1. Introduction
Membrane separation technique is widely used process for wastewater treatment as its easy to operate and low capital cost. General contaminants like dye or oil are present in effluents from textile or petrochemical industries respectively. Membrane fouling due to water soluble or insoluble residue reduce the efficiency and life span[1-5].
Since long time cellulose is used in water treatment [6-10]. But the cellulose fiber has large diameter which prevent it from membrane application such as ultra- filtration and nanofiltration. Cellulose nanofibrils (CNF) with diameter in nanoscale have high mechanical strength and chemical properties. Unlike CNF from plant source, BC are devoid of pectin, hemicellulose or lignin which is the reason for its very high crystallinity and excellent mechanical strength. Microorganism synthesize pure form of cellulose with reticular structure having small pore are biodegradable polymer. Nanopaper made from CNF are applied in the field of biomedical, energy storage, UF and NF.
With growing demand on consumer goods, wastewater released from industries like textile and coating are ever increasing[11-14]. With high aromaticity and longer conjugation in dye molecules, stability of color is much better than before. As a result, improvement of dye removal technique is need of the hour. Oily wastewater or oil-in-water emulsion is released to environment from petrochemical and mining sector as well as oil spillage from oil tanker. Although floating oil on water is easy to remove by simple process but purification of emulsion is much more complicated that needs improved process like membrane technology. Nuclear power plant release radioactive wastewater to the environment which is very dangerous compared to industrial wastewater. This review discuss membranes based on BC to improve the above discussed problems.
2. Wastewater treatment
As the demand for clean water glows, new ways of filtering water of pollutants are being created[15]. With current ways of filtration through nano-papers having issues of low permeance as well as its efficiency. To solve this issue, Mautner et al. evaluates efficiency of BC-org nanopapers prepared in organic liquids (org). The nano-papers produced from ethanol, acetone, and tetrahydrofuran (THF) provided up to 40 times the permeances than BC papers prepared by traditional aqueous dispersion method. Permeance of BC-org is about 1,000 L/m2 h MPa at 20 grammage. Porosity of the paper enhanced in the improvised method due to lower density. Along with its increased permeance, the process created nanopapers that had greater pore sizes of 15 nm, 19 nm, and 19.5 nm from ethanol, acetone and THF dispersios respectively, compared to the current BC-nanopapers with 10 nm. Tensile strength and tensile modulus of BC-org nanopapers are 16~33 MPa and 0.9~1.8 GPa respectively which is about 4~9 times lower than the traditional nanopapers.
2.1. Dye removal
In providing a solution to the process of removing pollutants from wastewater, Derami et al. researches further into the production of composite membrane created with bacterial nanocellulose (BNC) as well as mesoporous polydopamine (mPDA) and palladium (Pd) [16]. Fig. 2 represent schematic presentation of the membrane fabrication. Fig. 3 shows, SEM, TEM, EDX, XPS and XRD.
The membrane that created utilizes the aspect that both mPDA and Pd can be incorporated into the BNC matrix, making the creation process to be easy and efficient. With mPDA providing a large surface area and Pd with its “catalytic characteristics”, the membrane enjoys efficiency of 99 percent of dye removal while being evaluated to allow more water through the membrane. In addition, it is tested that different contaminants with varying structure can also be removed simultaneously by passing through the membrane. The ease of making the membrane and its high efficiency made the Pd-mPDA-BNC membrane to be the suitable ultrafiltration membrane for pollutant removal with very high water flux of 134.7 L/m2 h. With heavy metal ions and many of organic pollutants polluting in produced wastewater, Derami et al. notices the growing concerns and evaluates the efficacy of a combination of polydopamine (PDA) particles and bacterial nanocellulose (BNC) membrane in filtering the pollutants such as rhodamine 6G, methylene blue, and methyl orange[17]. Fig. 4 represents photograph of membranes. Fig. 5 represents photograph of composite solutions and SEM image.
PDA/BNC composite membrane provides effective, bio-friendly, and cost-effective method of removing “either a single pollutant or pollutant cocktail”. It was able to decrease the pollutant contamination level from 40-60 ppm to just only 0.05 ppm. Its characteristics of ease of production and modification, biodegradability and cost-effective regeneration provides versatile and efficient solution to the growing concerns over pollutants in wastewater.
