Catalytic effect of ultrananocrystalline Fe3O4 on algal bio-crude production via HTL process.

We report a comprehensive quantitative study of the production of refined bio-crudes via a controlled hydrothermal liquefaction (HTL) process using Ulva fasciata macroalgae (UFMA) as biomass and ultrananocrystalline Fe3O4 (UNCFO) as catalyst. X-ray diffraction and electron microscopy were applied to elucidate the formation of the high-quality nanocatalysts. Gas chromatography-mass spectroscopy (GC-MS) and CHNS analyses showed that the bio-crude yield and carbon/oxygen ratios increase as the amount of UNCFO increases, reaching a peak value of 32% at 1.25 wt% (a 9% increase when compared to the catalyst-free yield). The bio-crude is mainly composed of fatty acids, alcohols, ketones, phenol and benzene derivatives, and hydrocarbons. Their relative abundance changes as a function of catalyst concentration. FTIR spectroscopy and vibrating sample magnetometry revealed that the as-produced bio-crudes are free of iron species, which accumulate in the generated bio-chars. Our findings also indicate that the energy recovery values via the HTL process are sensitive to the catalyst loading, with a threshold loading of 1.25 wt%. GC-MS studies show that the UNCFO not only influences the chemical nature of the resulting bio-crudes and bio-chars, but also the amount of fixed carbons in the solid residues. The detailed molecular characterization of the bio-crudes and bio-chars catalyzed by UNCFO represents the first systematic study reported using UFMA. This study brings forth new avenues to advance the highly-pure bio-crude production employing active, heterogeneous catalyst materials that are recoverable and recyclable for continuous thermochemical reactions.

Landfills as a biorefinery to produce biomass and capture biogas.

While landfilling provides a simple and economic means of waste disposal, it causes environmental impacts including leachate generation and greenhouse gas (GHG) emissions. With the introduction of gas recovery systems, landfills provide a potential source of methane (CH4) as a fuel source. Increasingly revegetation is practiced on traditionally managed landfill sites to mitigate environmental degradation, which also provides a source of biomass for energy production. Combustion of landfill gas for energy production contributes to GHG emission reduction mainly by preventing the release of CH4 into the atmosphere. Biomass from landfill sites can be converted to bioenergy through various processes including pyrolysis, liquefaction and gasification. This review provides a comprehensive overview on the role of landfills as a biorefinery site by focusing on the potential volumes of CH4 and biomass produced from landfills, the various methods of biomass energy conversion, and the opportunities and limitations of energy capture from landfills.

Effect of cell rupturing methods on the drying characteristics and lipid compositions of microalgae.

This paper investigated the effect of cell rupturing methods on the drying characteristics and the lipid compositions of a green algae consortium grown in an open raceway pond. The ruptured microalgae samples obtained from French press, autoclave and sonication methods were used for conducting thin layer drying experiment at four drying temperatures (30, 50, 70 and 90 °C). The rate of moisture removal at each drying condition was recorded until no change in moisture loss. A typical drying curve for a microalgae consortium indicated that the rate of drying was limited by diffusion. Among three drying models (Newton, Page and Henderson-Pabis) used to fit the drying data, Page model fitted well on the experimental drying data with a coefficient of determination (R(2)) of 0.99. Solvent extraction of French press ruptured cells produced the highest total lipid yield with no significant change in lipid compositions.

Influence of biochar on nitrogen fractions in a coastal plain soil.

Interest in the use of biochar from pyrolysis of biomass to sequester C and improve soil productivity has increased; however, variability in physical and chemical characteristics raises concerns about effects on soil processes. Of particular concern is the effect of biochar on soil N dynamics. The effect of biochar on N dynamics was evaluated in a Norfolk loamy sand with and without NHNO. High-temperature (HT) (≥500°C) and low-temperature (LT) (≤400°C) biochars from peanut hull ( L.), pecan shell ( Wangenh. K. Koch), poultry litter (), and switchgrass ( L.) and a fast pyrolysis hardwood biochar (450-600°C) were evaluated. Changes in inorganic, mineralizable, resistant, and recalcitrant N fractions were determined after a 127-d incubation that included four leaching events. After 127 d, little evidence of increased inorganic N retention was found for any biochar treatments. The mineralizable N fraction did not increase, indicating that biochar addition did not stimulate microbial biomass. Decreases in the resistant N fraction were associated with the high pH and high ash biochars. Unidentified losses of N were observed with HT pecan shell, HT peanut hull, and HT and LT poultry litter biochars that had high pH and ash contents. Volatilization of N as NH in the presence of these biochars was confirmed in a separate short-term laboratory experiment. The observed responses to different biochars illustrate the need to characterize biochar quality and match it to soil type and land use.

