or related membrane processes, if of relevance to understand SRNF better. An overview of the different membrane materials and the methods to turn them into suitable SRNF-membranes will be given first. The membrane transport mechanism and its modelling will receive attention in order to understand the process and the reported membrane performances better. Finally, all SRNF-applications reported so far - in food chemistry, petrochemistry, catalysis, pharmaceutical manufacturing - will be reviewed exhaustively (324 references).