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.

Catalytic Membrane Nanoreactor with Cu-Agx Bimetallic Nanoparticles Immobilized in Membrane Pores for Enhanced Catalytic Performance.

A catalytic membrane nanoreactor (CMNR) with Cu-Agx (where x is the millimolar concentration of AgNO3) bimetallic catalysts immobilized in membrane pores has been fabricated via coupling flowing synthesis and replacement reaction. Surface characterization by transmission electron microscopy (TEM) gives obvious evidence of the formation of Cu-Ag bimetallic core-shell nanostructures with Ag islands deposited on the Cu core metal. An apparent high shift phenomenon for the Cu element and a low shift phenomenon for the Ag element was determined by X-ray photoelectron spectroscopy (XPS), indicating a close interaction with the transfer of electron density from the Cu atom to the Ag atom. The hydrogenation catalysis of p-nitrophenol (p-NP) was tested to evaluate the catalytic performance. During the catalytic process, the Cu core acts as an electron-deficient site to adsorb and activate the -NO2 group for p-NP, and the Ag shell is beneficial for enhancing active H spilling to the Cu surface and then performing hydrogenation. A volcano-shaped apparent reaction rate constant can be achieved, which rises initially with the increasing Ag content and subsequently drops with a further increase in the Ag content. The highest value of 1071 min-1 can be achieved for CMNR immobilized with Cu-Ag2 owing to the suitable adsorption activation behavior and the best hydrogen spillover behavior.

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.

Performance comparison of ethanol and butanol production in a continuous and closed-circulating fermentation system with membrane bioreactor.

Since both ethanol and butanol fermentations are urgently developed processes with the biofuel-demand increasing, performance comparison of aerobic ethanol fermentation and anerobic butanol fermentation in a continuous and closed-circulating fermentation (CCCF) system was necessary to achieve their fermentation characteristics and further optimize the fermentation process. Fermentation and pervaporation parameters including the average cell concentration, glucose consumption rate, cumulated production concentration, product flux, and separation factor of ethanol fermentation were 11.45 g/L, 3.70 g/L/h, 655.83 g/L, 378.5 g/m2/h, and 4.83, respectively, the corresponding parameters of butanol fermentation were 2.19 g/L, 0.61 g/L/h, 28.03 g/L, 58.56 g/m2/h, and 10.62, respectively. Profiles of fermentation and pervaporation parameters indicated that the intensity and efficiency of ethanol fermentation was higher than butanol fermentation, but the stability of butanol fermentation was superior to ethanol fermentation. Although the two fermentation processes had different features, the performance indicated the application prospect of both ethanol and butanol production by the CCCF system.

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.

Cell growth behaviors of Clostridium acetobutylicum in a pervaporation membrane bioreactor for butanol fermentation.

Acetone-butanol-ethanol fermentation using Clostridium acetobutylicum was studied in the continuous and closed-circulating fermentation (CCCF) system. The experiment lasting for 192 H was carried out by integrating fermentation with in situ pervaporation. In the entire process, the cell growth profile took place in the following two phases: the logarithmic phase during early 28 H and the linear phase from 130 to 150 H. This was a unique characteristic compared with the curve of traditional fermentation, and the fitting equations of two growth phases were obtained by Origin software according to the kinetic model of cell growth. Besides, the kinetic parameters that include the butanol yield, maximum specific growth rate, average specific formation rate, and volumetric productivity of butanol were measured as 0.19 g g(-1) , 0.345 H(-1) , 0.134 H(-1) and 0.23 g L(-1)  H(-1) , respectively. The C. acetobutylicum in the CCCF system showed good adaptability and fermentation performance, and the prolonged fermentation period and high production were also the main advantages of CCCF technology.

Designer synthetic media for studying microbial-catalyzed biofuel production.

BACKGROUND: The fermentation inhibition of yeast or bacteria by lignocellulose-derived degradation products, during hexose/pentose co-fermentation, is a major bottleneck for cost-effective lignocellulosic biorefineries. To engineer microbial strains for improved performance, it is critical to understand the mechanisms of inhibition that affect fermentative organisms in the presence of major components of a lignocellulosic hydrolysate. The development of a synthetic lignocellulosic hydrolysate (SH) media with a composition similar to the actual biomass hydrolysate will be an important advancement to facilitate these studies. In this work, we characterized the nutrients and plant-derived decomposition products present in AFEX™ pretreated corn stover hydrolysate (ACH). The SH was formulated based on the ACH composition and was further used to evaluate the inhibitory effects of various families of decomposition products during Saccharomyces cerevisiae 424A (LNH-ST) fermentation. RESULTS: The ACH contained high levels of nitrogenous compounds, notably amides, pyrazines, and imidazoles. In contrast, a relatively low content of furans and aromatic and aliphatic acids were found in the ACH. Though most of the families of decomposition products were inhibitory to xylose fermentation, due to their abundance, the nitrogenous compounds showed the most inhibition. From these compounds, amides (products of the ammonolysis reaction) contributed the most to the reduction of the fermentation performance. However, this result is associated to a concentration effect, as the corresponding carboxylic acids (products of hydrolysis) promoted greater inhibition when present at the same molar concentration as the amides. Due to its complexity, the formulated SH did not perfectly match the fermentation profile of the actual hydrolysate, especially the growth curve. However, the SH formulation was effective for studying the inhibitory effect of various compounds on yeast fermentation. CONCLUSIONS: The formulation of SHs is an important advancement for future multi-omics studies and for better understanding the mechanisms of fermentation inhibition in lignocellulosic hydrolysates. The SH formulated in this work was instrumental for defining the most important inhibitors in the ACH. Major AFEX decomposition products are less inhibitory to yeast fermentation than the products of dilute acid or steam explosion pretreatments; thus, ACH is readily fermentable by yeast without any detoxification.