Production of aromatic green gasoline additives via catalytic pyrolysis of acidulated peanut oil soap stock.

Catalytic pyrolysis was used to generate gasoline-compatible fuel from peanut oil soap stock (PSS), a high free fatty acid feedstock, using a fixed-bed reactor at temperatures between 450 and 550°C with a zeolite catalyst (HZSM-5). PSS fed at 81 gh(-1) along with 100 mL min(-1) inert gas was passed across a 15 g catalyst bed (WHSV=5.4h(-1), gas phase residence time=34s). Results indicate that fuel properties of PSS including viscosity, heating value, and O:C ratio were improved significantly. For PSS processed at 500°C, viscosity was reduced from 59.6 to 0.9 mm(2)s(-1), heating value was increased from 35.8 to 39.3 MJL(-1), and the O:C ratio was reduced from 0.07 to 0.02. Aromatic gasoline components (e.g., BTEX), were formed in concentrations as high as 94% (v/v) in catalytically-cracked PSS with yields ranging from 22% to 35% (v/v of PSS feed).

Transition of microbial communities during the adaption to anaerobic digestion of carrot waste.

In this study a microbial community suitable for anaerobic digestion of carrot pomace was developed from inocula obtained from natural environmental sources. The changes along the process were monitored using pyrosequencing of the 16S rRNA gene. As the community adapted from a diverse natural community to a community with a definite function, diversity decreased drastically. Major bacterial groups remaining after enrichment were Bacilli (31-45.3%), Porphyromonadaceae (12.1-24.8%) and Spirochaetes (12.5-18.5%). The archaeal population was even less diverse and mainly represented by a single OTU that was 99.7% similar to Methanosarcina mazei. One enrichment which failed to produce large amounts of methane had shifts in the bacterial populations and loss of methanogenic archaea.

Effect of operating conditions of thermochemical liquefaction on biocrude production from Spirulina platensis.

This study investigated the optimum thermochemical liquefaction (TCL) operating conditions for producing biocrude from Spirulina platensis. TCL experiments were performed at various temperatures (200-380°C), holding times (0-120 min), and solids concentrations (10-50%). TCL conversion at 350°C, 60 min holding time and 20% solids concentration produced the highest biocrude yield of 39.9% representing 98.3% carbon conversion efficiency. Light fraction biocrude (B(1)) appeared at 300°C or higher temperatures and represented 50-63% of the total biocrude. Biocrude obtained at 350-380°C had similar fuel properties to that of petroleum crude with energy density of 34.7-39.9 MJ kg(-1) compared to 42.9 MJ kg(-1) for petroleum crude. Biocrude from conversion at 300°C or above had 71-77% elemental carbon, and 0.6-11.6% elemental oxygen and viscosities in the range 40-68 cP. GC/MS of biocrude reported higher hydrocarbons (C(16)-C(17)), phenolics, carboxylic acids, esters, aldehydes, amines, and amides.

The effect of naphthalene-acetic acid on biomass productivity and chlorophyll content of green algae, coccolithophore, diatom, and cyanobacterium cultures.