Hu et al. discusses the issues with fouling in current methods of ultrafiltration of pollutants and explores the ways to introduce anti-fouling properties into BC membrane[ 18]. In producing traditional BC membrane, they incorporate “mussel-inspired dopamine” (DA) and with “2D graphene oxide” (GO) for it to provide anti-fouling properties. When experimented, the BC/PDA/RGO (RGO – reduced graphene oxide) showed great efficiency for filtering out dyes and oils used while maintaining high water permeability. Pure water permeability of the composite membrane is 1149.3 L/m2 h at 0.1 MPa. In addition, the superhydrophilicity and superoleophobity of the membrane allowed the lasting performance of anti-fouling properties. Overall, the ease of production and its great ultrafiltration efficiencies as well as its anti-fouling properties makes the BC-PDA-RGO membrane to be the suitable candidate for pollutant removal.
Zhiijang et al. evaluates the usage of chitosan hydrogel coated electrospun nanofiber composite membrane of carboxyl multiwall carbon nanotube grafter bacterial cellulose (BC-g-cMWCNTs) by testing its filtration properties and tensile strength[19]. When tested, the membrane showed almost double the tensile strength of just chitosan membrane with it increasing from 5.43 to 11.76 MPa in dry state and 5.06 to 10.11 MPa in wet state. In addition, it exhibited greater pure water flux, increasing from 52.1 to 140.7 L/m2 h with pressure range of 0.1 -0.6 MPa in chitosan coated BC-g-cMWCNTs. In addition, the successive dye testing was done to show the anti-fouling abilities of the membrane, to further highlight the benefits that the Chitosan coated BC-g-cMWCNTs membrane poses. In conclusion, the efficiency and the sustainability of the membrane function deemed it to be a good candidate for efficient pollutant removal from wastewater.
2.2. Oil removal
The study explores the potential efficiency of BC filter for removal of oil from wastewaters[20]. With BC being prepared in alternative medium with 2.5% corn steep liquor, various characteristics of the filter was tested after 6 and 10 days of cultivation. It was tested for its flexibility, thermal stability, mechanical strength, flowrate and as well as oil filtration capabilities on both day 6 and 10. After experimentation, it was revealed that while both BC from day 6 and day 10 showed “satisfactory flexibility, thermal stability and mechanical strength with 100 percent efficiency in removing oil from wastewater, the membrane after 10 day after emulsion showed that it could handle 100 percent more force applied to it than the membrane from day 6. The study is concluded with the fact that bacterial cellulose membranes are an effective and easy way of removing oil from water and suggests more research into characterization of such membranes. The current method of cellulose filtration is flawed in ways that the vegetable cellulose being used causes an environmental damage in trying to maintain environmental preservation[21]. This study comes to suggest that BC is more effective and easy method of utilizing cellulose for treatment of wastewater. In this study, BC membrane were produced in medium based on corn steep liquor as a more feasible and affordable way of producing BC membrane. After production two membranes over 6 and 10 days, the membrane was tested through various concentration of oil waters (10 ppm, 150 ppm and 230 ppm) and both showed 100 percent removal of the oil. In addition to its great filtering capabilities, the membranes also showed decreasing flowrate as well as filter diameter, inversely proportionate of the production time. As well as its great mechanical capabilities, the 10-day membrane also showed 100 percent more tensile strength than 6-day membrane. Due to nanometric property, greater purity, higher index of crystallinity, high water absorption power and higher tensile strength, BC proves to be a more effective way of filtering oily waters. The study is concluded with claiming the potential for BC membranes to be a great source of biomaterial and as a biotechnological filter in the future.
The study explores the efficiency of never-dried BC and crosslinked cellulose nanofibers (CNF)[22]. Fig. 6 and 7 represent SEM and photograph of membrane respectively.
After production of both BC and CNF, various characteristics were tested. Initially, utilizing SEM imagery, the surfaces of the membranes were evaluated for the microscopic structure. Then, usage of dead-end filtration cell, the water flux and oil rejection rate were tested. Some characteristics observed were that BC membrane showed a growth in the thickness of the membrane while showing no growth in the width of the fibers as well as the noticeable waterflow rate change between day 2 and 4. The study concludes that the never-dried BC had higher efficiency in removing unestablished and stabilized oil from water. The nanoporous structure, wet strength and as well as the micro- level filtration capabilities suggest that BC membranes are potentially an efficient and “green” option for ultrafiltration.
