Water and salt recovery from shale gas produced water by vacuum membrane distillation followed by crystallization.

A vacuum membrane distillation (VMD) followed by crystallization (VMD-C) was developed for the recovery of water and salts from shale gas produced water (SGPW). Before VMD, the pretreatment of SGPW with Fenton oxidation-flocculation is applied, with the chemical oxygen demand (COD) concentration reduction of 75% and the total removal of the total suspended solids (TSS), Ca2+, and Mg2+ in SGPW. The pretreatment of SGPW mitigated the membrane fouling in the VMD and effectively prevented the reduction of membrane flux over time. The average flux of the PTFE membrane reached 12.1 kg m-2 h-1 during the separation of the pretreated SGPW at a feed flux of 40 L h-1 and a feed temperature of 40 °C. The rejection rate of the membrane to TDS in SGPW was over 99%. Fresh water with a conductivity of below 20 µs cm-1 was produced by VMD-C. The salts concentrated upstream of the membrane were recovered by a stirring crystallization process. The VMD-C system resulted in a 61% cost savings compared to conventional SGPW treatment.

The pre-addition of "blocking" proteins decreases subsequent cellulase adsorption to lignin and enhances cellulose hydrolysis.

The pre-adsorption of non-catalytic/blocking proteins onto the lignin component of pretreated biomass has been shown to significantly increase the effectiveness of subsequent enzyme-mediated hydrolysis of the cellulose by limiting non-productive enzyme adsorption. Layer-by-layer adsorption of non-catalytic proteins and enzymes onto lignin was monitored using Quartz Crystal Micro balancing combined with Dissipation monitoring (QCM-D) and conventional protein adsorption. These methods were used to assess the interaction between soft/hardwood lignins, cellulases and the three non-catalytic proteins BSA, lysozyme and ovalbumin. The QCM-D analysis showed higher adsorption rates for all of the non-catalytic proteins onto the lignin films as compared to cellulases. This suggested that the "blocking" proteins would preferentially adsorb to the lignin rather than the enzymes. Pre-incubation of the lignin films with blocking proteins resulted in reduced adsorption of cellulases onto the lignin, significantly enhancing cellulose hydrolysis.

Cu-Ag Bimetallic Core-shell Nanoparticles in Pores of a Membrane Microreactor for Enhanced Synergistic Catalysis.

A bimetallic catalytic membrane microreactor (CMMR) with bimetallic nanoparticles in membrane pores has been fabricated via flowing synthesis. The bimetallic nanoparticle is successfully immobilized in membrane pores along its thickness direction. Enhanced synergistic catalysis can be expected in this CMMR. As a concept-of-proof, Cu-Ag core-shell nanoparticles have been fabricated and immobilized in membrane pores for p-nitrophenol (p-NP) hydrogenation. Transmission electron microscopy (TEM) for the characterization of the bimetallic core-shell nanostructure and X-ray photoelectron spectroscopy (XPS) for the characterization of the electron transfer behavior between Cu-Ag bimetal have been performed. The Ag shell on the core of Cu can improve the utilization of Ag atoms, and electron transfer between bimetallic components can promote the formation of high electron density active sites as well as active hydrogen with strong reducing properties on the Ag surface. The dispersed membrane pore can prevent nanoparticle aggregation, and the contact between the reaction fluid and catalyst is enhanced. The enhanced mass transfer can be achieved by the plug-flow mode during the process of hydrogenation catalysis. The p-NP conversion rate being over 95% can be obtained under the condition of a membrane flux of 1.59 mL·cm-2·min-1. This Cu-Ag/PES CMMR has good stability and has a potential application in industry.

Bioethanol production in vacuum membrane distillation bioreactor by permeate fractional condensation and mechanical vapor compression with polytetrafluoroethylene (PTFE) membrane.

A vacuum membrane distillation bioreactor (VMDBR) by permeate fractional condensation and mechanical vapor compression with PTFE membrane was developed for bioethanol production. Cell concentration of 11.5 g/L, glucose consumption rate of 5.2 g/L/h and ethanol productivity of 2.3 g/L/h could be obtained with fermentation continues lasting for 140 h. Membrane flux of over 10 kg/m2/h could be obtained for model solution separation. Higher temperature and flow rate could promote membrane separation. Membrane flux could be reduced to about 2000 g/m2/h with fermentation proceeding owing to the deposited cell on membrane surface. The membrane separation performance could be resumed by water rinse. High ethanol concentration of 421 g/L could be obtained by permeate fractional condensation with the process separation factor increased to 19.2. Energy of only 14 MJ/kg was required in VMDBR and the energy consumption would be reduced further if the compressed vapor could be used to heat the feed.