The application of biochemical stimulants to enhance biomass and metabolite productivity is being investigated here and may be a simpler approach to achieve our goals of higher productivity and lower costs than methods such as genetic modification. The research builds on prior work of screening various biochemical stimulants representing different types of plant growth regulators with the green alga, Chlorella sorokiniana. Here, we report the impact on biomass and chlorophyll productivity by comparing the delivery method of a previously identified superior stimulant, the synthetic auxin naphthalene-acetic acid (NAA), solubilized in ethanol or methanol. Algae evaluated included the green alga, C. sorokiniana, as well as a mixed consortium that includes C. sorokiniana along with two other wild-isolated green algae, Scenedesmus bijuga and Chlorella minutissima. It was found that NAA dissolved in ethanol was more effective in enhancing biomass productivity of C. sorokiniana. However, no differences were observed with the mixed consortia. The most effective treatment from this step, EtOH(500ppm) + NAA(5ppm), along with two other NAA concentrations (EtOH(500ppm) + NAA(2.5ppm) and EtOH(500ppm) + NAA(10ppm)), was then applied to six diverse species of microalgae to determine if the treatment dosage was effective for other freshwater and marine green algae, cyanobacteria, coccolithophore, and diatoms. It was found that three of the species bioassayed, Pleurochrysis carterae, C. sorokiniana, and Haematococcus pluvialis exhibited a substantial boost in biomass productivity over the 10-day growth period. The use of ethanol and NAA at a combined dosage of EtOH(500ppm) + NAA(5ppm) was found to generate the highest biomass productivity for each of the species that responded positively to the treatments. If scalable, NAA and ethanol may have the potential to lower production costs by increasing biomass yields for commercial microalgae cultivation.

Evaluation of microalgae cultivation using recovered aqueous co-product from thermochemical liquefaction of algal biomass.

This study characterized the ACP stream from the TCL of Spirulina and evaluated its potential as a nutrient source for cultivation of microalgae. TCL of 100 g of dry Spirulina resulted in 40% BioOil and 429.80% ACP. The ACP was found to have high nitrogen (16,200 mg L(-1)), phosphorus (795 mg L(-1)), potassium (11,260 mg L(-1)) and secondary and micronutrients. Growth media were prepared using ACP as sole nutrient source in deionized water at 0.2%, 0.33%, 1%, and 10% v/v concentration and compared with a standard growth medium (BG 11) for algal cultivation. Chlorella minutissima was grown in these media for 12 days and monitored for biomass concentration, total chlorophyll and lipids. Biomass productivities with the ACP added media at 0.2% and 0.1% concentration were 0.035 and 0.027 g L(-1) d(-1), respectively, compared to 0.07 g L(-1) d(-1) in BG 11.

An efficient system for carbonation of high-rate algae pond water to enhance CO2 mass transfer.

High-rate algal ponds have the potential to produce 59 T of dry biomass ha(-1)year(-1) based on the specific productivity of 20 g m(-2) day(-1). Atmospheric air provides only 5% of the CO(2) to the pond surface required for photosynthesis. Hence, CO(2) is usually provided via bubbling of concentrated CO(2)-air mixture into the algae ponds. This process is, however, not significantly effective in terms of mass transfer. Use of bubble column to increase the interfacial area of contact available for gas exchange is proposed as an efficient alternative. A carbonation column (CC) was modeled and designed to measure CO(2) absorptivity in-pond water at various pH regimes. The CC performed at 83% CO(2) transfer efficiency. An air-to-pond mass transport coefficient of 0.0037 m min(-1) was derived. The proposed device can be used with any exhaust gas stream with higher concentrations of CO(2) in conjunction with raceways for optimizing algae production.

Reducing nitrogen loss during poultry litter composting using biochar.

Poultry litter (PL) is a potentially underused fertilizer because it contains appreciable amounts of N, P, K, and micronutrients. However, treatments like composting to reduce potential pathogens, weed seeds, and odor often result in high losses of N through NH3 volatilization. Biochar (BC) has been shown to act as an absorber of NH3 and water-soluble NH4+ and might therefore reduce losses of N during composting of manure. We produced three PL compost mixtures that consisted of PL without added BC (BCO), PL + 5% BC (BC5), and PL + 20% BC (BC20). The BC was produced from pine chips and used without further modifications. Three replicates of each treatment were placed in nine bioreactors to undergo composting for 42 d. The entire composting experiment was repeated three times in a complete-block design. Moisture content, temperature, pH, mass loss, gas (NH3, CO2, H2S) emissions, C, and nutrient contents were measured periodically throughout the experiments. Results showed no difference in PL mass loss with BC addition. Moisture content decreased, pH increased significantly, and peak CO2 and temperatures were significantly higher with BC20 compared with BC0. These results indicate a faster decomposition of PL if amended with BC. Ammonia concentrations in the emissions were lower by up to 64% if PL was mixed with BC (BC20), and total N losses were reduced by up to 52%. Biochar might be an ideal bulking agent for composting N-rich materials.

