Crude oil and petroleum products made from it are increasingly being extracted and consumed worldwide as an important energy source. During necessary transportation, e.g., by tanker, an oil spill might occur, which leads to water pollution by oil. One of the methods of cleaning up oil spills is to use sorbents, preferably made from natural materials. This study evaluates the remediation efficiency of brackish water polluted with crude oil, marine diesel oil (MDO) and lubricating oil. The experiment was performed with three different sorbents (straw, straw modified with methoxytrimethylsilanes (MTMS) and wood chip shavings) and without them. The evaporation loss and the dissolved and sorbed fractions of oil were measured by gas chromatography (GC) to evaluate remediation efficiency. Hydrophobization made the natural sorbents buoyant for the duration of the experiment, with only a slight increase in the maximum sorption capacity. The sorbents increased the evaporation of the oils and also of the water, reduced the proportion of the oil dissolved in water and retained the sorbed proportion for the lubricating oil and partly for the MDO, to such an extent that it could not be extracted entirely even after a 60-min extraction time.
Background
With every oil tanker comes the risk of an accident and oil spill. Sorbents are the most suitable means to remove oil spills. Aerogels as sorbents have high porosity and can be made from cellulose from paper waste. The literature does not distinguish between paper and cardboard as sources of cellulose aerogels and little is known about composites of cellulose aerogels consisting of cellulose fibres and chemically untreated, unprocessed fibres or particles of straw, wool, macroalgae or cellulose acetate from cigarette butts. In this study, the sorption properties for marine diesel oil and biodiesel of such aerogels and their regenerative capacity with bioethanol were investigated.
Methods
Cellulose aerogels were prepared from office paper and cardboard waste without and with chemically untreated algae, straw, wool and cellulose acetate as a composite by freeze drying. All samples were hydrophobised with methylsilane. The density to calculate the porosity and the contact angle were determined. Then the sorption capacity was determined over five cycles of sorption of oil and regeneration with bioethanol.
Results
The average contact angle of all samples was 125°, indicating hydrophobicity. Paper-based aerogels were found to consistently have higher sorption capacities for biodiesel, marine diesel oil and bioethanol than cardboard-based aerogels. In particular, the wool/cellulose aerogel composite was found to have better sorption capacity for biodiesel, marine diesel oil and bioethanol than all other samples. The cellulose acetate/cellulose aerogel composite showed significantly higher sorption capacities than the paper and cardboard control samples (highest value is 32.25 g g−1) only when first used as a sorbent for biodiesel, but with a rapid decrease in the following cycles.
Cellulose aerogels with polyester resin as cross-linkers have attracted much attention. This study describes the route to produce a fully bio-based aerogel with high added value from waste paper and starch, cellulose acetate and starch–cellulose acetate mixture as cross-linkers for oil adsorption, instead of the environmentally harmful polyester resin. The manufacturing process is simple, sustainable and cost-efficient, without releasing harmful by-products into the environment. The effects of different cross-linkers on the oil adsorption, dynamic oil retention, reusability and morphology of the aerogels were studied in detail. Experimental results show that these environmentally friendly recycled aerogels have a very low density, i.e., —0.0110–0.0209 g cm−3, and highly porous structures, with a porosity of 96.74–99.18%. The synthesized hydrophobic aerogels showed contact angles of ∼124–129°. The compression moduli are lower than that of an aerogel with polyester as a cross-linker, but the compression modulus of the mixture of starch and cellulose acetate especially shows a higher value than expected. The sorption capacity of the aerogels with bio-based cross-linkers was significantly increased compared to the aerogels with polyester; it is now up to 56 times their own weight. The aerogels also have good oil-retention properties.
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