Energy efficient of ethanol recovery in pervaporation membrane bioreactor with mechanical vapor compression eliminating the cold traps.

An energy efficient pervaporation membrane bioreactor with mechanical vapor compression was developed for ethanol recovery during the process of fermentation coupled with pervaporation. Part of the permeate vapor at the membrane downstream under the vacuum condition was condensed by running water at the first condenser and the non-condensed vapor enriched with ethanol was compressed to the atmospheric pressure and pumped into the second condenser, where the vapor was easily condensed into a liquid by air. Three runs of fermentation-pervaporation experiment have been carried out lasting for 192h, 264h and 360h respectively. Complete vapor recovery validated the novel pervaporation membrane bioreactor. The total flux of the polydimethylsiloxane (PDMS) membrane was in the range of 350gm(-2)h(-1) and 600gm(-2)h(-1). Compared with the traditional cold traps condensation, mechanical vapor compression behaved a dominant energy saving feature.

Kinetic model of continuous ethanol fermentation in closed-circulating process with pervaporation membrane bioreactor by Saccharomyces cerevisiae.

Unstructured kinetic models were proposed to describe the principal kinetics involved in ethanol fermentation in a continuous and closed-circulating fermentation (CCCF) process with a pervaporation membrane bioreactor. After ethanol was removed in situ from the broth by the membrane pervaporation, the secondary metabolites accumulated in the broth became the inhibitors to cell growth. The cell death rate related to the deterioration of the culture environment was described as a function of the cell concentration and fermentation time. In CCCF process, 609.8 g L(-1) and 750.1 g L(-1) of ethanol production were obtained in the first run and second run, respectively. The modified Gompertz model, correlating the ethanol production with the fermentation period, could be used to describe the ethanol production during CCCF process. The fitting results by the models showed good agreement with the experimental data. These models could be employed for the CCCF process technology development for ethanol fermentation.

Inhibition effect of secondary metabolites accumulated in a pervaporation membrane bioreactor on ethanol fermentation of Saccharomyces cerevisiae.

The secondary metabolites accumulated in a pervaporation membrane bioreactor during ethanol fermentation were mostly composed of acetic acid, lactic acid, propionic acid, citric acid, succinic acid and glycerol. The inhibition effect of these compounds at a broad concentration range was studied through ethanol fermentation by Saccharomyces cerevisiae. An increasing concentration of the secondary metabolites led to longer lag time and a reduction of cell growth. The specific cell growth rate, cell yield, ethanol productivity were only 0.061 h(-1), 0.024, 0.47 g L(-1) h(-1) respectively, when the medium contained 3.12 g of acetic acid, 10.23 g of lactic acid, 2.72 g of propionic acid, 1.35 g of citric acid, 2.26 g of succinic acid and 49.25 g of glycerol per liter (a concentration level in pervaporation membrane bioreactor at later fermentation period). By increasing pH of the medium to 6.0-8.0, the inhibition of these secondary metabolites could be greatly relieved.

Enhanced ethanol fermentation in a pervaporation membrane bioreactor with the convenient permeate vapor recovery.

A continuous and closed-circulating fermentation (CCCF) system with a pervaporation membrane bioreactor was built for ethanol fermentation without a refrigeration unit to condense the permeate vapor. Two runs of experiment with a feature of complete and continuous coupling of fermentation and pervaporation were carried out, lasting for 192h and 264h, respectively. The experimental measurement indicated that the enhanced fermentation could be achieved with additional advantages of convenient permeate recovery and energy saving of the process. During the second experiment, the average cell concentration, glucose consumption rate, ethanol productivity, ethanol yield and total ethanol amount produced reached 19.8gL(-1), 6.06gL(-1)h(-1), 2.31gL(-1)h(-1), 0.38, and 609.8gL(-1), respectively. During the continuous fermentation process, ethanol removal in situ promoted the cell second growth obviously, but the accumulation of the secondary metabolites in the broth became the main inhibitor against the cell growth and fermentation.