A continuous process for biodiesel production in a fixed bed reactor packed with cation-exchange resin as heterogeneous catalyst

Continuous esterification of free fatty acids (FFA) from acidified oil with methanol was carried out with NKC-9 cation-exchange resin in a fixed bed reactor with an internal diameter of 25 mm and a height of 450 mm to produce biodiesel. The results showed that the FFA conversion increased with increases in methanol/oil mass ratio, reaction temperature and catalyst bed height, whereas decreased with increases in initial water content in feedstock and feed flow rate. The FFA conversion kept over 98.0% during 500 h of continuous esterification processes under 2.8:1 methanol to oleic acid mass ratio, 44.0 cm catalyst bed height, 0.62 ml/min feed flow rate and 65°C reaction temperature, showing a much high conversion and operational stability. Furthermore, the loss of sulfonic acid groups from NKC-9 resin into the production was not found during continuous esterification. In sum, NKC-9 resin shows the potential commercial applications to esterification of FFA.     

Fructose oleate synthesis in a fixed catalyst bed reactor

Summary Fructose oleate undergoes continuous synthesis in a fixed catalyst bed reactor using an industrial fixed lipase. The effects of the time spent in the reactor, substrate concentration and effluent recycling are studied. A yield of 83% is obtained by recycling the effluent 3 times.     

Pressurised pyrolysis of Miscanthus using a fixed bed reactor

Miscanthus x giganteus was pyrolysed, in a fixed bed reactor in a constant flow of dinitrogen gas, at a rate of 13°C/min from ambient to 550°C, then held for 25 min at this temperature. The pressures employed ranged from atmospheric to 26 bar. The major compounds identified in the bio-oil were water, phenol, and phenol derivatives. The water contents impact on the usefulness of the bio-oil as a fuel. However, the phenols could provide useful platform chemicals and products. The properties of the char were determined using elemental analyses, surface area measurements using the Brunauer-Emmett-Teller equation, a calorimetric bomb, Scanning Electron Microscopy, and solid state (13)C NMR spectroscopy. The chars were highly carbonised, especially at the higher pressures, and provided thermally stable materials. Pressure impacted greatly on the surface area. Char formed at atmospheric pressure had a surface area of 162 m(2)/g, whereas that from the highest pressure applied was only 0.137 m(2)/g.     

Immobilization of lipases and assay in continuous fixed bed reactor

Lipases are versatile enzymes regarding the range of reactions they catalyse and substrates on which they act. They are as well important as catalyst in organic synthesis. Their immobilization on appropriate supports confer them greater stability besides the possibility of operating in continuous reactors. In order to explore these abilities, the reactions involving hydrolysis of p-nitrophenyl acetate (PNPA) and transesterification of PNPA with n-butanol were chosen. Lipases from two different sources were assayed, namely: microbial (Candida rugosa, CRL, Sigma Type VII) and pancreatic (PPL, Sigma, Type II). Two immobilization methods were also used, namely: 1). adsorption, using as support the following silica derivatives (150-300 microm e 450micro): phenyl, epoxy, amino and without derivation, and 2). covalent binding, using glutaraldehyde as binding agent and silica amino as support. This later method led to better results. Hydrolytic activity was 6.1 U/g(support) for CRL and 0.97 U/g(support) for PPL, and of transesterification, 2,8 U/g(support) for CRL and 1,9 U/g(support) for PPL. Stability of the immobilized enzyme as a function of temperature was evaluated for CRL at 40 degrees C and 50 degrees C and for PPL at 32 degrees C and 40 degrees C. The assays were initially carried out batchwise, both for soluble and immobilized enzymes, aiming to the obtention of parameters for the continuous reactor. Lipases immobilized by covalent binding were used in the assays of operational stability in continuous reactors. For PPL in aqueous medium, at 32 degrees C, and CRL in organic medium at 40 degrees C, both operating continuously, no significant loss of activity was detected along the analysis period of 17 days. In the case of CRL in aqueous medium at 40 degrees C there was a loss of activity around 40% after 18 days. For PPL in organic medium at 40 degrees C the loss was 33% after 20 days. Comparing both sources with each other, very different results were obtained. Higher activity was found for CRL, both for hydrolysis and for transesterification reactions, with higher stability in organic medium. PPL showed lower activity as well as higher stability in aqueous medium. The immobilization method by covalent binding showed to be the most appropriate. Immobilized lipases are therefore relatively stable both in aqueous and organic medium.     

