Development of Kraft Lignin and Coating Technique to Prepare Coated Urea Fertilizers with Increased Nutrient Use Efficiency
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Coating urea to prepare controlled release N-fertilizer has been considered as an effective way to increase its nutrient use efficiency, thus reduce its waste and the consequent harmful environmental impacts. Inorganic sulphur and synthetic polymers have been used in the industry as coating materials together with utilization of various types of expensive coating equipment which commonly requires also complicated technical setup and controls. As development trends, biopolymers are attention-grabbing to replace the synthetic polymers. Alternative simple coating technique is also desired. So far, polylactic acid (PLA) has been reported as a more promising biopolymer than several synthetic polymers for coating. On the other hand, highly purified industrial softwood kraft lignin (SKL) produced after LignoBoost process is now available in a large quantity, which should also be a promising biopolymer for the coating application. Aiming at increase of the efficiency of PLA-coated urea and development of alternative coating technique to generally make the preparation of control-released fertilizer more effective, economic and environmentally sustainable, in this study, SKL has been used in a PLA-SKL blending form as complex coating material and simple dip-coating technique has been investigated and applied. In order to lower the wettability of PLA-SKL coat layer, four different anhydrides, namely acetic anhydride, palmitic anhydride, lauric anhydride and trifluoroacetic anhydride, were used to esterify SKL to form AcSKL, PaSKL, LauSKL and TFASKL respectively before its utilization. NMR and FTIR analyses showed that the esterification reactions have been completed for AcSKL and PaSKL. LauSKL was partly esterified due to the low charge of lauric anhydride regent, while TFASKL was not esterified expectantly due to the steric hindrance between the three F atoms and polymeric SKL. In order to obtain organically bound nitrogen structure to also create slow-release type of N-fertilizer, Mannich reaction on SKL using diethylamine was also conducted to prepare ManSKL. The reaction was completed as shown by NMR and FTIR spectroscopy. To bring further functionality of metal chelation to open the possibility to also bring essential trace element into the final fertilizer, ethylenediaminetriacetic acid (ED3A) was synthesized and further used via Mannich reaction to modify SKL to form ED3ASKL. ED3A is not commercially available and it was synthesized successfully with an environmentally friendly method from commercial EDTA and the structure was verified by NMR spectroscopy. However, the Mannich reaction using ED3A was not very successful as shown by product s NMR and FTIR spectra. In a comparison experiment using vanillyl alcohol as a lignin model structure, ED3A was successfully coupled onto the vanillyl alcohol structure as shown by NMR and FTIR spectra. Apparently there was a severe steric hindrance from SKL for the Mannich reaction using the larger molecule of ED3A than diethylamine for Mannich reaction. For utilization of dip-coating technique, dichloromethane (DCM) and tetrahydrofuran (THF) were chosen to dissolve PLA and SKL or the modified SKL respectively. Cast films of PLA/modified lignin complex were prepared using Teflon Petri-dishes. The optimal concentration of PLA in DCM and the effect of DCM/THF ratios on the prepared cast film which expectantly represents the quality of the complex coat in the coated urea were compared with SEM images and contact angle determination. It has been found that a 30 wt\% of PLA in DCM was the best and this solution mixed with modified lignin solution (6 % in THF) in a ratio of DCM/THF =3/2 (v/v) had the best film performances and water barrier properties. Generally, the cast films from PLA/modified lignin complexes showed better properties compared with the neat PLA cast film. No pores and cracks were found on the surface. Comparatively, the LauSKL film showed the most homogeneous surface. But the AcSKL film had the best water barrier properties. The PLA/modified lignin complex coated urea was then prepared by dip-coating process. The coat thickness and weight increase showed statistically positive correlations against the repeating times of the dip-coating process. The coating layer also showed one single layer structure. The speed of urea releasing for coated urea was tested and the results showed that it was much slower than the un-coated or PLA-coated urea. The single-layered PLA/AcSKL and PLA/ManSKL were both observed with sound properties in delaying the release of urea cores in water. Conclusively, the PLA/modified SKL coated urea fertilizers prepared by dip-coating technique demonstrated in this study have highly efficiency with better effects of water barrier, organically N slow release, and nitrification inhibiting (due to free phenolic functional groups) properties. Both SKL and the dip-coating technique are promising in the fertilizer applications.