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.

Continuous acetone-butanol-ethanol (ABE) fermentation and gas production under slight pressure in a membrane bioreactor.

Two rounds of acetone-butanol-ethanol (ABE) fermentation under slight pressure were carried out in the continuous and closed-circulating fermentation (CCCF) system. Spores of the clostridium were observed and counted, with the maximum number of 2.1 × 10(8) and 2.3 × 10(8)ml(-1) separately. The fermentation profiles were comparable with that at atmospheric pressure, showing an average butanol productivity of 0.14 and 0.13 g L(-1)h(-1). Moreover, the average gas productivities of 0.28 and 0.27 L L(-1)h(-1) were obtained in two rounds of CCCF, and the cumulative gas production of 52.64 and 25.92 L L(-1) were achieved, with the hydrogen volume fraction of 41.43% and 38.08% respectively. The results suggested that slight pressures have no obvious effect on fermentation performance, and also indicated the significance and feasibility of gas recovery in the continuous ABE fermentation process.

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.

Adaptive evolution of Saccharomyces cerevisiae in a continuous and closed circulating fermentation (CCCF) system coupled with PDMS membrane pervaporation.

As an efficient means of strain improvement, adaptive evolution is a technique with great potential. Long-term cultivation of Saccharomyces cerevisiae was performed in a polydimethylsiloxane membrane bioreactor system which was constructed by coupling the fermentation with pervaporation. A parent strain was subjected to three rounds of fermentation-screening-transfer procedure lasting 1,500 h in a continuous and closed circulating fermentation (CCCF) system, and its 600-generation descendant S33 was screened. In shaking flask culture test, the selected strain S33 from the third round showed great superiority over the parent strain in the residual broth medium, with the ethanol yield and specific ethanol productivity increasing by 34.5 and 34.7 %, respectively. In the long-term CCCF test, the fermentation performance of the descendant strain in the third round was higher than that of its parent strain in the second round. These results show the potential of this novel adaptive evolution approach in optimization of yeast strains.

Acetone-butanol-ethanol fermentation in a continuous and closed-circulating fermentation system with PDMS membrane bioreactor.

Acetone-butanol-ethanol (ABE) fermentation by combining a PDMS membrane bioreactor and Clostridium acetobutylicum was studied, and a long continuous and closed-circulating fermentation (CCCF) system has been achieved. Two cycles of experiment were conducted, lasting for 274 h and 300 h, respectively. The operation mode of the first cycle was of fermentation intermittent coupling with pervaporation, and the second cycle was of continuous coupling. The average cell weight, glucose consumption rate, butanol productivity and butanol production of the first cycle were 1.59 g L(-1), 0.63 g L(-1)h(-1), 0.105 g L(-1)h(-1) and 28.03 g L(-1), respectively. Correspondingly, the four parameters of the second cycle were 1.68 g L(-1), 1.12 g L(-1)h(-1), 0.205 g L(-1)h(-1) and 61.43 g L(-1), respectively. The results indicate the fermentation behaviors under continuous coupling mode were superior to that under intermittent coupling mode. Besides, two peak values were observed in the time course profiles, which means the microorganism could adapt the long CCCF membrane bioreactor system.

Ethanol fermentation kinetics in a continuous and closed-circulating fermentation system with a pervaporation membrane bioreactor.

The kinetics of ethanol fermentation by Saccharomyces cerevisiae was studied in a continuous and closed-circulating fermentation (CCCF) system with a polydimethylsiloxane (PDMS) pervaporation membrane bioreactor. Three sequential 500-h cycles of CCCF experiments were carried out. A glucose volumetric consumption of 3.8 g L(-1) h(-1) and ethanol volumetric productivity of 1.39 g L(-1) h(-1) were obtained in the third cycle, with a specific glucose utilization rate of 0.32 h(-1) and ethanol yield rate of 0.13 h(-1). The prolonged fermentation time and good fermentation performance indicate that the CCCF would be a feasible and promising fermentation process technology.