A control strategy of partial nitritation in a fixed bed biofilm reactor

To achieve an appropriate mixture of ammonium and nitrite for anaerobic ammonium oxidation (ANAMMOX), 50% partial nitritation was optimized in a fixed bed biofilm reactor treating synthetic wastewater. Results suggested that 50% partial nitritation could be achieved by stepwise increases of influent NH₄⁺-N at pH of 7.8 ± 0.2, temperature of 30 ± 1 °C and dissolved oxygen (DO) of 0.5-0.8 mg l⁻¹. Hydraulic retention time (HRT) and influent alkalinity did significantly affect partial nitritation. At HRT 12 h, 50% partial nitritation could be kept stable, regardless of influent NH₄⁺-N variation, by controlling the influent HCO₃⁻/NH₄⁺ molar ratio at 1:1. The fluorescent in situ hybridization (FISH) results indicated the abundance of evolution of ammonia-oxidizing bacteria (AOB) and the nitrite-oxidizing bacteria (NOB) coincided well with the performance of partial nitritation. Furthermore, the AOB were highly affiliated with Nitrosomonas spp. and Nitrosospira spp. dominated (64.1%) in the biofilm with a compact structure during the stable 50% partial nitritation period.     

Perchlorate reduction by a mixed culture in an up-flow anaerobic fixed bed reactor

Wolinella succinogenes HAP-1 is a Gram-negative microaerophile which reduces perchlorate to chloride by the proposed pathway ClO₄ to ClO₃ to ClO₂ to Cl + O₂. A cost-effective perchlorate treatment process has been established using a consortium of facultative anaerobic organisms and W. succinogenes HAP-1. The mixed anaerobic bacterial culture containing W. succinogenes HAP-1 was examined for the ability to form a biofilm capable of perchlorate reduction. An up-flow anaerobic fixed bed reactor (UAFBR) was packed with diatomaceous earth pellets and operated at residence times of 1.17 and 0.46 h to insure a viable biofilm had attached to the diatomaceous earth pellets. Reduction rates of perchlorate to chloride in the UAFBR could be maintained at 1 g of perchlorate reduced h⁻¹ L⁻¹. Studies with the same bacterial consortium in continuously stirred tank reactors (CSTR) generally reduced 0.5–0.7 g of perchlorate h⁻¹. Viable cell counts were performed periodically on the diatomaceous earth pellets and demonstrated that the W. succinogenes HAP-1 population was maintained at 28–47% of the total microbial population. Scanning electron micrographs demonstrated that the external and internal surfaces of the diatomaceous pellets were densely colonized with microbial cells of multiple cell types. This is the first report of an anaerobic mixed culture forming a biofilm capable of perchlorate reduction. Received 22 May 1997/ Accepted in revised form 07 January 1998     

Jute stick pyrolysis for bio-oil production in fluidized bed reactor

Pyrolysis of jute stick for bio-oil production has been investigated in a continuous feeding fluidized bed reactor at different temperatures ranging from 300 degrees C to 600 degrees C. At 500 degrees C, the yields of bio-oil, char and non-condensable gas were 66.70 wt%, 22.60 wt% and 10.70 wt%, respectively based on jute stick. The carbon based non-condensable gas was the mixture of carbon monoxide, carbon dioxide, methane, ethane, ethene, propane and propene. The density and viscosity of bio-oil were found to be 1.11 g/mL and 2.34 cP, respectively. The lower heating value (LHV) of bio-oil was found to be 18.2 5 MJ/kg. Since bio-oil contains some organic acids such as formic acid, acetic acid, etc., the pH and acid value of the bio-oil were found to be around 4 and 135 mg KOH/g, respectively. The water, lignin, solid and ash contents of bio-oil were determined and found to be around 15 wt%, 4.90 wt%, 0.02 wt% and 0.10 wt%, respectively.     

Proposed pathways for the reduction of a reactive azo dye in an anaerobic fixed bed reactor

Some process has been proposed for azo dye degradation and anaerobic bioreactors are one of them, since for their reduction, the dye has to be the electron acceptor. An anaerobic fixed bed bioreactor packed with activated carbon (AC) is proposed to degradate the Reactive Red 272 azo dye. In the present paper a dye degradation mechanism in an anaerobic environment is explained. It is very important to consider the interaction dye-microorganism-AC, because the groups in the AC surface take part in the reaction besides being an excellent carrier for microorganism and an adsorbent for the dye. The aromatic compounds produced in the dye reduction are partially degraded as a function of inlet dye concentration and reactor residence time. In anaerobic environment the aromatic compounds are decomposed through hydroxylation, carboxylation and redox reactions, due to enzymatic reactions.     

Transesterification of phenylalanine by means of chymotrypsin in a continuous fixed bed reactor.

