The demands of energy sustainability drive efforts to bio-chemical conversion of biomass into biofuels through pretreatment, enzymatic hydrolysis, and microbial fermentation. Pretreatment leads to significant structural changes of the complex lignin polymer that affect yield and productivity of the enzymatic conversion of lignocellulosic biomass. Structural changes of lignin after pretreatment include functional groups, inter unit linkages and compositions. These changes influence non-productive adsorption of enzyme on lignin through hydrophobic interaction and electrostatic interaction as well as hydrogen bonding. This paper reviews the relationships between structural changes of lignin and enzymatic hydrolysis of pretreated lignocellulosic biomass. The formation of pseudo-lignin during dilute acid pretreatment is revealed, and their negative effect on enzymatic hydrolysis is discussed.
In this study, performances of mesoporous Mo/Al2O3 catalysts prepared by sol-gel and post-hydrolysis methods in hydrocracking of atmospheric residual oil were compared. In addition, different methods: (i) the single step and (ii) conventional impregnation method to incorporate active metal over the mesoporous support were also investigated. For single step method, Mo/Al2O3 catalysts were synthesized directly by sol-gel and post-hydrolysis method. On the other hand, the impregnation method was a two step procedure which involved the production of alumina via sol-gel or post-hydrolysis method and followed by respective Mo impregnation. In general, mesoporous Mo/Al2O3 catalysts prepared by sol-gel method resulted in relatively higher surface area (> 400 m2/g) and large pore volume (- 0.8 cm3/g). Mo/Al2O3 catalysts prepared by sol-gel method exhibited higher hydrocracking activity as well. The Mo crystal size was found to relate directly with the hydrocracking result.
Catalytic hydrolysis of sodium borohydride can potentially be considered as a convenient and safe method to generate hydrogen, an environmentally clean and sustainable fuel for the future. The present effort establishes the development of FeCuCo tri-metallic oxide catalyst by a simple, single-step solution combustion synthesis (SCS) method for hydrogen generation from NaBH4 hydrolysis. Amongst series of FeCuCo tri-metallic oxide catalyst synthesized, FeCuCo with 50:37.5:12.5 wt% respective precursor loading displayed remarkable activity by generating hydrogen at the rate of 1380 mL min-1 g-1 (1242 mL in 18 min) with turnover frequency (TOF) of 62.02 mol g-1 min-1. The catalyst was characterized by using various techniques to understand their physiochemical and morphological properties. The results revealed that the catalyst synthesized by combustion method led to the formation of FeCuCo with appreciable surface area, porous foam-like morphology and high surface acidity. Major factors affecting the hydrolysis of NaBH4 such as catalyst loading, NaOH concentration and temperature variation were studied in detail. Additionally, the FeCuCo catalyst also displayed substantial recyclability performance up to eight cycles without considerable loss in its catalytic activity. Therefore, FeCuCo oxide can be demonstrated as one of the most efficient, cost effective tri-metallic catalyst so far for application in the hydrogen generation.
In recent years, visualization and characterization of lignocellulose at different scales elucidate the modifications of its ultrastructural and chemical features during hydrothermal pretreatment which include degradation and dissolving of hemicelluloses, swelling and partial hydrolysis of cellulose, melting and redepositing a part of lignin in the surface. As a result, cell walls are swollen, deformed and de-laminated from the adjacent layer, lead to a range of revealed droplets that appear on and within cell walls. Moreover, the certain extent morphological changes significantly promote the downstream processing steps, especially for enzymatic hydrolysis and anaerobic fermentation to bioethanol by increasing the contact area with enzymes. However, the formation of pseudo-lignin hinders the accessibility of cellulase to cellulose, which decreases the efficiency of enzymatic hydrolysis. This review is intended to bridge the gap between the microstructure studies and value-added applications of lignocellulose while inspiring more research prospects to enhance the hydrothermal pretreatment process.
