Sang Hyoun Kim

A review of thermochemical conversion of microalgal biomass for biofuels: chemistry and processes

Renewable biomass sources are organic materials, in which solar energy is stored in bio-chemical bonds, and which commonly contain carbon, hydrogen, oxygen, and nitrogen constituents, along with traces of sulfur. Renewable biomass is now considered as a crucial energy resource, which is able to meet a range of energy requirements, including generating electricity and fueling vehicles. Among all the renewable energy sources, microalgal biomass is unique, since it profitably stores solar energy. It is one of the renewable sources of carbon that can be effectively converted into expedient solid, liquid, and gaseous biofuels through different conversion techniques. In this review, thermochemical conversion technologies involving microalgal biomass are highlighted, with emphasis on the background chemistry and chemical processes. Thermochemical conversion of microalgal biomass via pyrolysis, hydrothermal liquefaction, gasification, torrefaction, and direct combustion for bioenergy production from microalgal species is discussed, though there are limited literature sources available on these technologies. The unique features of hydrothermal gasification and supercritical gasification technologies are described, with the chemical reactions involved in these processes. The decomposition pathways of the main chemical components present in the microalgal biomass, such as carbohydrates and proteins, are well elucidated with the chemical pathways. The pros and cons of direct combustion are also spotlighted.

Changes in performance and bacterial communities in response to various process disturbances in a high-rate biohydrogen reactor fed with galactose.

High-rate biohydrogen production was achieved via hybrid immobilized cells fed with galactose in a continuous reactor system. The hybrid immobilized cells were broken down after 20 days and began to form granules by self-aggregation. The peak hydrogen production rate (HPR) and hydrogen yield (HY) of 11.8 ± 0.6 LH2/L-d and 2.1 ± 0.1 mol H2/molgalactose(added), respectively, were achieved at the hydraulic retention time (HRT) of 8h with an organic loading rate (OLR) of 45 g/L-d. This is the highest yet reported for the employment of galactose in a continuous system. Various process disturbances including shock loading, acidification, alkalization and starvation were examined through bacterial community analysis via pyrosequencing of the 16S rRNA genes. The proportion of Clostridia increased during the stable biohydrogen production periods, while that of Bacilli increased when the reactor was disturbed. However, due to the stability of the self-aggregated granules, the process performance was regained within 4-7 days.

Anaerobic digestibility of algal bioethanol residue.

The aim of this work was to investigate anaerobic digestibility of algal bioethanol residue from saccharification and fermentation processes. A series of batch anaerobic digestion tests using saccharification and fermentation residue showed that the maximum methane yields of saccharification residue and fermentation residue were 239 L/kg VS (Volatile Solids) and 283 L/kg VS (Volatile Solids), respectively. Energy recovered by anaerobic digestion of the residue was 2.24 times higher than that from the ethanol produced in the main process. 5-HMF (5-hydroxymethylfurfural), a saccharification byproduct, could retard methanogenesis at over 3g/L however, the inhibition was prevented by increasing cell biomass concentration. Anaerobic digestion of residue has the potential to enhance bioenergy recovery and environmental sustainability of algal bioethanol production.

Predominance of cluster I Clostridium in hydrogen fermentation of galactose seeded with various heat-treated anaerobic sludges.

To identify the key bacterial populations in hydrogen fermentation of galactose, a fermentor seeded with a heat-treated sludge was operated. After 27h of fermentation, the proportion of butyric acid increased to 69.4wt.% and the gas production yield reached 1.0molH2/molgalactose. In the pyrosequencing of 16S rDNA, an increase of the proportion of the phylum Firmicutes from 4.2% to 92% (mostly cluster I Clostridium) was observed. To verify the predominance and the ubiquity of the cluster, five fermentors seeded with different heat-treated anaerobic sludges having different feedstock compositions and digestion temperatures were investigated using qPCR analyses. The abundance of the cluster increased >100-fold during the fermentation, regardless of the inocula. Moreover, the abundance was negatively correlated with the lag time of hydrogen production and positively correlated with the hydrogen production rate, demonstrating the relevance of the cluster to hydrogen production. Taken together, the results clearly revealed the importance of cluster I Clostridium in the hydrogen fermentation of galactose.

Evidence of syntrophic acetate oxidation by Spirochaetes during anaerobic methane production.

To search for evidence of syntrophic acetate oxidation by cluster II Spirochaetes with hydrogenotrophic methanogens, batch reactors seeded with five different anaerobic sludge samples supplemented with acetate as the sole carbon source were operated anaerobically. The changes in abundance of the cluster II Spirochaetes, two groups of acetoclastic methanogens (Methanosaetaceae and Methanosarcinaceae), and two groups of hydrogenotrophic methanogens (Methanomicrobiales and Methanobacteriales) in the reactors were assessed using qPCR targeting the 16S rRNA genes of each group. Increase in the cluster II Spirochaetes (9.0±0.4-fold) was positively correlated with increase in hydrogenotrophic methanogens, especially Methanomicrobiales (5.6±1.0-fold), but not with acetoclastic methanogens. In addition, the activity of the cluster II Spirochaetes decreased (4.6±0.1-fold) in response to high hydrogen partial pressure, but their activity was restored after consumption of hydrogen by the hydrogenotrophic methanogens. These results strongly suggest that the cluster II Spirochaetes are involved in syntrophic acetate oxidation in anaerobic digesters.

