This study investigated on the co-pyrolysis of microalgae Chlorella vulgaris and high-density polyethylene (HDPE) waste mixtures which was performed with three types of catalysts, namely limestone (LS), HZSM-5 zeolite, and novel bi-functional LS/HZSM-5/LS. Kissinger-Kai (K-K) model-free method was coupled with Particle Swarm Optimization (PSO) model-fitting method using the thermogravimetric experimental data. A global sensitivity analysis was carried out using Latin Hypercube Sampling and rank transformation to assess the extent of impact of the input kinetic parameters on the output results. Furthermore, a thermodynamic analysis was performed to obtain parameters such as enthalpy change (ΔH), Gibb's free energy (ΔG), and entropy change (ΔS). The activation energy (EA) of the microalgae Chlorella vulgaris and HDPE binary mixture were found to be lower upon the addition of catalysts. Among the catalyst used, bi-functional LS/HZSM-5 catalyst exhibited the lowest EA (83.59 kJ/mol) and ΔH (78 kJ/mol) as compared to LS and HZSM-5 catalysts.
Catalytic cracking of vegetable oil mainly processed over zeolites, and among all the zeolites particularly HZMS-5 has been investigated on wide range for renewable and clean gasoline production from various plant oils. Despite the fact that HZSM-5 offers a higher conversion degree and boost aromatics yield, the isomerate yield reduces due to high cracking activity and shape selectivity of HZSM-5. Hence, to overcome these problems, in this study the transition metals, such as nickel and copper doped over HZSM-5 were tested for its efficiencies to improve the isoparaffin compounds. The catalysts were screened with linoleic acid in a catalytic cracking reaction conducted at 450 ᵒC for 90 min in an atmospheric condition in batch reactor. Then, the gasoline composition of the organic liquid product (OLP) was analysed in terms of paraffin, isoparaffin, olefin, naphthenes and aromatics (PIONA). The results showed that Cu/ZSM-5 produced the highest liquid yield of 79.1%, at the same time reduced the production of gas and coke to 18.8% and 0.7%. Furthermore, the desired isoparaffin composition in biogasoline increased from 1.6% to 6.8% and at the same time reduced the oxygenated and aromatic compounds to 15.4% and 59.7%, respectively. The linoleic acid as model compound of rubber seed oil, in the catalytic cracking reaction provides a clearer understanding of the process. Besides, the water gas shift (WGS) reaction in catalytic cracking reaction provides insitu hydrogen production to saturate the branched olefin into the desired isoparaffin and the aromatics into naphthenes.
Crude rubber seed oil is a potential source for biofuel production. However it contains undesirable impurities such as peroxides and high oxidative components that not only affect the oil stability, colour and shelf-life but promote insoluble gums formation with time that could cause deposition in the combustion engines. Therefore to overcome these problems the crude rubber seed oil is refined by undergoing degumming and bleaching process. The effect of bleaching earth dosage (15-40 wt %), phosphoric acid dosage (0.5-1.0 wt %) and reaction time (20-40 min) were studied over the reduction of the peroxide value in a refined crude rubber seed oil. The analysis of variance shows that bleaching earth dosage was the most influencing factor followed by reaction time and phosphoric acid dosage. A minimum peroxide value of 0.1 milliequivalents/gram was achieved under optimized conditions of 40 wt % of bleaching earth dosage, 1.0 wt % of phosphoric acid dosage and 20 min of reaction time using Response Surface Methodology design.
Employment of edible oils as alternative green fuel for vehicles had raised debates on the sustainability of food supply especially in the third-world countries. The non-edible oil obtained from the abundantly available rubber seeds could mitigate this issue and at the same time reduce the environmental impact. Therefore, this paper investigates the catalytic cracking reaction of a model compound named linoleic acid that is enormously present in the rubber seed oil. Batch-scale experiments were conducted using 8.8 mL Inconel batch reactor having a cyclic horizontal swing span of 2 cm with a frequency of 60 cycles per minute at 450 °C under atmospheric condition for 90 min. The performance of HZSM-5, HBeta, HFerrierite, HMordenite and HY catalysts was tested for their efficiency in favouring gasoline range hydrocarbons. The compounds present in the organic liquid product were then analysed using GC-MS and classified based on PIONA which stands for paraffin, isoparaffin, olefin, naphthenes and aromatics respectively. The results obtained show that HZSM-5 catalyst favoured gasoline range hydrocarbons that were rich in aromatics compounds and promoted the production of desired isoparaffin. It also gave a higher cracking activity; however, large gaseous as by-products were produced at the same time.