This work investigated the effects of 3-aminopropyl triethoxy silane (APTES) hydrolysis time on the physicochemical properties of the resulting starch/epoxidized soybean oil (ESO) bioplastics comprehensively. FTIR analysis confirmed that APTES hydrolyzed for 4 h had the best modification effect on starch. The results of XRD and TGA demonstrated the successful silylation of starch by APTES despite hydrolysis time. Silylation treatment reduced the thermal stability of starch slightly, but enhanced the thermal stability of the resultant bioplastics, revealing better interaction between silylated starch and ESO. The interfacial adhesion of starch and ESO in the bioplastics was obviously enhanced when APTES was hydrolyzed for 2-24 h. The bioplastics with APTES hydrolyzed for 2-4 h showed more desirable tensile properties as the silane hydrolysis was complete and self-condensation of hydrolyzed silanes was avoided. The bioplastics containing silylated starch still showed superior opacity and biodegradability.
Biodiesel production from Calophyllum inophyllum oil in Indonesia produces significant biomass waste, including seed shells. This study explores the conversion of the seed shell of Calophyllum inophyllum into nanocrystalline cellulose (NCC) via consecutive alkalization, bleaching and hydrolysis using various organic acids. Scanning electron microscopy (SEM) analysis showed a reduction in the diameter of cellulose fibers from 21.7 μm to 9.6 μm after alkalinization and bleaching. The hydrolysis process using several organic acids was optimized to produce thermally stable nanocellulose while maintaining its crystallinity. The diameter of the resulting nanofibrous cellulose was 20.53 nm for citric acid, 21.69 nm for maleic acid, and 22.06 nm for formic acid hydrolysis. In particular, lactic acid-derived NCC (NCC-LA) showed the highest crystallinity of 64.22 % with an average diameter of ~13.69 nm. Optimization of hydrolysis parameters using Response Surface Methodology (RSM) suggested 74.79 % crystallinity could be achieved with 6.01 M lactic acid following 3.46 h of hydrolysis at 91.12 °C.
To express and determine the hydrolytic activity of a cellobiohydrolase (TTCBH6B) from the thermophilic fungus Thielavia terrestris in Pichia pastoris.
Managing plastic waste remains an urgent environmental concern and switching to biodegradable plastics can reduce the dependence on depleting fossil fuels. This study emphasises the efficacy of macroalgae wastes, Eucheuma denticulatum residues (EDRs), as potential alternate feedstock to produce l-lactic acid (l-LA), the monomer of polylactic acid, through fermentation. An innovative environmental friendly strategy was explored in this study to develop a glucose platform from EDRs: pretreatment with microwave-assisted autohydrolysis (MAA) applied to enhance enzymatic hydrolysis of EDRs. The results indicate that MAA pretreatment significantly increased the digestibility of EDRs during the enzymatic hydrolysis process. The optimum pretreatment conditions were 120 °C and 50 min, resulting in 96.5% of enzymatic digestibility after 48 h. The high l-LA yield of 98.6% was obtained using pretreated EDRs and supplemented with yeast extract. The energy analysis implies that MAA pretreatment could further improve the overall energy efficiency of the process.
Intensive studies have been performed on the improvement of bioethanol production by transformation of lignocellulose biomass. In this study, the digestibility of corn stover was dramatically improved by using laccase immobilized on Cu2+ modified recyclable magnetite nanoparticles, Fe3O4-NH2. After digestion, the laccase was efficiently separated from slurry. The degradation rate of lignin reached 40.76%, and the subsequent cellulose conversion rate 38.37% for 72 h at 35 °C with cellulase at 50 U g-1 of corn stover. Compared to those of free and inactivated mode, the immobilized laccase pre-treatment increased subsequent cellulose conversion rates by 23.98% and 23.34%, respectively. Moreover, the reusability of immobilized laccase activity remained 50% after 6 cycles. The storage and thermal stability of the fixed laccase enhanced by 70% and 24.1% compared to those of free laccase at 65 °C, pH 4.5, respectively. At pH 10.5, it exhibited 16.3% more activities than its free mode at 35 °C. Our study provides a new avenue for improving the production of bioethanol with immobilized laccase for delignification using corn stover as the starting material.