2.3. Heavy metal removal
In recent times, there have been an increase in usage of environmentally dangerous Tellurium (IV) ion (Te) in industrial production and other fields of development[ 23]. Due to its toxicity, the study realizes its importance of removing Te ions from contaminants and tries to solve this problem through the development of BC membrane along with novel TiO2. As experiments carried out, TiO2 @ BCM proved to be a great resource for Tellurium removal from contaminants due to higher surface area of 54.72 m2/g and pore volume of 0.25 m3/g. With absorption capacity getting to 103.64 mg/g as its high surface area and pore volumes proved to be the factor in the filtration. Further testing revealed that TiO2. @ BCM showed decreased efficiency when interfering ions SO42- was introduced in the filtration process. In addition, addition of cations in the contaminants had no effect in the filtration while high acidity proved to also decrease the absorption capacity of TiO2. @ BCM. Despite its shortcomings in specific situations, research concluded with providing filtration method with high potential that could be used to remove Tellurium (IV) from contaminants.
Stocia-Guzun explored the potential solution for removal of Chromium (VI) ion through the usage of BC – magnetite composites[24]. The experiments consisted of various measuring methods, such as Fourier transform infrared spectroscopy, scanning electron microscopy, for it to suggest the valid and efficient structure of BC-magnetite composite produced. Despite the incorporation of magnetite into the bacterial cellulose, it revealed the maintaining of the magnetic properties of magnetite with saturation magnetization to be 40 emu/g. In addition, the study deals with potential iron ion release while filtration. Upon further testing, it revealed that the BC-Fe3O4 composite had the greatest efficiency in pH value of 4 while having the lowest iron ion release in reducing the Chromium (VI) into Chromium (III). Despite its shortcomings at very low and high pH rates, the study concludes that BC-Fe3O4 still proves to be an effective solution for removal of Chromium (VI) ions from initial solutions acidity near pH of 4.
The study investigates the in situ and ex situ production of chitosan (ch) incorporated BC membrane for it to evaluate the efficiency in removing copper from wastewaters[25]. In situ membranes were prepared with varying concentration of chitosan in the culture while ex situ membrane was produced by addition of BC into ch-acetic acid solution. In experimentation, various aspects and characteristics of both membranes were tested. Starting from mechanical properties, water holding capacity and morphological characterization, in situ preparation of BC-chitosan membrane proved to be superior. In addition to its physical properties, despite that in situ and ex situ preparation both had similar percentages of chitosan incorporated in the membrane (35% and 37% respectively), the more “homogenous network” was created in in situ preparation of BC-chitosan membrane, leading to less swelling and higher efficiency in removing copper ion. The study concludes with reaffirming that the membrane only lost 10 percent of efficiency after two cycles and suggests that it has high potential in being used for copper removal in wastewater.
In recent rise in development of nuclear power and its waste production, especially in the case with cesium ions, its radioactivity and chemical toxicity in nuclear wastewater poses a great risk to our environment[26]. This study explores the potential solution for removing these ions out of wastewater through the usage of BC membrane as well as incorporation of sodium nickel hexacyanoferrate (NiHCF) for it to absorb the cesium ions. With experiments carried out determining its porosity, flexibility, stability and removal efficiency through various methods such as scanning electron microscopy and energy-dispersive x-ray spectroscopy, the BC-NiHCF membrane proved to be an efficient solution for cesium removal. Absorption capacity of cesium ions maximizing at 176.44 mg/g, and taking 150 minutes to remove 96.3% removal of Cesium ions. The study concludes with hope that BC-NiHCF could be used in the future for an effective solution for removal of radioactive cesium removal from wastewater.
2.4. Chemical removal
This study research into the usage of 2-D metal organic frameworks along with BC membrane for effective removal of nitrobenzene from wastewater[27]. Through incorporation of copper benzene diazonium chloride Cu(BDC)], the membrane showed better characteristics in pore size, water stability and morphology as well as its permeance and filtration. After experimentation, the membrane showed permeance of 10.85 L/m2 h psi and rejection of nitrobenzene with 68.3 percent rejection rate, showing its capabilities to serve as a filtration system for such contaminants. Compared to the BC membrane without Cu(BDC), the rejection rate showed far inferior efficiencies with rejection rate being 23.4 percent. The study concludes that, though not capable of removing nitrobenzene completely off wastewater, the membrane still showed superior properties than any other filtration methods currently being used.
3. Conclusions
Cellulose derived from plant consist of pectin, hemicellulose and lignin. But bacteria synthesized cellulose are in pure form with high crystallinity, better mechanical strength and highly porous structure. Membrane technology are ever increasing industrial process for treatment of wastewater released from petroleum refining industry, mining activity, textile industry, nuclear power plant etc. Increasing stability of pollutant like organic dye molecules in wastewater need improvisation in membrane separation process. BC is growing area of research for application as UF and NF membrane. In this review BC based membrane for treatment of wastewater containing dye, oil and heavy metals are discussed.