Effect of fractionation and pyrolysis on fuel properties of poultry litter.

Raw poultry litter has certain drawbacks for energy production such as high ash and moisture content, a corrosive nature, and low heating values. A combined solution to utilization of raw poultry litter may involve fractionation and pyrolysis. Fractionation divides poultry litter into a fine, nutrient-rich fraction and a coarse, carbon-dense fraction. Pyrolysis of the coarse fraction would remove the corrosive volatiles as bio-oil, leaving clean char. This paper presents the effect of fractionation and pyrolysis process parameters on the calorific value of char and on the characterization of bio-oil. Poultry litter samples collected from three commercial poultry farms were divided into 10 treatments that included 2 controls (raw poultry litter and its coarse fraction having particle size greater than 0.85 mm) and 8 other treatments that were combinations of three factors: type (raw poultry litter or its coarse fraction), heating rate (30 or 10 degrees C/min), and pyrolysis temperature (300 or 500 degrees C). After the screening process, the poultry litter samples were dried and pyrolyzed in a batch reactor under nitrogen atmosphere and char and condensate yields were recorded. The condensate was separated into three fractions on the basis of their density: heavy, medium, and light phase. Calorific value and proximate and nutrient analysis were performed for char, condensate, and feedstock. Results show that the char with the highest calorific value (17.39 +/- 1.37 MJ/kg) was made from the coarse fraction at 300 degrees C, which captured 68.71 +/- 9.37% of the feedstock energy. The char produced at 300 degrees C had 42 +/- 11 mg/kg arsenic content but no mercury. Almost all of the Al, Ca, Fe, K, Mg, Na, and P remained in the char. The pyrolysis process reduced ammoniacal-nitrogen (NH4-N) in char by 99.14 +/- 0.47% and nitrate-nitrogen (NO3-N) by 95.79 +/- 5.45% at 500 degrees C.

Effect of biochemical stimulants on biomass productivity and metabolite content of the microalga, Chlorella sorokiniana.

The influence of 12 biochemical stimulants, namely 2-phenylacetic acid (PAA; 30 ppm), indole-3 butyric acid (IBA; 10 ppm), 1-naphthaleneacetic acid (NAA; 2.5, 5 and 10 ppm ), gibberellic acid (GA3, 10 ppm), zeatin (ZT; 0.002 ppm), thidiazuron (0.22 ppm), humic acid (20 ppm), kelp extract (250 ppm), methanol (500 ppm), ferric chloride (3.2 ppm ), putrescine (0.09 ppm), spermidine (1.5 ppm) were prescreened for their impact on growth and chlorophyll for the green alga--Chlorella sorokiniana. C. sorokiniana responded best to phytohormones in the auxin family, particularly NAA. Thereafter, two studies were conducted on combinations of phytohormones to compare blends from within the auxin family as well as against other families. These treatments were NAA(5 ppm)+PAA(30 ppm), NAA(2.5 ppm)+PAA(15 ppm), NAA(5 ppm)+IBA(10 ppm), NAA(5 ppm)+GA3(10 ppm), NAA(5 ppm)+ZT(1 ppm), and NAA(5 ppm)+GA3(10 ppm)+ZT(1 ppm). Combinations of NAA with other auxins did not have synergistic or antagonistic effects on the growth. However, combinations of compounds from different phytohormone families, such as NAA(5 ppm)+GA3(10 ppm)+ZT(1 ppm), dramatically increased the biomass productivity by 170% over the control followed by the treatments: NAA(5 ppm)+GA3(10 ppm) (138%), NAA(5 ppm)+ZT(1 ppm) (136%), and NAA(5 ppm) ( 133%). The effect of biochemical stimulants were also measured on metabolites such as chlorophyll, protein, and lipids in C. sorokiniana. Renewed interest in microalgae for biotechnology and biofuel applications may warrant the use of biochemical stimulants for cost reduction in large-scale cultivation through increased biomass productivity.

Biomass and bioenergy production potential of microalgae consortium in open and closed bioreactors using untreated carpet industry effluent as growth medium.