HRT dependent performance and bacterial community population of granular hydrogen-producing mixed cultures fed with galactose.

The effects of hydraulic retention times (HRTs-6, 3 and 2 h) on H2 production, operational stability and bacterial population response in a continuously stirred tank reactor (CSTR) were evaluated using galactose. A peak hydrogen production rate (HPR) of 25.9 L H2/L-d was obtained at a 3 h HRT with an organic loading rate (OLR) of 120 g/L-d, while the maximum hydrogen yield (HY) of 2.21 mol H2/mol galactose was obtained at a 6 h HRT (60 g galactose/L-d). Butyrate was dominant and the lactate concentration increased as HRT decreased, which significantly affected the HY. Biomass concentration (VSS) decreased from 16 to 3g/L at a 2 h HRT, leading to failure. A 3 h HRT supported the favorable growth of Clostridium species, as indicated by an increase in their populations from 25.4% to 27%, while significantly reducing Bacilli populations from 61.6% to 54.2%, indicating that this was the optimal condition.

Feasibility of anaerobic digestion from bioethanol fermentation residue.

The focus of this study was the reuse of red algal ethanol fermentation residue as feedstock for anaerobic digestion. Levulinic acid and formic acid, the dilute-acid hydrolysis byproducts, inhibited methanogenesis at concentrations over 3.0 and 0.5 g/L, respectively. However, the inhibition was overcome by increasing inoculum concentration. A series of batch experiments with the fermentation residue showed increased methane yield and productivity at higher inoculum concentration. The maximum methane conversion rate of 84.8% was found at 5 g COD/L of fermentation residue at 0.25 g COD/g VSS of food-to-microorganism (F/M) ratio. The red algal ethanol fermentation residue can possibly be used as a feedstock in anaerobic digestion at appropriate concentration and F/M ratio.

Microbial responses to various process disturbances in a continuous hydrogen reactor fed with galactose.

In this study, microbial responses of a continuous hydrogen reactor fed with galactose have been investigated. Process disturbances reduced H2 production performance as well as large fluctuations in microbial diversity. The peak values of the hydrogen yield (HY) was not influenced greatly during the steady state period, and accounted as 2.01xa0±xa00.05 and 2.14xa0±xa00.03xa0mol/mol galactoseadded, while hydraulic retention time (HRT) was at 12 and 8xa0h, respectively. Microbial community analysis via 454 pyrosequencing revealed that functional redundancy following changes in the microbial community distribution led to the stability of the fermentation performance. The butyrate to acetate (B/A) ratio well correlated with changes in the microbial community. The energy generation rate and energy yield resulted in the peak values of 134xa0kJ/L-d and 612xa0kJ/moladded.

Effects of anti-foaming agents on biohydrogen production

The effects of antifoaming agents on fermentative hydrogen production using galactose in batch and continuous operations were investigated. Batch hydrogen production assays with LS-303 (dimethylpolysiloxane), LG-109 (polyalkylene), LG-126 (polyoxyethylenealkylene), and LG-299 (polyether) showed that the doses and types of antifoaming agents played a significant role in hydrogen production. During batch tests, LS-303 at 100μL/L resulted in the maximum hydrogen production rate (HPR) and hydrogen yield (HY) of 2.5L/L-d and 1.08mol H2/mol galactoseadded, respectively. The following continuously stirred tank reactor operated at 12h HRT with LS-303 at 100μL/L showed a stable HPR and HY of 4.9L/L-d and 1.17mol H2/mol galactoseadded, respectively, which were higher than those found for the control reactor. Microbial community analysis supported the alterations in H2 generation under different operating conditions and the stimulatory impact of certain antifoaming chemicals on H2 production was demonstrated.

Surfactant assisted disperser pretreatment on the liquefaction of Ulva reticulata and evaluation of biodegradability for energy efficient biofuel production through nonlinear regression modelling

The present study aimed to increase the disintegration potential of marine macroalgae, (Ulva reticulata) through chemo mechanical pretreatment (CMP) in an energy efficient manner. By combining surfactant with disperser, the specific energy input was considerably reduced from 437.1u202fkJ/kg TS to 264.9u202fkJ/kg TS to achieve 10.7% liquefaction. A disperser rpm (10,000), pretreatment time (30u202fmin) and tween 80 dosage (21.6u202fmg/L) were considered as an optimum for effective liquefaction of algal biomass. CMP was designated as an appropriate pretreatment resulting in a higher soluble organic release 1250u202fmg/L, respectively. Anaerobic fermentation results revealed that the volatile fatty acid (VFA) concentration was doubled (782u202fmg/L) in CMP when compared to mechanical pretreatment (MP) (345u202fmg/L). CMP pretreated algal biomass was considered as the suitable for biohydrogen production with highest H2 yield of about 63u202fmL H2/g COD than (MP) (45u202fmL H2/g COD) and control (10u202fmL H2/g COD).