An enzymic transesterification was carried out in a continuously operated fixed bed reactor. The reaction system consisted of immobilized alpha-chymotrypsin (E.C. 3.4.21.1) catalysing the transfer of the L-phenylalanine radical from the racemic propyl ester to 1,4-butanediol, yielding L-phenylalanine 4-hydroxybutyl ester. The desired reaction was accompanied by alcoholysis due to the presence of 1-propanol liberated during the reaction and by hydrolysis of both the propyl and the hydroxybutyl ester. The problem of shifting pH during the reaction due to ester hydrolysis was overcome by adjusting the initial pH of the substrate feed solution appropriately in order to obtain a sufficiently high buffer capacity provided by the free amino group of the esters. Thus, it was possible to work with shifting pH, an obvious disadvantage for operating reactors of low backmixing for this kind of reaction system. The overall reaction scheme was characterized by the appearance of a maximum ester yield as a function of the operating time in case of batch reactors. Surprisingly, the yield was found to become constant as a function of space-time for continuous operation due to a steeper pH drop. The maximum productivity achieved with respect to the hydroxybutyl ester was about 65 mol d-1 l-1 referred to the catalyst volume.     

Investigation of parameters affecting a fixed bed bioreactor process for recombinant cell lines

A BHK 21 cell line expressing a recombinant antibody was grown in a fixed bed reactor (FBR) system using a porous support made of Siran glass beads. The contribution of five process variables (bead and inoculum sizes; circulation and dilution rates; glutamine concentration of the feed) to the productivity of the process (defined as production rate, effluent product concentration or yield of product on medium supplied) was investigated using a partial factorial experimental design. Individually, none of the variables tested had a significant affect upon productivity. The combination of smaller bead and inoculum sizes, higher circulation and dilution rates, plus higher feed glutamine concentration gave a markedly higher productivity than any other combination of variable levels tested. This combination of variable levels suggested that better results shold be obtained using a fluidised bed reactor system. However, comparison of the productivities of the two systems showed that the FBR gave the better results. This result can be explained in terms of the relationship of Qs_rAb to .Abbreviations C concentration - D dilution rate - FBR fixed bed bioreactor - FIBR fluidised bed bioreactor - Gln glutamine - Qs cell specific rate - Qv volumetric rate - rAb recombinant antibody - X_v viable cell density - specific growth rate     

Antibiotics production in a fluidized bed reactor utilizing a transverse magnetic field

A mathematical model is developed to describe the performance of a three-phase fluidized bed reactor utilizing a transverse magnetic field. The model is based on the axially dispersed plug flow model for the bulk of liquid phase and on the Michaelis-Menten kinetics. The model equations are solved by the explicit finite difference method from transient to steady state conditions. The results of the numerical simulation indicate that the magnetic field increases the degree of bioconversion. The mathematical model is experimentally verified in a three-phase fluidized bed reactor with Penicillium chrysogenum immobilized on magnetic beads. The experimental results are well described by the developed model when the reactor operates in the stabilized regime. At low and relatively high magnetic field intensities certain discrepancy in the model solution is observed when the model over estimates the product concentration.     

Butanol production by Clostridium acetobutylicum in a continuous packed bed reactor

In this study, we report on a butanol production process by immobilized Clostridium acetobutylicum in a continuous packed bed reactor (PBR) using Tygon^® rings as a carrier. The medium was a solution of lactose (15–30 g/L) and yeast extract (3 g/L) to emulate the cheese whey, an abundant lactose-rich wastewater. The reactor was operated under controlled conditions with respect to the pH and to the dilution rate. The pH and the dilution rate ranged between 4 and 5, the dilution rate between 0.54 and 2.4 h^?1 (2.5 times the maximum specific growth rate assessed for suspended cells). The optimal performance of the reactor was recorded at a dilution rate of 0.97 h^?1: the butanol productivity was 4.4 g/Lh and the selectivity of solvent in butanol was 88%_w.     

The influence of different substrate pH values on the performance of a downflow anaerobic fixed bed reactor treating a petrochemical effluent

Summary Neutralizing requirements for the anaerobic treatment of an acidic petrochemical effluent in a downflow anaerobic fixed bed reactor were examined. Neutralization (pH 6.0 with NaOH) of the effluent prior to digestion resulted in a Na⁺ concentration of over 3 g/l which was detrimental. Decreasing the Na⁺ concentration and subsequent replacement of NaOH by a mixture of Ca(OH)₂, NaOH and KOH resulted in an increase in reactor performance. The addition of different alkalines resulted in the best loading rates thusfar applied in the anaerobic treatment of this petrochemical effluent. During the final stages of this study, the effluent (pH 3.95) was treated at a loading rate of 10.37 kg COD/m³. d (HRT=1.35 d) with more than 94% fatty acid removal.     