A study was carried out to determine the effect of enzyme concentration, temperature and incubation time of bromelain on nitrogen content (NC) and degree of hydrolysis (DH) of hydrolysate from cockle (Anadara granosa) meat wash water. Protein precipitation of cockle meat wash water was conducted at pH 4. The precipitate was then hydrolyzed using bromelain at concentrations of 0.5, 1.5 and 2.5% (enzyme/substrate). The best enzyme concentration was subsequently used to study the effect of incubation temperature at 30, 45 and 60°C. The best temperature was then used to determine the effect of incubation time at 0, 24 and 48 hours. Increasing bromelain concentration from 0 to 2.5% produced an increase in NC and DH. Similarly, increasing the incubation time from 0 to 48 hours also increased the value of NC and DH. However, while the increasing of incubation temperature from 30 to 60°C produced an increase in NC, no significant difference was observed for DH.
Green mussel (Perna viridis) was hydrolysed with alcalase under two different conditions consisting of pH7, E/S5% or pH 9, E/S 3% at 60°C for two hours. Hydrolysis at pH 9, E/S3% resulted in a higher degree of hydrolysis (DH) than pH7, E/S5% with degree of hydrolysis of 37.00% and 28.33%, respectively. The green mussel hydrolysates were characterized by molecular weight of
The rate of aqueous cleavage of N-(2’-hydroxyphenyl)phthalimide (A), monitored at 320 nm, 1.0 10–3 M NaOH, 35ºC and within CH3CN content range 1% – 80% v/v in mixed aqueous solvents, follows the reaction scheme: A + HO-/H2O ➝ B + HO-/H2O ➝ P1 + P2 where B, P1 and P2 represent N-(2’-hydroxyphenyl)phthalamic acid, phthalic acid and 2-hydroxyaniline, respectively. The values of k1 and k2 at different content of CH3CN have been calculated from a kinetic equation based upon a reaction scheme with two irreversible pseudo-first-order consecutive reaction paths. The values of k1/k2 are > 104 within CH3CN content range 1% – 80% v/v in mixed aqueous solvents. The intermediate hydrolysis product (B) exists in 72% dianionic, 27.9% monoanionic and 0.1% nonionic form under the present experimental conditions. Both dianionic and monoanionic forms of B are non-reactive while the nonionic form of B is reactive towards hydrolysis under such conditions.
The present study sheds light on the physical and chemical characteristics of microcrystalline cellulose (MCC) isolated from oil palm fronds (OPF) pulps. It was found that the OPF MCC was identified as cellulose II polymorph, with higher crystallinity index than OPF α-cellulose (CrIOPFMCC: 71%>CrIOPFα-cellulose: 47%). This indicates that the acid hydrolysis allows the production of cellulose that is highly crystalline. BET surface area of OPF MCC was found to be higher than OPF α-cellulose (SBETOPFMCC: 5.64m(2)g(-1)>SBETOPFα-cellulose:Qa(0) 2.04m(2)g(-1)), which corroborates their potential as an adsorbent. In batch adsorption studies, it was observed that the experimental data fit well with Langmuir adsorption isotherm in comparison to Freundlich isotherm. The monolayer adsorption capacity (Qa(0)) of OPF MCC was found to be around 51.811mgg(-1) and the experimental data fitted well to pseudo-second-order kinetic model.
This paper reviews reported studies on the hydrolysis of starch especially sago via acid and enzyme. The review begins with overview of sago palm and the starch industry, followed by process of extracting the starch from sago pith. Physicochemical properties of sago starch were tabulated for better understanding of hydrolysis process. Factors or process condition influencing hydrolysis process is discussed based on results from previous researches. Advantages and disadvantages of each hydrolysis is also discussed. Generally, there are very few researches dedicated on sago starch as compared to other starches. It can be concluded that, enzyme hydrolysis gives higher yield at milder process conditions. However, the reaction rate of enzyme hydrolysis is still low compared to acid hydrolysis.
