Membrane distillation for treating hydraulic fracturing produced waters

The reuse of wastewater for beneficial uses has become increasingly important in recent years. There is an urgent need to develop innovative and more effective technologies for treatment of wastewaters. Many of these wastewaters such as hydraulic fracturing produced waters, contain very high total dissolved solids (TDS). Treatment of hydraulic fracturing produced waters can be very challenging as not only can they exhibit very high TDS, in excess of 200,000 ppm, they also contain surfactants and small organic compounds. Pressure driven membrane processes such as reverse osmosis are impractical for treating very high salinity wastewaters due to the high osmotic back pressure that must be overcome. Membrane distillation has been proposed as a new unit operation for treatment of very high TDS wastewaters. Vapor pressure is the driving force for water recovery in membrane distillation. An advantages of membrane distillation is the fact that low grade waste heat may be used. Here we have screened a number of commercially available microporous hydrophobic membranes. We have characterized membrane surface as well as bulk properties. Using bulk membrane properties, we calculate a structural parameter that indicates membranes that display high permeate flux. Next these membranes were challenged with feed streams containing 100,000 ppm (1.7 M) NaCl. The feeds stream was concentrated until breakthrough of the feed liquid into the permeate. Breakthrough occurred when the permeate flux rose rapidly while the conductivity of the permeate increased above 50 mS cm-1. Finally, these membranes were tested with real produced waters. Membranes that enabled the greatest concentration of TDS were selected for testing. While membrane distillation could be used to concentrate the feed to the solubility limit of the dissolved species present, leakage of feed water through the membrane pores into the distillate often occurs well before this level of water recovery. Leakage occurs due the presence of oil and suspended solids in the feed which can adsorb on the membrane surface. Thus pretreatment of the feed is essential. Here we have investigated the use of electrocoagulation as a pretreatment step for membrane distillation. Suspended solids and oil can be effectively coagulated followed by sedimentation prior to membrane distillation. A laboratory scale electrocoagulation system containing aluminum electrodes was designed, optimized and employed successfully to pretreat the feed. Please click Additional Files below to see the full abstract

Proceedings of the 38th Annual Biochemical Engineering Symposium

The 38th Annual Biochemical Engineering Symposium was held at the Pingree Park Campus and Conference Center, Colorado State University, 22-23 May 2009. The following institutions were represented; Colorado State University, Iowa State University, Kansas State University and the South Dakota School of Mines. This Proceeding contains papers based on most of the oral presentations. The first symposium was first held in 1971. It has been held annually since then except for a one year break. The following institutions have hosted the symposium. Contents History of the Annual Biochemical Engineering Symposium - Larry E. Erickson, Department of Chemical Engineering Kansas State University, Manhattan, Kansas 66506 Enhanced Solid-Liquid Clarification of Lignocellulosic Slurries Using Polyelectrolyte Flocculating Agents - Devon R. Burke, Jason Anderson, Patrick C. Gilcrease and Todd J. Menkhaus, Department of Chemical and Biological Engineering South Dakota School of Mines and Technology, Rapid City, SO 57701 Removal and Recovery of Inhibitory Compounds from Pine Slurry Hydrolysates using a Polyelectrolyte Flocculating Agent - Brian Carter, Todd J. Menkhaus, and Patrick C. Gilcrease Department of Chemical and Biological Engineering, South Dakota School of Mines and Technology, Rapid City, SO 57701 The thioesterases: A new perspective based on their primary and tertiary structures - David C. Cantu, Yingfei Chen, and Peter J. Reilly Department of Chemical and Biological Engineering, Iowa State University, Ames, lA 50011 Tailoring Polysaccharide-Based Nanostructured Biomaterials for Guided Mesenchymal Stem Cell (MSC) Response - Jorge Almodóvar, Matt J. Kipper, Department of Chemical and Biological Engineering, Colorado State University, School of Biomedical Engineering, Colorado State University, Fort Collins, CO 80523-1370 Nanoassembly of polysaccharide based polyelectrolytes: Tuning morphology and Size - Soheil Boddohit, Jorge Almodóvar, Hao Zhang, Patrick A. Johnson, and Matt J. Kipper, Department of Chemical and Biological Engineering, Colorado State University, School of Biomedical Engineering, Colorado State University, Fort Collins CO, 80523, Department of Chemical and Petroleum Engineering, University of Wyoming, Laramie WY, 82071 Vertical Cell Assembly of Colloidal Crystal Films for Making Inverse Colloidal Crystal Membrane: A New Generation Ultrafiltration Membrane for Protein Separation - Xinying Wang, Scott M. Husson, Xianghong Qian, S. Ranil Wickramasinghe, Department of Chemical and Biological Engineering, Colorado State University, Fort Collins, CO 80523, Department of Chemical and Biomolecular Engineering, Clemson University, Clemson, SC 29634, Department of Mechanical Engineering, Colorado State University, Fort Collins, CO 80523https://lib.dr.iastate.edu/bce_proceedings/1037/thumbnail.jp

