Extraction, modification and characterization of lignin from oil palm fronds as corrosion inhibitors for mild steel in acidic solution

Abstract : Lignocellulosic biomass in Malaysia can be considered as one of the promising sources of renewable energy. It is mainly composed of cellulose, hemicellulose, and lignin and best-suited for energy and chemical applications due to its sufficient availability, inexpensive and is sustainable. In general, the production of lignocellulosic biomass in Malaysia was considered high and mainly derived from the palm oil industries (approximately 60 million tonnes of oil palm waste were generated in a year). The oil palm biomass waste could possibly be used as alternative resources for the production of paper and cardboard. However, massive amounts of lignin by-product could also be discarded in huge quantities (by the pulp and paper industry) due to lack of awareness on its potential. Having high content of diverse functional groups (phenolic and aliphatic –OH, carbonyls, carboxyls, etc.) and phenylpropanoid structure, lignin can lead to substitutes in industrial applications such as in corrosion inhibition of metals and alloys. Since the oil palm fronds (OPF) are one of the largest biomass waste contributors in Malaysia, it was therefore used as raw material in this study. In order to improve the lignin extractability and properties, the extraction was conducted in different ways (via direct delignification and/or combined pretreatment methods). Due to the high hydrophobicity of lignin, it limits the capability to act as efficient corrosion inhibitors. Hence, modifications of the OPF lignin structure were conducted in two ways; (1) by incorporating organic scavengers (2-naphthol and 1,8-dihydroxyanthraquinone) during autohydrolysis pretreatment before organosolv treatment (percentage yield of lignin: AHN EOL = 13.42±0.71 % and AHD EOL = 9.64±0.84 %) and (2) fractionation of lignin from direct delignification processes (Kraft, soda and organosolv) via ultrafiltration membrane technique (percentage yield of permeate lignin fractions: Kraft = 5.41±2.04 %; soda = 12.29±0.54 % and organosolv = 1.48±0.15 %). The physical and chemical properties of the modified lignins were evaluated by using Fourier Transform Infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography (GPC), thermal analysis and high performance liquid chromatography (HPLC). Modified lignin fractions with higher phenolic –OH content but lower molecular weight, polydispersity as well as aliphatic –OH content resulted in higher values of antioxidant activities. The antioxidant activity seems be dependent on the increase of their free phenolic –OH and ortho-methoxyl content, through the stability of the radical formed and the ability to reduce Fe3+ ions to Fe2+ ions. Indeed, the improved physicochemical properties and antioxidant activity of modified lignin gave positive correlation with the mild steel corrosion inhibition action in 0.5 M HCl solution that were evaluated by electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and weight loss measurements. The best percentage of inhibition efficiencies (IE: 81 – 90 %) were attained at the concentration of 500 ppm for all lignin inhibitors but decreased with the increase in temperature (303 – 333 K). Thermodynamic data indicated that the adsorption of the modified lignin onto the mild steel was spontaneous and the inhibitors were mainly physically adsorbed (physiosorption), supported by the activation energy of adsorption, Ea. The enhanced protective properties of the modified lignin will pave way for an alternative approach for the utilization of these natural waste materials
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Mohd Hazwan Bin Hussin. Extraction, modification and characterization of lignin from oil palm fronds as corrosion inhibitors for mild steel in acidic solution. Food and Nutrition. Université de Lorraine, 2014. English. ⟨NNT : 2014LORR0135⟩. ⟨tel-01750984⟩

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