Experimental studies and two-dimensional modelling of a packed bed bioreactor used for production of galacto-oligosaccharides (GOS) from milk whey

In the present study, extensive experimental investigations and detailed theoretical analysis of a two-dimensional packed bed bioreactor, employed for the production of galacto-oligosaccharides (GOS) from milk whey were performed. Model equations, in one- and two-dimensions, capable of predicting the substrate concentration distribution in the bioreactor were developed by coupling mass balance equation with appropriate velocity distribution equation and solved numerically. Validation of the proposed model equations was done by a set of experimental data obtained from the bioreactor. The effects of reactor to catalyst particle diameter ratio (d _t/d _p), feed flowrate (10^?6–10^?9 m³ s^?1), and initial lactose concentration (50–200 kg m^?3) on substrate concentration distribution were investigated in detail. While, the distribution of substrate concentration in axial direction was independent of d _t/d _p, it was observed that for d _t/d _p <40, significant radial concentration distribution existed. It was further observed that the substrate conversion and product yield obtained experimentally showed an excellent agreement (97 ± 2 %) with the results predicted by the two-dimensional model equation, whereas, the results predicted by the one-dimensional model equation did not lie within the desired confidence level (<90 %). The results were confirmed by both curve fitting and statistical analysis. The prediction of substrate concentration distribution in axial and radial directions using the developed two-dimensional model equation is necessary for computing the bioreactor volume to achieve the desired GOS yield.     

In-situ upgrading of biomass pyrolysis vapors: catalyst screening on a fixed bed reactor

In-situ catalytic upgrading of biomass fast pyrolysis vapors was performed in a fixed bed bench-scale reactor at 500 °C, for catalyst screening purposes. The catalytic materials tested include a commercial equilibrium FCC catalyst (E-cat), various commercial ZSM-5 formulations, magnesium oxide and alumina materials with varying specific surface areas, nickel monoxide, zirconia/titania, tetragonal zirconia, titania and silica alumina. The bio-oil was characterized measuring its water content, the carbon-hydrogen-oxygen (by difference) content and the chemical composition of its organic fraction. Each catalytic material displayed different catalytic effects. High surface area alumina catalysts displayed the highest selectivity towards hydrocarbons, yielding however low organic liquid products. Zirconia/titania exhibited good selectivity towards desired compounds, yielding higher organic liquid product than the alumina catalysts. The ZSM-5 formulation with the highest surface area displayed the most balanced performance having a moderate selectivity towards hydrocarbons, reducing undesirable compounds and producing organic liquid products at acceptable yields.     

Lactic acid production by Lactobacillus delbrueckii in a dual reactor system using packed bed biofilm reactor

Aims:  An integrated dual reactor system for continuous production of lactic acid by Lactobacillus delbrueckii using biofilms developed on reticulated polyurethane foam (PUF) is demonstrated.
Methods and Results:  Lactobacillus delbrueckii was immobilized on PUF, packed in a bioreactor and used in lactic acid fermentation. The rate of lactic acid production was significantly high with a volumetric productivity of 5 g l⁻¹ h⁻¹ over extended period of time. When coupled to a bioreactor, the system could be operated as dual reactor for over 1000 h continuously without augmentation of inoculum and no compromise on productivity.
Conclusions:  Polyurethane foams offer an excellent support for biofilm formation.
Significance and Impact of the Study:  The system was very robust and could be operated for prolonged period at a volumetric productivity of 4–6 g l⁻¹ h⁻¹.     

Citric acid production by immobilized Aspergillus niger in a fluidized bed reactor

Summary Citric acid production by immobilized of Aspergillus niger in a fluidized bed reactor was performed, evaluating the productivity and the stability of the process when pulsing device was used. The application of a pulsing flow to fluidized bed reactor and the feed nitrogen limited allow to control of bioparticles morphology avoiding bed compactation. When operated at optimum pulsation frequency (0.3 s^–1) the stability of the bioreactor was maintained for more than 30 days, increasing the citric acid production in more than 52.2%.     

Continuous thorium biosorption--dynamic study for critical bed depth determination in a fixed-bed reactor

The objective of the work was to evaluate the biosorption of thorium by the seaweed Sargassum filipendula in a dynamic system. Different bed depths were tested with the purpose of evaluating the critical bed depth for total uptake of the radioactive element. Several bed depths were tested, ranging from 5.0 to 40.0 cm. Bed depths tested presented distinct capacities to accumulate thorium. An increase in biosorption efficiency was observed with an increase in bed depth. The 30.0 cm bed produced an effluent still containing detectable levels of thorium. The critical bed depth suitable for a complete removal of thorium by S.filipendula biomass was equal to 40.0 cm.