Long-term evaluation of palm oil mill effluent (POME) steam reforming over lanthanum-based perovskite oxides.

To replace the obsolete ponding system, palm oil mill effluent (POME) steam reforming (SR) over net-acidic LaNiO3 and net-basic LaCoO3 were proposed as the POME primary treatments, with promising H2-rich syngas production. Herein, the long-term evaluation of POME SR was scrutinized with both catalysts under the optimal conditions (600 °C, 0.09 mL POME/min, 0.3 g catalyst, & 74-105 µm catalyst particle size) to examine the catalyst microstructure changes, transient process stability, and final effluent evaluation. Extensive characterization proved the (i) adsorption of POME vapour on catalysts before SR, (ii) deposition of carbon and minerals on spent SR catalysts, and (iii) dominance of coking deactivation over sintering deactivation at 600 °C. Despite its longer run, spent LaCoO3 (50.54 wt%) had similar carbon deposition with spent LaNiO3 (50.44 wt%), concurring with its excellent coke resistance. Spent LaCoO3 (6.12 wt%; large protruding crystals) suffered a harsher mineral deposition than spent LaNiO3 (3.71 wt%; thin film coating), confirming that lower reactivity increased residence time of reactants. Transient syngas evolution of both SR catalysts was relatively steady up to 4 h but perturbed by coking deactivation thereafter. La2O2CO3 acted as an intermediate species that hastened the coke removal via reverse Boudouard reaction upon its decarbonation. La2O2CO3 decarbonation occurred continuously in LaCoO3 system but intermittently in LaNiO3 system. LaNiO3 system only lasted for 13 h as its compact ash blocked the gas flow. LaCoO3 system lasted longer (17 h) with its porous ash, but it eventually failed because KCl crystallites blocked its active sites. Relatively, LaCoO3 system offered greater net H2 production (72.78%) and POME treatment volume (30.77%) than LaNiO3 system. SR could attain appreciable POME degradation (>97% COD, BOD5, TSS, & colour intensity). Withal, SR-treated POME should be polished to further reduce its incompliant COD and BOD5.

Potential application of Allium Cepa seeds as a novel biosorbent for efficient biosorption of heavy metals ions from aqueous solution.

Abatement of pollutants i.e. heavy metals by using green biomaterials is an emerging area of interest due to its cost-effective and renewability. In the present study, the potential of Alium Cepa seed biomass (ACSB) as a novel biosorbent for the adsorption of Cr(VI), Cd(II), Zn(II), Cu(II) and Pb(II) was investigated. The FTIR spectrum of ACSB confirmed a presence of surface OH bond, an essential functional group for metal uptake. Biosorption factors such as pH (2-10), time (15-190 min), dosage (1-5 g/L) and initial metal concentration (50-200 mg/L) were optimized at the ambient conditions. The equilibrium adsorption time was obtained at 90 min for Cd(II), Cu(II) and Pb(II), as well as 120 min for Cr(VI) and Zn(II), respectively, for the mentioned metal ions removal. The maximum removal efficiency was obtained at 4 g/L of ASCB for 50 mg/L adsorbate and a neutral pH. Under this condition, the maximum uptake was 0.67, 1.50, 1.68, 1.03 and 1.75 mg/L for Cr(VI), Cd(II), Zn(II), Cu(II) and Pb(II), respectively. Monolayer biosorption was determined for the studied heavy metals. The removal of the metal ions by ACSB followed a pseudo 2nd order sorption kinetics. The results suggested that ACSB is more suitable to remove (99%) Pb(II), Cu(II), Cd(II) as compared to Zn(II) and Cr(VI).

Integration of machine learning-based prediction for enhanced Model's generalization: Application in photocatalytic polishing of palm oil mill effluent (POME).

