Processing and Characterization of Membranes Based on Cellulose Nanocrystals for Water Purification

Membrane technology is being extensively used in water purification as an energy efficient and low cost process. Nanostructured (NSM) and nanoenabled (NEM) membranes are favored in this context as nanoscaled entities are expected to provide high surface area, high mechanical properties and versatile surface chemistry as well as provide better control on the pore size and distribution, flux and selectivity of the membrane. Biobased nanoparticles as nanocrystals are expected to have a significant advantage in this context. Thus, the main aim of this work was to explore the use of cellulose nanocrystals as functional entities for the fabrication of nanoenabled composite membranes and apply these fabricated membranes for the removal of dyes and metal ions from polluted water. The first study deals with the isolation of cellulose nanocrystals (CNCBE) from wood using the bioethanol pilot scale setup. Cellulose was prepared from wood by diluted acid treatment in the bioethanol plant followed by dewaxing and bleaching. The cellulose was converted into cellulose nanocrystals by mechanical grinding using lab scale homogenizer. The isolated nanoparticles had a diameter of 5-15 nm and formed a thick gel at 2 wt%. X-ray photoelectron spectroscopy illustrated the presence of O=C-O surface functional groups, directly related to the negative zetapotential values. Fabricated films of CNCBE denoted good mechanical properties, optical properties and cytocompatibility. Thus, a new isolation route that can be followed to produce nanocrystals in large quantities (600 g/ day) has been developed. In a second study, fully biobased nanocomposite membranes of cellulose nanocrystals and chitosan have been fabricated by freeze-drying and crosslinking with gluteraldehyde in vapor phase. The chitosan bound the CNCSL in a stable and nanoporous membrane network with thickness of 250-270 μm. Homogenous dispersion of CNCSL within chitosan matrix was reported based on scanning electron microscopy (SEM). The Brunauer Emmett and Teller (BET) studies showed a decrease in surface area (3.1 to 2.9 m/g) and average pore size (17 to 13 nm) after crosslinking. The mechanical performance of composite membranes was low, being 0.98 ± 0.4 and 1.1 ± 0.3 MPa of tensile strength for uncross-linked and cross-linked membranes, respectively. In spite of low water flux (64 L m h), the composite membranes successfully removed 98%, 84% and 70% respectively of positively charged dyes like Victoria Blue 2B, Methyl Violet 2B and Rhodamine 6G, from a model wastewater after a contact time of 24 h. In the third study layered membranes containing a highly porous support layer and a dense functional layer has been fabricated following a filtration and hot pressing method. Microsized cellulose fibers from sludge bioresidues was used as the support layer to provide mechanical stability and allow water flow without any hindrance. A nanocomposite system of nanocrystals (CNCSL, CNCBE and PCNCSL) with gelatin as matrix was used as the functional layer. Bubble point measurement confirmed the membrane pore sizes (5-6 mm), in microfiltration range, which resulted in high water permeability < 4000 Lhm at 1.5 bars. Efficient removal of Ag, Cu and Fe from industrial wastewater was achieved using these membranes. The removal of metal ions was expected to be driven by the electrostatic attraction between negatively charged nanocellulose and the positively charged metal ions. The work has demonstrated that highly efficient water treatment membranes can be fabricated from nanocellulose via tailoring their ability to interact and selectively adsorb heavy metal ions and dyes. List of appended papers Paper A Aji P. Mathew, Kristiina Oksman, Zoheb Karim, Peng Liu, Saad Ahmed Khan, Narges Naseri, Process scale up and characterization of wood cellulose nanocrystals hydrolysed using bioethanol pilot plant. Industrial Crop and Products 58 (2014) 212219. Paper B Zoheb Karim, Aji P. Mathew, Mattias Grahn, Johanne Mouzon, Kristtina Oksman, Nanoporous membranes with cellulose nanocrystals as functional entity in chitosan: Removal of dyes from water. Carbohydrate Polymers 112 (2014) 668-676. Paper C Zoheb Karim, Aji P. Mathew, Mojca Bozic, Vanja Kokol, Jiang Wei, Mattias Grahn, Kristiina Oksman, High flux affinity membranes based on cellulose nanocomposite for removal of heavy metal ions from industrial effluent. Submitted to Environmental Science and Technology.