A recent rise in crab aquaculture activities has intensified the generation of waste shells. In the present study, the waste shells were utilized as a source of calcium oxide to transesterify palm olein into methyl esters (biodiesel). Characterization results revealed that the main component of the shell is calcium carbonate which transformed into calcium oxide when activated above 700 degrees C for 2 h. Parametric studies have been investigated and optimal conditions were found to be methanol/oil mass ratio, 0.5:1; catalyst amount, 5 wt.%; reaction temperature, 65 degrees C; and a stirring rate of 500 rpm. The waste catalyst performs equally well as laboratory CaO, thus creating another low-cost catalyst source for producing biodiesel. Reusability results confirmed that the prepared catalyst is able to be reemployed up to 11 times. Statistical analysis has been performed using a Central Composite Design to evaluate the contribution and performance of the parameters on biodiesel purity.
The (R)-3-hydroxyacyl-ACP-CoA transferase catalyses the conversion of (R)-3-hydroxyacyl-ACP to (R)-3-hydroxyacyl-CoA derivatives, which serves as the ultimate precursor for polyhydroxyalkanoate (PHA) polymerisation from unrelated substrates in pseudomonads. PhaG was found to be responsible for channelling precursors for polyhydroxyalkanoate (PHA) synthase from a de novo fatty acid biosynthesis pathway when cultured on carbohydrates, such as glucose or gluconate. The phaG gene was cloned from Pseudomonas sp. USM 4-55 using a homologous probe. The gene was located in a 3660 bp Sal I fragment (GenBank accession number EU305558). The open reading frame (ORF) was 885 bp long and encoded a 295 amino acid protein. The predicted molecular weight was 33251 Da, and it showed a 62% identity to the PhaG of Pseudomonas aeruginosa. The function of the cloned phaG of Pseudomonas sp. USM 4-55 was confirmed by complementation studies. Plasmid pBCS39, which harboured the 3660 bp Sal I fragment, was found to complement the PhaG-mutant heterologous host cell, Pseudomonas putida PhaGN-21. P. putida PhaGN-21, which harboured pBCS39, accumulated PHA that accounted for up to 18% of its cellular dry weight (CDW). P. putida PhaGN-21, which harboured the vector alone (PBBR1MCS-2), accumulated only 0.6% CDW of PHA.
Aquaculture activity has increased the population of crab, hence increasing the generation of related wastes, particularly the shell. In addition, the number of molting process in crabs compounds further the amount of waste shell generated. As such, in the present work, the application of the waste crab shell as a source of CaO in transesterification of palm olein to biodiesel (methyl ester) was investigated. Preliminary XRD results revealed that thermally activated crab shell contains mainly CaO. Parametric study has been investigated and optimal conditions were found to be methanol/oil mass ratio, 0.5:1; catalyst amount, 4 wt. %; and reaction temperature, 338 K. As compared to laboratory CaO, the catalyst from waste crab shell performs well, thus creating another low-cost catalyst source for producing biodiesel as well as adding value to the waste crab shell. Reusability of crab shell CaO has also been studied and the outcome confirmed that the catalyst is capable to be reutilized up to 11 times, without any major deterioration.
Oxidation of sulfide in aqueous solution by hydrogen peroxide was investigated in the presence of hydrated ferric oxide catalyst. The ferric oxide catalyst was synthesized by sol gel technique from ferric chloride and ammonia. The synthesized catalyst was characterized by Fourier transform infrared spectroscopy, X-Ray diffraction analysis, scanning electrom microscope and energy dispersive X-ray analysis. The catalyst was quite effective in oxidizing the sulfide by hydrogen peroxide. The effects of sulfide concentration, catalyst loading, H2O2 dosing and temperature on the kinetics of sulfide oxidation were investigated. Kinetic equations and activation energies for the catalytic oxidation reaction were calculated based on the experimental results.
N,N'-Carbonyl difatty amides (CDFAs) have been synthesized from palm oil using sodium ethoxide as catalyst. Ethyl fatty esters (EFEs) were produced as a by-product as well as glycerol. The synthesis was carried out by reflux palm oil and urea in presence of ethanol. In this process, palm oil gave 79% pure CDFAs after 8 hours and molar ratio of urea to palm oil was 6.2: 1 at 78 degrees C. Both CDFAs and EFEs have been characterized using elemental analysis, Fourier transform infrared (FTIR) spectroscopy and (1)H nuclear magnetic resonance (NMR) technique.