Surface engineering for developing new membrane adsorbers

Significant increases in product titers during cell culture means that development of purification processes that can efficiently recover and purify high titer feed streams is a major challenge in the biopharmaceutical industry. On the other hand, introduction of new unit operations is complicated by the significant cost involved in meeting the regulatory requirements for validation and approval of a new unit operation. Recently the development of bio-similars or clones of products for which patent protection has expired, has provided an added competitive incentive for the development of low cost, high efficiency purification processes. Membrane adsorbers are routinely used in the downstream processing of biopharmaceuticals in flow through mode to remove contaminants e.g. host cell proteins, DNA and virus particles. Membrane adsorbers overcome the limitations of resin-based chromatography. Convective flow through the membrane pores overcomes the problems associated with slow internal pore diffusion that plagues resin particles. In addition, scale up of membrane devices is simpler than packed beds. Nevertheless use of membrane adsorbers in bind and elute mode remains limited. This presentation focuses on the importance of engineering membrane surface ligands in order to maximize capacity and recovery in bind and elute operation. Two examples are presented. Bisphosphonate derived ligands have been grafted from the surface of regenerated cellulose membranes. The capacity and flexibility of the ligands are enhanced by copolymerization of N(2-hydroxypropyl) methacrylamide (HPMA). These ligands selectively bind arginine rich proteins. Binding studies indicate the importance of tailoring the three dimensional structure of the ligands in order to maximize capacity and recovery. The mechanism for poly(bisphosphonate-co-polyHMPA) binding has been determined by molecular dynamic simulations. The results obtained highlight the importance of the phosphonate groups as well as HPMA for strong binding interactions and high recoveries. The second example uses responsive ligands that change their conformation in response to changes in external conditions. Membrane based hydrophobic interaction chromatography (HIC) has been conducted using poly(N-vinylcaprolactam) (PVCL) and its copolymers grafted from the surface of regenerated cellulose membranes. PVCL displays a lower critical solution temperature (LCST). The LCST depends on salt type and concentration. At high salt concentration e.g. 1.8 M (NH4)2SO4, used during loading in HIC, the ligand is above its LCST. Consequently it adopts a dehydrated conformation enhancing protein binding. At low ionic strength, during elution, the ligand is below its LCST. It adopts a hydrated conformation leading to protein desorption