A huge amount of feathers is generated as a waste every year. Feathers can be a protein source if it is treated with an appropriate method. The present study investigates feasibility of autoclave alkaline and microwave alkaline pretreatments to be combined with enzymatic treatment for feather solubilization and protein production. Hydrolysis of chicken feather by autoclave alkaline pretreatment followed by an enzymatic method (AAS) or microwave alkaline pretreatment followed by an enzymatic method (MAS) was optimized by response surface methodology. Various NaOH concentrations for autoclave alkaline pretreatment (0.01-0.1 M) and microwave-alkaline pretreatment (0.01-0.05 M) were applied. The holding time for both pretreatments ranged from 1 to 10 min. The pretreated feathers were subjected to enzymatic hydrolysis using a commercial enzyme prior to analysis of protein content, feather solubilization, functional groups, and elemental composition (carbon, hydrogen, nitrogen and sulfur) of the treated feathers. The results revealed that both autoclave alkaline pretreatment and microwave alkaline pretreatment under optimized conditions of 0.068 M NaOH, 2 min holding time, 105 °C and 450 W, 0.05 M NaOH for 10 min, respectively, enhanced the subsequent Savinase hydrolysis of chicken feathers to achieve more than 80% degradation and more than 70% protein recovery. Fourier transform infrared spectroscopy results showed that both thermal-alkaline pretreatments weakened the structure of the feather. Reduction of carbon, nitrogen, and sulfur occurred in both thermal-alkaline pretreatments of feathers indicating degradation of the feather as well as protein release. Thermal-alkaline pretreatment may be a promising method for enhancing the enzymatic hydrolysis of chicken feathers and for producing a protein-rich hydrolysate.
Production of cellulases and xylanase by a novel Trichoderma asperellum UC1 (GenBank accession no. MF774876) under solid state fermentation (SSF) of raw oil palm frond leaves (OPFL) was optimized. Under optimum fermentation parameters (30 °C, 60-80% moisture content, 2.5 × 106 spores/g inoculum size) maximum CMCase, FPase, β-glucosidase and xylanase activity were recorded at 136.16 IU/g, 26.03 U/g, 130.09 IU/g and 255.01 U/g, respectively. Cellulases and xylanase were produced between a broad pH range of pH 6.0-12.0. The enzyme complex that comprised of four endo-β-1,4-xylanases and endoglucanases, alongside exoglucanase and β-glucosidase showed thermophilic and acidophilic characteristics at 50-60 °C and pH 3.0-4.0, respectively. Glucose (16.87 mg/g) and fructose (18.09 mg/g) were among the dominant sugar products from the in situ hydrolysis of OPFL, aside from cellobiose (105.92 mg/g) and xylose (1.08 mg/g). Thermal and pH stability tests revealed that enzymes CMCase, FPase, β-glucosidase and xylanase retained 50% residual activities for up to 15.18, 4.06, 17.47 and 15.16 h of incubation at 60 °C, as well as 64.59, 25.14, 68.59 and 19.20 h at pH 4.0, respectively. Based on the findings, it appeared that the unique polymeric structure of raw OPFL favored cellulases and xylanase productions.