New solid acid catalyst consisting of zirconium sulfate (ZS) supported on a pure-HMS hexagonal mesoporous material (HMS) have been prepared and characterized. This heterogeneous catalyst is able to make a contribution to the field of acid catalyst involving bulky organic molecules. XRD analysis shows that ZS is intact after impregnated on HMS surface and formed finely dispersed species. No ZS crystal phase was developed even at ZS loadings as high as 40 wt %. The occurrence of chemical interaction between ZS and HMS was observed by XPS analysis. Further, XRF results demonstrated that there is no leaching of ZS elements after impregnation. This study shows that ZS can be impregnated on HMS and would be a promising solid acid catalyst for acid-type reactions espcially invovling bulky organic molecuels.
Biocatalytic reaction is a type of reaction which uses enzyme or whole-cell as a (bio)-catalyst to achieve a desired conversion, under controlled conditions in a bioreactor. Temperature produces opposed effects on enzyme activity and stability, and is therefore a key variable in any biocatalytic processes. An exothermic biocatalytic reaction, in a continuous-stirred-tank reactor (CSTR), was analyzed where dynamic equations (non-linear differential equations) could be derived from the Michaelis-Menten and Arrhenius equations, by performing mass and energy balances on the reactor. In this work, the effects of the different parameters such as dilution rate, proportional control constant and dimensionless total enzyme concentration, on the stability of the system, were studied. The stability of the reaction could be analyzed, based on the ODE (ordinary differential equation), solved using the numerical technique in MATLAB® and the analytical investigation using Mathematica.® The numerical analysis can be carried out by considering the hase-plane behaviour and bifurcation diagrams of the dynamic equations, while the analytical analysis using Mathematica® can be undertaken by evaluating the eigenvalues of the system. In order to model the operational stability of biocatalysts, modulation factors need to be considered so that a proper design of bioreactors can be done. Temperature, as a key variable in such bioprocess systems, can be conveniently optimized through the use of appropriate models.
Decomposition of oil palm fruit press fiber (FPF) to various liquid products in subcritical water was investigated using a high-pressure autoclave reactor with and without the presence of catalyst. When the reaction was carried in the absence of catalyst, the conversion of solid to liquid products increased from 54.9% at 483 K to 75.8% at 603 K. Simultaneously, the liquid yield increased from 28.8% to 39.1%. The liquid products were sub-categorized to bio-oil (benzene soluble, diethylether soluble, acetone soluble) and water soluble. When 10% ZnCl(2) was added, the conversion increased slightly but gaseous products increased significantly. However, when 10% Na(2)CO(3) and 10% NaOH were added independently, the solid conversion increased to almost 90%. In the presence of catalyst, the liquid products were mainly bio-oil compounds. Although solid conversion increased at higher reaction temperature, but the liquid yield did not increase at higher temperature.
The ambient sonocatalytic degradation of congo red, methyl orange, and methylene blue by titanium dioxide (TiO(2)) catalyst at initial concentrations between 10 and 50mg/L, catalyst loadings between 1.0 and 3.0mg/L and hydrogen peroxide (H(2)O(2)) concentrations up to 600 mg/L is reported. A 20 kHz ultrasonic processor at 50 W was used to accelerate the reaction. The catalysts were exposed to heat treatments between 400 and 1000 degrees C for up to 4h to induce phase change. Sonocatalysts with small amount of rutile phase showed better sonocatalytic activity but excessive rutile phase should be avoided. TiO(2) heated to 800 degrees C for 2h showed the highest sonocatalytic activity and the degradation of dyes was influenced by their chemical structures, chemical phases and characteristics of the catalysts. Congo red exhibited the highest degradation rate, attributed to multiple labile azo bonds to cause highest reactivity with the free radicals generated. An initial concentration of 10mg/L, 1.5 g/L of catalyst loading and 450 ppm of H(2)O(2) gave the best congo red removal efficiency of above 80% in 180 min. Rate coefficients for the sonocatalytic process was successfully established and the reused catalyst showed an activity drop by merely 10%.