In predicting palm oil mill effluent (POME) degradation efficiency, previous developed quadratic model quantitatively evaluated the effects of O2 flowrate, TiO2 loadings and initial concentration of POME in labscale photocatalytic system, which however suffered from low generalization due to the overfitting behaviour. Evidently, high RMSE (131.61) and low R2 (-630.49) obtained indicates its insufficiency in describing POME degradation at unseen factor ranges, hence verified the fact of poor generalization. To overcome this issue, several models were developed via machine learning-assisted techniques, namely Gaussian Process Regression (GPR), Linear Regression (LR), Decision Tree (DT), Supported Vector Machine (SVM) and Regression Tree Ensemble (RTE), subsequently being assessed systematically. To achieve high generalization, all models were subjected to 'train-all-test-all' strategy, 5-fold and 10-fold cross validation. Specifically, GPR model was furnished with high accuracy in 'train-all-test-all' strategy, judging from its low RMSE (1.0394) and high R2 (0.9962), which however menaced by the risk of overfitting. In contrast, despite relatively poorer RMSE and R2 (1.7964 and 0.9886) obtained in 5-fold cross validation, GPR model was rendered with highest generalization, while sufficiently preserving its accuracy in development process. Besides, SVM and RTE models were also demonstrated promising R2 (0.9372 and 0.9208), which however shadowed by their high RMSEs (4.2174 and 4.7366). Furthermore, the extraordinary generalization of GPR model was coincidentally verified in 10-fold cross validation. The lowest RMSE (2.1624) and highest R2 (0.9835) obtained with feature number of 36 asserted its sufficiency in both generalization and accuracy prospect. Other models were all rendered with slight lower R2 (> 0.9), plausibly due to the higher RMSE (> 4.0). According to GPR model, optimized POME degradation (52.52%) can be obtained at 70 mL/min of O2, 70.0 g/L of TiO2 and 250 ppm of POME concentration, with only ∼3% error as compared to the actual data.

Biodiesel synthesized from waste cooking oil in a continuous microwave assisted reactor reduced PM and NOx emissions.

A synergistic effect of the activated limestone-based catalyst (LBC) and microwave irradiation on the transesterification of waste cooking oil (WCO) was screened using a two-level factorial design and response surface methodology. The catalyst was prepared using a wet-impregnation method and was characterised for its surface element, surface morphology, surface area and porosity. The reaction was performed in a purpose-built continuous microwave assisted reactor (CMAR), while the conversion and yield of biodiesel were measured using a gas chromatography. The results showed that the catalyst loading, methanol to oil molar ratio and the reaction time significantly affect the WCO conversion. The optimum conversion of oil to biodiesel up to 96.65% was achieved at catalyst loading of 5.47 wt%, methanol to oil molar ratio of 12.21:1 and the reaction time of 55.26 min. The application of CMAR in this work reduced the transesterification time by about 77% compared to the reaction time needed for a conventional reactor. The biodiesel produced in this work met the specification of American Society for Testing and Materials (ASTM D6751). Engine test results shows the biodiesel has a lower NOx and particulate matters emissions compared to petrodiesel.

Photocatalytic treatment of palm oil mill effluent by visible light-active calcium ferrite: Effects of catalyst preparation technique.

Palm oil mill effluent (POME) is a serious and expensive environmental problem in Malaysia. In this paper, CaFe2O4 is introduced as a novel photocatalyst for the degradation of POME under visible light irradiation. Two synthesis routes, auto-combustion and co-precipitation, and two calcination temperatures 550 °C and 700 °C were used to produce four CaFe2O4 catalysts AC550, AC700, CP550 and CP700. CP550 exhibited the greatest photocatalytic degradation at 56% chemical-oxygen-demand (COD) removal after 8 h of irradiation which dropped to 49% after three consecutive cycles indicating reasonable conversion and high recyclability. BET analysis indicated CP550 had the highest SBET (27.28 m2/g) and pore volume (0.077 cm3/g) which dropped precipitously for CP700 upon increasing the calcination temperature to an SBET of 9.73 m2/g and pore volume of 0.025 cm3/g due to annealing which created a smoother surface area as evidenced by the SEM images. UV-Vis DRS indicated CP550 had the highest band-gap (1.52 eV) which is likely due to the presence of a highly crystalline pure CaFe2O4 phase compared to the other products which existed as a mixture of Fe oxidation states evidenced by the XRD data. The PL spectra for all catalysts indicated significantly lower recombination rate for both CP550 and CP700. Introduction of IPA into the reaction mixture to eliminate hydroxyl radicals resulted in a diminishing of COD removal from 56% to 7% proving hydroxyl radicals to be the primary reactive species responsible for photodegradation of POME.