Improved wastewater management with beneficial utilization will result in enhanced sustainability and enormous cost savings in industries. Algae cultivation systems viz. raceway ponds, vertical tank reactors (VTR) and polybags were evaluated for mass production of algal consortium using carpet industry (CI) untreated wastewater. Overall areal biomass productivity of polybags (21.1 g m(-2)d(-1)) was the best followed by VTR (8.1 g m(-2)d(-1)) and raceways (5.9 g m(-2)d(-1)). An estimated biomass productivity of 51 and 77 tons ha(-1)year(-1) can be achieved using 20 and 30 L capacity polybags, respectively with triple row arrangement. Biomass obtained from algal consortium was rich in proteins (approximately 53.8%) and low in carbohydrates (approximately 15.7%) and lipids (approximately 5.3%). Consortium cultivated in polybags has the potential to produce 12,128 m(3) of biomethane ha(-1)year(-1). To be economically viable, the capital expenditure for polybag reactors needs to be reduced to $10 m(-2) for bioenergy/biofuel production.

DSC studies to evaluate the impact of bio-oil on cold flow properties and oxidation stability of bio-diesel.

This paper describes the use of Differential Scanning Calorimetry (DSC) to evaluate the impact of varying mix ratios of bio-oil (pyrolysis oil) and bio-diesel on the oxidation stability and on some cold flow properties of resulting blends. The bio-oils employed were produced from the semi-continuous Auger pyrolysis of pine pellets and the batch pyrolysis of pine chips. The bio-diesel studied was obtained from poultry fat. The conditions used to prepare the bio-oil/bio-diesel blends as well as some of the fuel properties of these blends are reported. The experimental results suggest that the addition of bio-oil improves the oxidation stability of the resulting blends and modifies the crystallization behavior of unsaturated compounds. Upon the addition of bio-oil an increase in the oxidation onset temperature, as determined by DSC, was observed. The increase in bio-diesel oxidation stability is likely to be due to the presence of hindered phenols abundant in bio-oils. A relatively small reduction in DSC characteristic temperatures which are associated with cold flow properties was also observed but can likely be explained by a dilution effect.

Microalgae cultivation in a wastewater dominated by carpet mill effluents for biofuel applications.

Industrial and municipal wastewaters are potential resources for production of microalgae biofuels. Dalton - the Carpet Capital of the World generates 100-115 million L of wastewater d(-1). A study was conducted using a wastewater containing 85-90% carpet industry effluents with 10-15% municipal sewage, to evaluate the feasibility of algal biomass and biodiesel production. Native algal strains were isolated from carpet wastewater. Preliminary growth studies indicated both fresh water and marine algae showed good growth in wastewaters. A consortium of 15 native algal isolates showed >96% nutrient removal in treated wastewater. Biomass production potential and lipid content of this consortium cultivated in treated wastewater were approximately 9.2-17.8 tons ha(-1) year(-1) and 6.82%, respectively. About 63.9% of algal oil obtained from the consortium could be converted into biodiesel. However further studies on anaerobic digestion and thermochemical liquefaction are required to make this consortium approach economically viable for producing algae biofuels.

Chlorella minutissima--a promising fuel alga for cultivation in municipal wastewaters.

It is imperative to slash the cost of algal oil to less than $50 bbl(-1) for successful algal biofuel production. Use of municipal wastewater for algal cultivation could obviate the need for freshwater and the nutrients--N and P. It would also add CO2 through bacterial activity. Chlorella minutissima Fott et Nova dominated the entire phycoflora year around and through each stage of the wastewater treatment at the oxidation pond system of Wazirabad (Delhi) in India. The ability to grow so profusely in such varied and contrasting situations made this alga unique. Besides pollution tolerance, it grew heterotrophically in dark under acidic conditions and as a mixotroph in presence of light over a range of organic C substrates. It could utilize both ammoniacal and nitrate nitrogen, survived anaerobicity, 5% NaCl and-10 bar of osmotic stress. C. minutissima grew at pH 4-11 and raised the pH set initially by 1 to 3 units in 7.5 h. It showed gigantism and largely kept afloat in presence of utilizable organic carbon, while flocculated in mineral medium and on aging. The alga also possessed potential for biofuel production. The studied parameters indicate why C. minutissima was a potential biomass builder in municipal sewage and could be used to determine which other alga(e) may serve the purpose.