A study was carried out to produce polyurethane (PU) as a wood laminating adhesive from liquefied kenaf core (LKC) polyols by reacting it with toluene-2,4-diisocyanate (TDI) and 1,4-butanediol (BDO). The LKC polyurethane (LKCPU) adhesive has a molecular weight (MW) of 2666, viscosity of 5370 mPa s, and solids content of 86.9%. The average shear strength of the rubberwood (RW) bonded with LKCPU adhesive was 2.9 MPa. Most of the sheared specimens experienced a total adhesive failure. The formation of air bubbles through the liberation of carbon dioxide was observed to reduce the adhesive penetration and bonding strength which was obviously seen on the sheared specimens. The percentage of catalyst used can be varied based on the usage and working time needed. Nonetheless, the physical properties of LKCPU produced in this work had shown good potential as edge-bonding adhesive.
In this study, fatty acid methyl esters (FAME) have been successfully produced from transesterification reaction between triglycerides and methyl acetate, instead of alcohol. In this non-catalytic supercritical methyl acetate (SCMA) technology, triacetin which is a valuable biodiesel additive is produced as side product rather than glycerol, which has lower commercial value. Besides, the properties of the biodiesel (FAME and triacetin) were found to be superior compared to those produced from conventional catalytic reactions (FAME only). In this study, the effects of various important parameters on the yield of biodiesel were optimized by utilizing Response Surface Methodology (RSM) analysis. The mathematical model developed was found to be adequate and statistically accurate to predict the optimum yield of biodiesel. The optimum conditions were found to be 399 degrees C for reaction temperature, 30 mol/mol of methyl acetate to oil molar ratio and reaction time of 59 min to achieve 97.6% biodiesel yield.
Electrochemical dechlorination of chlorobenzenes in the presence of various arene mediators such as naphthalene, biphenyl, phenanthrene, anthracene, and pyrene, was studied. The amount of mediator required was able to be reduced to 0.01 equiv. for all mediators except for anthracene, with the complete dechlorination of mono-, 1,3-di- and 1,2,4-trichlorobenzene still achieved. This catalytic amount of mediator plays an important role in accelerating the dechlorination through the rapid formation of radical anions prior to reduction of the chlorobenzenes.
Photocatalytic degradation of phenol was investigated using the supported nano-TiO(2)/ZSM-5/silica gel (SNTZS) as a photocatalyst in a batch reactor. The prepared photocatalyst was characterized using XRD, TEM, FT-IR and BET surface area analysis. The synthesized photocatalyst composition was developed using nano-TiO(2) as the photoactive component and zeolite (ZSM-5) as the adsorbents, all supported on silica gel using colloidal silica gel binder. The optimum formulation of SNTZS catalyst was observed to be (nano-TiO(2):ZSM-5:silica gel:colloidal silica gel=1:0.6:0.6:1) which giving about 90% degradation of 50mg/L phenol solution in 180 min. The SNTZS exhibited higher photocatalytic activity than that of the commercial Degussa P25 which only gave 67% degradation. Its high photocatalytic activity was due to its large specific surface area (275.7 m(2)/g), small particle size (8.1 nm), high crystalline quality of the synthesized catalyst and low electron-hole pairs recombination rate as ZSM-5 adsorbent was used. The SNTZS photocatalyst synthesized in this study also has been proven to have an excellent adhesion and reusability.
Magnetically separable photocatalyst beads containing nano-sized iron oxide in alginate polymer were prepared. This magnetic photocatalyst beads are used in slurry-type reactors. The magnetism of the catalyst arises from the nanostructured particles gamma-Fe(2)O(3), by which the catalyst can be easily recovered by the application of an external magnetic field. These synthesized beads are sunlight-driven photocatalyst. In the system without magnetic photocatalyst beads, no chromium reduction was observed under sunlight irradiation due to the stability of the chromium (VI). Upon the addition of magnetic photocatalyst beads, the photo-reduction of Cr(VI) was completed in just after only 50min under sunlight irradiation due to the photocatalytic activity of the beads. However when placed away from sunlight, the reduction rate of the chromium is just about 10%. These observations were explained in terms of absorption occurrence of chromium (VI) onto the catalyst surface which took place in this reaction. In addition, photo-reduction rate of chromium (VI) was more significant at lower pH. The results suggest that the use of magnetic separable photocatalyst beads is a feasible strategy for eliminating Cr(VI).
Selected Brønsted acidic ionic liquids were tested as homogeneous catalysts for the dehydration of methanol to dimethyl ether. Ionic liquids incorporating an alkanesulfonic acid as a part of the cation, a complex acidic anion, [A(2)H](-), or both, proved to be good catalysts for this process, providing high conversions and selectivities. Homogeneous catalysis in the liquid state represents a novel approach to dimethyl ether synthesis.