Oil and grease, carbohydrate, protein, and lignin are the main constituents of high strength wastewaters such as dairy wastewater, cheese whey wastewater, distillery wastewater, pulp and paper mill wastewater, and slaughterhouse wastewaters. These constituents have contributed to various operational problems faced by the high-rate anaerobic bioreactor (HRAB). During the hydrolysis stage of anaerobic digestion (AD), these constituents can be hydrolyzed. Since hydrolysis is known to be the rate-limiting step of AD, the overall AD can be enhanced by improving the hydrolysis stage. This can be done by introducing pretreatment that targets the degradation of these constituents. This review mainly focuses on the biological pretreatment on various high-strength wastewaters by using different types of enzymes namely lipase, amylase, protease, and ligninolytic enzymes which are responsible for catalyzing the degradation of oil and grease, carbohydrate, protein, and lignin respectively. This review provides a summary of enzymatic systems involved in enhancing the hydrolysis stage and consequently improve biogas production. The results show that the use of enzymes improves the biogas production in the range of 7 to 76%. Though these improvements are highly dependent on the operating conditions of pretreatment and the types of substrates. Therefore, the critical parameters that would affect the effectiveness of pretreatment are also discussed. This review paper will serve as a useful piece of information to those industries that face difficulties in treating their high-strength wastewaters for the appropriate process, equipment selection, and design of an anaerobic enzymatic system. However, more intensive studies on the optimum operating conditions of pretreatment in a larger-scale and synergistic effects between enzymes are necessary to make the enzymatic pretreatment economically feasible.
Microwave assisted acid hydrolysis (H2SO4 and HCl with >0.5 mol/L) to produce bioethanol from sago pith waste (SPW) was studied. The energy consumption for microwave hydrolysis at different energy inputs and acid concentration were calculated. The overall energy consumption for bioethanol fuel production from SPW was assessed. A maximum of 88% glucose yield and 80% ethanol yield (3.1 g ethanol per 10 g SPW) were obtained using 1.0 mol/L H2SO4. Microwave hydrolysis using 1.0 mol/L H2SO4 consumed the minimum energy of 8.1 kJ to produce 1 g glucose from SPW when energy input was fixed at 54 kJ (900 W for 1 min). In general, 1 g glucose can produce 16 kJ. The overall energy consumption for fuel grade bioethanol production from SPW was 31.77 kJ per g ethanol, which was slightly higher than the lower heating values of ethanol (26.74 kJ/g ethanol).
Oil palm empty fruit bunch (EFB) fibres were pretreated by gamma irradiation followed by sodium carbonate (Na2
CO3
)
before the acid hydrolysis process to produce reducing sugars using diluted sulphuric acid (H2
SO4
). In this study, EFB
fibres were irradiated at different doses, i.e. 0, 100 and 200 kGy. Meanwhile, the gamma irradiated sample were then
subjected to Na2
CO3 pretreatment with 0 and 5% total titratable alkali (TTA). The effect of the pretreatment using gamma
irradiation and Na2
CO3
on the physical and chemical properties of the EFB fibres and the yield of the reducing sugar
obtained from the acid hydrolysis process was investigated. The obtained results showed that the content of holocellulose
was increased significantly with the increase of irradiation doses combined with Na2
CO3 pretreatment, whereas lignin
content of the EFB was decreased. The gamma irradiation and Na2
CO3 pretreatment resulted in structure breakage
and removal of silica of EFB fibres which can be due to the swelling of the fibres. A synergistic effect between gamma
irradiation and Na2
CO3 was observed, in which the yield of reducing sugars was increased by combining the gamma
irradiation and Na2
CO3 pretreatment.
Poplar trees rapidly yield wood and are therefore suitable as a biofuel feedstock; however, the quality of poplar is modest, and the profitability of poplar cultivation depends on the efficiency of the harvesting process. This study offers a simple and sustainable technique to harvest lignocellulosic resources from poplar for bioethanol production. The proposed two-step pretreatment method increased the surface lignin content and decreased the surface polysaccharide content. The cellulose content increased to 54.9% and the xylan content decreased to 6.7% at 5% AC. The cellulose yield of poplar residues (Populus L.) reached 65.5% by this two-step acetic acid (AC) and sodium sulphite (SS) treatment method. Two-step pretreatment using 5% AC and 4% SS obtained a recovery of nearly 80% of the total available fermentable sugar. The surface characterization showed a higher porosity in treated samples, which improved their hydrolysability. This method decreased the amount of lignin in plant biomass, making it applicable for further wood resource recovery or waste recycling for biorefinery purposes at very low costs.