Catalytic ozonation of ammonia using biomass char and wood fly ash.

Catalytic ozonation of gaseous ammonia was investigated at room temperature using wood fly ash (WFA) and biomass char as catalysts. WFA gave the best results, removing ammonia (11 ppmv NH(3), 45% conversion) at 23 degrees C at a residence time of 0.34 s, using 5 g of catalyst or ash at the lowest ozone concentration (62 ppmv). Assuming pseudo zero order kinetics in ozone, a power rate law of -r(NH3) = 7.2 x 10(-8) C(NH3)(0.25) (r, mol g(-1)s(-1), C(NH3)molL(-1)) was determined at 510 ppmv O(3) and 23 degrees C for WFA. Water vapor approximately doubled the oxidation rate using WFA and catalytic ozonation activity was not measured for the char without humidifying the air stream. Overall oxidation rates using the crude catalysts were lower than commercial catalysts, but the catalytic ozonation process operated at significantly lower temperatures (23 vs. 300 degrees C). Nitric oxide was not detected and the percentage of NO(2) formed from NH(3) oxidation ranged from 0.3% to 3% (v/v), with WFA resulting in the lowest NO(2) level (at low O(3) levels). However, we could not verify that N(2)O was not formed, so further research is needed to determine if N(2) is the primary end-product. Additional research is required to develop techniques to enhance the oxidation activity and industrial application of the crude, but potentially inexpensive catalysts.

Pyrolysis conditions and ozone oxidation effects on ammonia adsorption in biomass generated chars.

Ammonia adsorbents were generated via pyrolysis of biomass (peanut hulls and palm oil shells) over a range of temperatures and compared to a commercially available activated carbon (AC) and solid biomass residuals (wood and poultry litter fly ash). Dynamic ammonia adsorption studies (i.e., breakthrough curves) were performed using these adsorbents at 23 degrees C from 6 to 17 ppmv NH(3). Of the biomass chars, palm oil char generated at 500 degrees C had the highest NH(3) adsorption capacity (0.70 mg/g, 6 ppmv, 10% relative humidity (RH)), was similar to the AC, and contrasted to the other adsorbents (including the AC), the NH(3) adsorption capacity significantly increased if the relative humidity was increased (4 mg/g, 7 ppmv, 73% RH). Room temperature ozone treatment of the chars and activated carbon significantly increased the NH(3) adsorption capacity (10% RH); resultant adsorption capacity, q (mg/g) increased by approximately 2, 6, and 10 times for palm oil char, peanut hull char (pyrolysis only), and activated carbon, respectively. However, water vapor (73% RH at 23 degrees C) significantly reduced NH(3) adsorption capacity in the steam and ozone treated biomass, yet had no effect on the palm shell char generated at 500 degrees C. These results indicate the feasibility of using a low temperature (and thus low energy input) pyrolysis and activation process for the generation of NH(3) adsorbents from biomass residuals.

Slow pyrolysis of poultry litter and pine woody biomass: impact of chars and bio-oils on microbial growth.

Accidental or prescribed fires in forests and in cultivated fields, as well as primitive charcoal production practices, are responsible for the release of large amounts of gases, char and condensable organic molecules into the environment. This paper describes the impact of condensable organic molecules and chars resulting from the slow pyrolysis of poultry litter, pine chips and pine pellets on the growth of microbial populations in soil and water. The proximate and elemental analyses as well as the content of proteins, cellulose, hemicellulose, lignin, and ash for each of these bio-materials are reported. The yields and some properties of char and condensable liquids are also documented. The behavior of microbial populations in soil and water is followed through respiration studies. It was found that biological activity was highest when aqueous fractions from poultry litter were applied in water. Cumulative oxygen consumption over a 120-h period was highest in the aqueous phases from poultry litter coarse fraction (1.82 mg/g). On average the oxygen consumption when oily fractions from poultry litter were applied represented 44 to 62% of that when aqueous fractions were applied. Pine chip and pine pellet derived liquids and chars produced respiration activity that were an order of magnitude lower than that of poultry litter liquid fractions. These results suggest that the growth observed is due to the effect of protein-derived molecules.