This work examines the impregnated carbon-based sorbents for simultaneous removal of SO(2) and NOx from simulated flue gas. The carbon-based sorbents were prepared using palm shell activated carbon (PSAC) impregnated with several metal oxides (Ni, V, Fe and Ce). The removal of SO(2) and NOx from the simulated flue gas was investigated in a fixed-bed reactor. The results showed that PSAC impregnated with CeO(2) (PSAC-Ce) reported the highest sorption capacity among other impregnated metal oxides for the simultaneous removal of SO(2) and NOx. PSAC-Ce showed the longest breakthrough time of 165 and 115 min for SO(2) and NOx, respectively. The properties of the pure and impregnated PSAC were analyzed by BET, FTIR and XRF. The physical-chemical features of the PSAC-Ce sorbent indicated a catalytic activity in both the sorption of SO(2) and NOx. The formation of both sulfate (SO(4)(2-)) and nitrate (NO(3-)) species on spent PSAC-Ce further prove the catalytic role played by CeO(2).
Tungsten-loaded TiO(2) photocatalyst has been successfully prepared and characterized. TEM analysis showed that the photocatalysts were nanosize with the tungsten species forming layers of coverage on the surface of TiO(2), but not in clustered form. This was confirmed by XRD and FT-Raman analyses where tungsten species were well dispersed at lower loading (<6.5 mol%), but were in crystalline WO(3) at higher loadings (>12 mol%). In addition, loading with tungsten could stabilize the anatase phase from transforming into inactive rutile phase and did not shift the optical absorption to the visible region as shown by DRUV-vis analysis. PZC value of TiO(2) was found at 6.4, but the presence of tungsten at 6.5 mol% WO(3), decreased the PZC value to 3. Tungsten-loaded TiO(2) was superior to unmodified TiO(2) with 2-fold increase in degradation rate of methylene blue, and equally effective for the degradation of different class of dyes such as methyl violet and methyl orange at 1 mol% WO(3) loading.
Decolorization of reactive azo dye, reactive black 5 (RB5), was conducted using Fe(III) immobilized on Montmorillonite K10 (MK10) as a catalyst in the presence of H(2)O(2) using Fenton-like oxidation process. The effect of different parameters such as iron ions loading on supported catalyst, catalyst dosage, initial pH of dye solution, initial concentration of H(2)O(2) and dye and reaction temperature on the decolorization efficiency of the process were studied. The results indicated that by using 12 mM of H(2)O(2) and 3.50 g L(-1) of the 0.11 wt.% Fe(III) oxide on MK10 catalyst at pH of 2.5, 99% of decolorization efficiency was achieved within 150 min in a batch process.
The decolorization of Acid Red 1 (AR1) in aqueous solution was investigated by Fenton-like process. The effect of different reaction parameters such as different iron ions loading on rice husk ash (RHA), dosage of catalyst, initial pH, the initial hydrogen peroxide concentration ([H(2)O(2)](o)), the initial concentration of AR1 ([AR1](o)) and the reaction temperature on the decolorization of AR1 was studied. The optimal reacting conditions were found to be 0.070 wt.% of iron (III) oxide loading on RHA, dosage of catalyst=5.0 g L(-1), initial pH=2.0, [H(2)O(2)](o)=8 mM, [AR1](o)=50 mg L(-1) at temperature 30 degrees C. Under optimal condition, 96% decolorization efficiency of AR1 was achieved within 120 min of reaction.
Chemical recycling of bio-based polymers polyhydroxyalkanoates (PHAs) by thermal degradation was investigated from the viewpoint of biorefinery. The thermal degradation resulted in successful transformation of PHAs into vinyl monomers using alkali earth compound (AEC) catalysts. Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)s (PHBVs) were smoothly and selectively depolymerized into crotonic (CA) and 2-pentenoic (2-PA) acids at lower degradation temperatures in the presence of CaO and Mg(OH)(2) as catalysts. Obtained CA from 3-hydroxybutyrate sequences in PHBV was copolymerized with acrylic acid to produce useful water-soluble copolymers, poly(crotonic acid-co-acrylic acid) that have high glass-transition temperatures. The copolymerization of CA derived from PHA pyrolysis is an example of cascade utilization of PHAs, which meets the idea of sustainable development.