Selectvie Modification of Membrane Pore and External Surfaces

Modification of membrane surfaces by grafting polymer brushes from the surface has been shown to impart unique surface properties. These polymer brushes can be used as ligands in membrane for adsorbers, they can be used to reduce membrane fouling as well as for the development of responsive membranes that can change their conformation in response to an external stimulus1,2. Here we focus on magnetically responsive membranes where magnetically responsive polymer chains are grown from the membrane surface. We have developed a range of microfiltration3, ultrafiltration and nanofiltration4,5 membranes by grafting magnetically responsive polymer brushes from the membrane surface. Here we focus on regenerated cellulose based ultrafiltration membranes. Atom transfer radical polymerization (ATRP) has been used to graft poly-hydroxyethyl methacrylate (polyHEMA) from the surface of the membrane. Superparamagnetic particles have been attached to the chain ends. In an oscillating magnetic field, movement of the magnetically responsive nanobrushes leads to suppression of concentration polarization resulting in higher permeate fluxes and better rejection. We have also grafted with poly(N-isopropylacrylamide) a thermo-responsive polymer that exhibits a lower critical solution temperature, using ATRP, from the surface of the membrane. By carefully choosing the frequency of the oscillating magnetic field, movement of the polymer chains can used to induce mixing. Using much higher frequencies, around 1,000 Hz, heating will lead to collapse of poly(N-isopropylacrylamide) layer as the temperature of the grafted polymer layer increase above the lower critical solution temperature of the grafted poly(N-isopropylacrylamide). Unlike nanofiltration and microfiltration membranes where the majority the polymer chains are grafted from the barrier layer or the inside pore surface respectively, in the case of ultrafiltration membranes significant grafting can occur from both the barrier layer and the internal pore surface. In addition given the smaller pore sizes compared to microfiltration membranes, pore plugging by the grafted polymer chains must be avoided We have developed a novel technique to selectively graft from the external barrier layer or the internal membrane pore surface. We show that the magnetically responsive polymer brushes can have a significant different effect on rejection and flux of model feed streams consisting of proteins such as bovine serum albumin, depending on their location on the membrane barrier layer or in the pores. Our work highlights the importance of being able to control not only the three dimensional structure of the grafted polymers but also their location; from the membrane barrier layer or from the inside pore surface References 1. D. Bhattacharyya, T. Schäfer, S. R. Wickramasinghe, S. Daunert, eds., Responsive Membranes and Materials, John Wiley & Sons, 2013, West Sussex, UK. 2. S. Darvishmanesh, , Qian, X., Wickramasinghe, S. R. (2015), ‘Responsive membranes for advanced separations’, Current Opinions in Chemical Engineering, 8, 98-104. 3. H. H. Himstedt, Q. Yang, X. Qian, S. R. Wickramasinghe, M. Ulbricht, M., Toward remote-controlled valve functions via magnetically responsive capillary pore membranes’, J Membr. Sc., 423 (2012) 257-266. 4. Q. Yang, Q., H. H. Himstedt, M. Ulbricht, X. Qian, X., S. R. Wickramasinghe, Designing magnetic field responsive nanofiltration membranes, J Membr. Sc., 430 (2013) 70-78. 5. X. Qian, Yang, Q., Vu, A. T., Wickramasinghe, S. R. (2016), ‘Localized Heat generation from Magnetically Responsive Membranes’, Industrial & Engineering Research, 55 (33), 9015–9027

Produced water treatment by nanofiltration and reverse osmosis membranes

Produced water, water that is co-produced during oil and gas manufacturing, represents the largest source of oily wastewaters. Given high oil and gas prices, oil and gas production from non-conventional sources such as tar sands, oil shale and coal bed methane will continue to expand resulting in large quantities of impaired produced water. Treatment of this produced water could improve the economic viability of these oil and gas fields and lead to a new source of water for beneficial use. Two nanofiltration and one low-pressure reverse osmosis membrane have been tested using three produced waters from Colorado, USA. The membranes were analyzed before and after produced water filtration using field emission scanning electron microscopy (FESEM), attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). In addition, membrane–water contact angles have been measured. XPS data indicate adsorption of organic and inorganic species during filtration. FESEM and ATR-FTIR data support theses findings. Water contact angles indicate the effect of membrane hydrophilicity on fouling. Our results highlight the value of using multiple surface characterization methods with different depths of penetration in order to determine membrane fouling. Depending on the quality of the produced water and the water quality requirements for the beneficial uses being considered, nanofiltration may be a viable process for produced water treatment. © 2008 Elsevier B.V. All rights reserved

Purification Of Minute Virus Of Mice Using High Performance Tangential Flow Filtration