Biomass wastes exhibit a great potential to be used as a source of non-depleting renewable energy and synthesis of value-added products. The key to the valorization of excess lignocellulosic biomass wastes in the world lies on the pretreatment process to recalcitrant barrier of the lignocellulosic material for the access to useful substrates. A wide range of pretreatment techniques are available and advances in this field is continuously happening, in search for cheap, effective, and environmentally friendly methods. This review starts with an introduction to conventional approaches and green solvents for pretreatment of lignocellulosic biomass. Subsequently, the mechanism of actions along with the advantages and disadvantages of pretreatment techniques were reviewed. The roles of choline chloride (ChCl) in green solvents and their potential applications were also comprehensively reviewed. The collection of ideas in this review serve as an insight for future works or interest on biomass-to-energy conversion using green solvents.
The environmental footprints of H2productionviacatalytic gasification of wheat straw using straw-derived biochar catalysts were examined. The functional unit of 1 kg of H2was adopted in the system boundaries, which includes 5 processes namely biomass collection and pre-treatment units (P1), biochar catalyst preparation using fast pyrolysis unit (P2), two-stage pyrolysis-gasification unit (P3), products separation unit (P4), and H2distribution to downstream plants (P5). Based on the life-cycle assessment, the hot spots in this process were identified, the sequence was as follows: P4 > P2 > P1 > P3 > P5. The end-point impacts score for the process was found to be 93.4017 mPt. From benchmarking analysis, the proposed straw-derived biochar catalyst was capable of offering almost similar catalytic performance with other metal-based catalysts with a lower environmental impact.
The valorization and conversion of biomass into various value-added products and bioenergy play an important role in the realization of sustainable circular bioeconomy and net zero carbon emission goals. To that end, microwave technology has been perceived as a promising solution to process and manage oil palm waste due to its unique and efficient heating mechanism. This review presents an in-depth analysis focusing on microwave-assisted torrefaction, gasification, pyrolysis and advanced pyrolysis of various oil palm wastes. In particular, the products from these thermochemical conversion processes are energy-dense biochar (that could be used as solid fuel, adsorbents for contaminants removal and bio-fertilizer), phenolic-rich bio-oil, and H2-rich syngas. However, several challenges, including (1) the lack of detailed study on life cycle assessment and techno-economic analysis, (2) limited insights on the specific foreknowledge of microwave interaction with the oil palm wastes for continuous operation, and (3) effects of tunable parameters and catalyst's behavior/influence on the products' selectivity and overall process's efficiency, remain to be addressed in the context of large-scale biomass valorization via microwave technology.
One of the greatest challenges in biorefinery is to reduce biomass' recalcitrance and enable valorization of lignin into higher value compounds. Likewise, green solvents and hydrothermal liquefaction (HTL) with feasible economic viability, functionality, and environmental sustainability have been widely introduced in extraction and conversion of lignin. This review starts with the underscore of disadvantages and limitations of conventional pretreatment approaches and role of green solvents in lignin extraction. Subsequently, the effect of process parameters along with the reaction mechanisms and kinetics on conversion of lignin through HTL were comprehensively reviewed. The limitations of green solvents in extraction and HTL of lignin from biomass were discussed based on the current advancements of the field and future research scopes were also proposed. More details info on HTL of biomass derived lignin which avoid the energy-intensive drying procedures are crucial for the accelerated development and deployment of the advanced lignin biorefinery.
The rising pressure on both cleaner production and sustainable development have been the main driving force that pushes mankind to seek for alternative greener and sustainable feedstocks for chemical and energy production. The biomass 'waste-to-wealth' concept which convert low value biomass into value-added products which contain high economic potential, have attracted the attentions from both academicians and industry players. With a tropical climate, Malaysia has a rich agricultural sector and dense tropical rainforest, giving rise to abundance of biomass which most of them are underutilized. Hence, the biomass 'waste-to-wealth' conversion through various thermochemical conversion technologies and the prospective challenges towards commercialization in Malaysia are reviewed in this paper. In this paper, a critical review about the maturity status of the four most promising thermochemical conversion routes in Malaysia (i.e. gasification, pyrolysis, liquefaction and hydroprocessing) is given. The current development of thermochemical conversion technologies for biomass conversion in Malaysia is also reviewed and benchmarked against global progress. Besides, the core technical challenges in commercializing these green technologies are highlighted as well. Lastly, the future outlook for successful commercialization of these technologies in Malaysia is included.