Pyrolysis production of fruit peel biochar for potential use in treatment of palm oil mill effluent.

Fruit peel, an abundant waste, represents a potential bio-resource to be converted into useful materials instead of being dumped in landfill sites. Palm oil mill effluent (POME) is a harmful waste that should also be treated before it can safely be released to the environment. In this study, pyrolysis of banana and orange peels was performed under different temperatures to produce biochar that was then examined as adsorbent in POME treatment. The pyrolysis generated 30.7-47.7 wt% yield of a dark biochar over a temperature ranging between 400 and 500 °C. The biochar contained no sulphur and possessed a hard texture, low volatile content (≤34 wt%), and high amounts of fixed carbon (≥72 wt%), showing durability in terms of high resistance to chemical reactions such as oxidation. The biochar showed a surface area of 105 m2/g and a porous structure containing mesopores, indicating its potential to provide many adsorption sites for use as an adsorbent. The use of the biochar as adsorbent to treat the POME showed a removal efficiency of up to 57% in reducing the concentration of biochemical oxygen demand (BOD), chemical oxygen demand COD, total suspended solid (TSS) and oil and grease (O&G) of POME to an acceptable level below the discharge standard. Our results indicate that pyrolysis shows promise as a technique to transform banana and orange peel into value-added biochar for use as adsorbent to treat POME. The recovery of biochar from fruit waste also shows advantage over traditional landfill approaches in disposing this waste.

Restoration of liquid effluent from oil palm agroindustry in Malaysia using UV/TiO2 and UV/ZnO photocatalytic systems: A comparative study.

In this study, we have employed a photocatalytic method to restore the liquid effluent from a palm oil mill in Malaysia. Specifically, the performance of both TiO2 and ZnO was compared for the photocatalytic polishing of palm oil mill effluent (POME). The ZnO photocatalyst has irregular shape, bigger in particle size but smaller BET specific surface area (9.71 m2/g) compared to the spherical TiO2 photocatalysts (11.34 m2/g). Both scavenging study and post-reaction FTIR analysis suggest that the degradation of organic pollutant in the TiO2 system has occurred in the bulk solution. In contrast, it is necessary for organic pollutant to adsorb onto the surface of ZnO photocatalyst, before the degradation took place. In addition, the reactivity of both photocatalysts differed in terms of mechanisms, photocatalyst loading and also the density of photocatalysts. From the stability test, TiO2 was found to offer higher stability, as no significant deterioration in activity was observed after three consecutive cycles. On the other hand, ZnO lost around 30% of its activity after the 1st-cycle of photoreaction. The pH studies showed that acidic environment did not improve the photocatalytic degradation of the POME, whilst in the basic environment, the reaction media became cloudy. In addition, longevity study also showed that the TiO2 was a better photocatalyst compared to the ZnO (74.12%), with more than 80.0% organic removal after 22 h of UV irradiation.

Optimization of photocatalytic degradation of palm oil mill effluent in UV/ZnO system based on response surface methodology.

This paper reports on the optimization of palm oil mill effluent (POME) degradation in a UV-activated-ZnO system based on central composite design (CCD) in response surface methodology (RSM). Three potential factors, viz. O2 flowrate (A), ZnO loading (B) and initial concentration of POME (C) were evaluated for the significance analysis using a 23 full factorial design before the optimization process. It is found that all the three main factors were significant, with contributions of 58.27% (A), 15.96% (B) and 13.85% (C), respectively, to the POME degradation. In addition, the interactions between the factors AB, AC and BC also have contributed 4.02%, 3.12% and 1.01% to the POME degradation. Subsequently, all the three factors were subjected to statistical central composite design (CCD) analysis. Quadratic models were developed and rigorously checked. A 3D-response surface was subsequently generated. Two successive validation experiments were carried out and the degradation achieved were 55.25 and 55.33%, contrasted with 52.45% for predicted degradation value.