Membrane technology has proven to be a mainstay separation technology over the past two decades. Some major advantages of membrane technology are application without the addition of chemicals and a comparatively low energy use. With its current applications, membrane technology has been widely used in biotechnology processes. Cell harvesting and virus purification/removal are important processes in many downstream purifications of biopharmaceutical products. For this project, ultrafiltration (UF) for virus purification from cell culture broth was used. Recently, it has been demonstrated that UF is a powerful tool for purification of other viruses such as Aedes aegypti and virus-like particles. More precisely, high-performance tangential flow filtration (HPTFF) will be used, which was first introduced by Robert van Reis in 1997. To date HPTFF has been used in other projects, as for protein concentration, purification, and buffer exchange as a single unit operation. The virus used in this study was the parvovirus Minute Virus of Mice (MVM); characterized by an average diameter of 22-26 nm and icosahedral symmetry. Experiments were conducted with 300, 100 and 50 kDa Sartorius membranes. Results obtained indicate that using the 50 or 100 kDa membrane, viral particles get excluded, whereas the 300 kDa membrane allows the passage of the virus particles into the permeate. In HPTFF mode the permeate flux decline of the 300 kDa ultrafiltration membrane is much greater than for the other membranes used. One possible explanation for this decay could have to do with the virus particles’ access to the membrane pores (gradual pore narrowing). Additionally the permeate flux and level of protein rejection as well, are strongly affected by the cell culture medium

Nanofiltration/reverse osmosis for treatment of coproduced waters

Current high oil and gas prices have lead to renewed interest in exploration of nonconventional energy sources such as coal bed methane, tar sand, and oil shale. However oil and gas production from these nonconventional sources has lead to the coproduction of large quantities of produced water. While produced water is a waste product from oil and gas exploration it is a very valuable natural resource in the arid Western United States. Thus treated produced water could be a valuable new source of water. Commercially available nanofiltration and low pressure reverse osmosis membranes have been used to treat three produced waters. The results obtained here indicate that the permeate could be put to beneficial uses such as crop and livestock watering. However minimizing membrane fouling will be essential for the development of a practical process. Field Emission Scanning Electron Microscopy imaging may be used to observe membrane foulin

Glucose production from lignocellulosic biomass using a membrane-based polymeric solid acid catalyst

Large-scale production of biomass-derived fuels and chemicals requires the economical and efficient depolymerization of lignocellulosic biomass into sugars and fuels. Catalytic hydrolysis of raw wheat straw for the production of glucose was conducted using a designed porous membrane-based polymeric solid acid catalyst consisting of poly (ionic liquid) and polysulfonic acid chains. The catalyst demonstrated superior activity and selectivity with glucose yield reached over 50% from the un-pretreated raw straw. Under the optimal conditions, over 80% of cellulose and over 90% of xylan were converted to soluble sugars and furans with over 60% glucose or xylose yields reached respectively from pretreated straw biomass. Our catalyst demonstrates high glucose and total reducing sugar (TRS) yields from lignocellulosic biomass with promising application for the future lignocellulosic biorefinery

Removal of Emerging Contaminants from Wastewater Streams Using Membrane Bioreactors: A Review

Water is a very valuable natural resource. As the demand for water increases the presence of emerging contaminants in wastewater has become a growing concern. This is particularly true when one considers direct reuse of wastewater. Obtaining sufficient removal of emerging contaminants will require determining the level of removal for the various unit operations in the wastewater treatment process. Membrane bioreactors are attractive as they combine an activated sludge process with a membrane separation step. They are frequently used in a wastewater treatment process and can operate at higher solid loadings than conventional activated sludge processes. Determining the level of removal of emerging contaminants in the membrane bioreactor step is, therefore, of great interest. Removal of emerging contaminants could be by adsorption onto the biomass or membrane surface, biotransformation, size exclusion by the membrane, or volatilization. Given the fact that most emerging contaminants are low molecule weight non-volatile compounds, the latter two methods of removal are usually unimportant. However, biotransformation and adsorption onto the biomass are important mechanisms of removal. It will be important to determine if the microorganisms present at given treatment facility are able to remove ECs present in the wastewater