Electrochemical mitigation of hydrogen sulfide in deep-pit swine manure storage.

Hydrogen sulfide (H2S) is a toxic and hazardous gas and is commonly present in livestock operations, which occasionally causes associated exposure accidents. This study evaluated the effectiveness of electrochemical control of H2S in lab-scale swine manure storage using different electrode materials, and further selected suitable materials to demonstrate the performance of a pilot-scale field test in the deep-pit manure storage of a 200-head swine barn. In the lab-scale test, electrochemical sulfide oxidation mainly contributed to the H2S mitigation, resulting in high H2S removal efficiencies when using low carbon steel (LCS) and stainless steel 304 (SS304) as electrodes. Based on their better H2S treatment performance and lower material costs, LCS and SS304 were selected for the pilot-scale test. In a 92-day operation, the pilot-scale demonstration showed H2S removal efficiencies of 84.0% and 63.5% for LCS and SS304, respectively. A techno-economic assessment indicated that the installation and operation of the electrochemical system accounted for 16% of barn construction cost using LCS as electrodes. Further optimization may substantially decrease the electrode material consumption and the overall cost.

Low-voltage electrochemical treatment to precipitate sulfide during anaerobic digestion of beet sugar wastewater.

Sugar beet processing generates a large amount of wastewater with a high chemical oxygen demand (COD). During wastewater storage and treatment, the hydrogen sulfide (H2S) generated from anaerobic digestion (AD) poses unique safety and environmental challenges due to air emissions to the local environment. A new approach of low-voltage electrochemical treatment using low-cost sacrificial anode material was developed in this study to remove sulfide, maintain a proper pH, and produce low-H2S biogas during the AD of beet sugar wastewater. The wastewater collected was categorized as the medium or high strength wastewater depending on the COD content. By using the medium strength wastewater as the test media, the effects of electrochemical and storage conditions, including the applied voltage, immersed electrode area, initial sulfate level, and operating temperature, on the sulfide removal were studied. The effective electrical charge consumption ranged from 6.0 to 14.4 C·mg-1 S2-, and the headspace H2S concentration was reduced by over 96% for most conditions after 204 h treatment. During the 10-week experiment on high strength wastewater, intermittent electrochemical treatment at 0.7 V applied voltage and 1.2 cm2·L-1 electrode area for two weeks reduced the H2S content in the biogas by up to 96%. The cathodic hydroxyl anion generation during the electrochemical treatment significantly increased the pH from 4.61 to 6.95 and led to earlier biogas production than the one without electrochemical treatment. This technique may feasibly be applied in the AD of other sulfur-compound-rich waste streams.

Improving biohydrogen production through dark fermentation of steam-heated acid pretreated Alternanthera philoxeroides by mutant Enterobacter aerogenes ZJU1.

Alternanthera philoxeroides, a notorious invasive aquatic weed, is a typical lignocellulosic feedstock for fermentative biohydrogen production. To improve the dark fermentation performance, steam-heated acid pretreatment and enzymolysis were employed to release reducing sugars from A. philoxeroides, and Enterobacter aerogenes ZJU1 mutagenized by 60Co-γ irradiation was used as the inoculum. Dilute acid accompanied by steam heating significantly disrupted the fiber structures of A. philoxeroides. Scanning electron microscopic images revealed that many pores and fissures were generated in the surface of A. philoxeroides after pretreatment. X-ray diffraction and Fourier transform infrared spectroscopy analyses showed that the pretreatment facilitated the transformation of cellulose I to cellulose II in A. philoxeroides biomass, resulting in the increase of amorphous regions and the decrease of crystallinity. Under the optimum pretreatment condition (1.0 v/v% H2SO4, 135 °C for 15 min), the reducing sugar yield reached 0.354 g/g A. philoxeroides, which was further increased to 0.575 g/g A. philoxeroides after enzymolysis. The biohydrogen yield increased by 59.9% from 38.9 mL/g volatile solids (VS) of raw A. philoxeroides to 62.2 mL/gVS of the pretreated one. As compared to the wild strain, E. aerogenes ZJU1 contributed to an increase of 31.8% in the biohydrogen yield from pretreated A. philoxeroides. Further optimization of bacteria suspensions significantly increased the maximum biohydrogen production rate from 1.42 to 4.64 mL/gVS/h, advanced the biohydrogen production peak, and resulted in an increase of 42.8% in biohydrogen yield to 89.8 mL/gVS.

Investigating hydrothermal pretreatment of food waste for two-stage fermentative hydrogen and methane co-production.

The growing amount of food waste (FW) in China poses great pressure on the environment. Complex solid organics limit the hydrolysis of FW, hence impairing anaerobic digestion. This study employed hydrothermal pretreatment (HTP) to facilitate the solubilization of FW. When HTP temperature increased from 100 to 200°C, soluble carbohydrate content first increased to a peak at 140°C and then decreased, whereas total carbohydrate content was negatively correlated with increasing temperature due to the enhanced degradation and Maillard reactions. Protein solubilization was dramatically promoted after HTP, whereas protein degradation was negligibly enhanced. The hydrogen and methane yields from hydrothermally pretreated FW under the optimum condition (140°C, 20min) through two-stage fermentation were 43.0 and 511.6mL/g volatile solids, respectively, resulting in an energy conversion efficiency (ECE) of 78.6%. The ECE of pretreated FW was higher than that of untreated FW by 31.7%.

Enhanced hydrogen production of Enterobacter aerogenes mutated by nuclear irradiation.

Nuclear irradiation was used for the first time to generate efficient mutants of hydrogen-producing bacteria Enterobacter aerogenes, which were screened with larger colour circles of more fermentative acid by-products. E. aerogenes cells were mutated by nuclear irradiation of 60Co γ-rays. The screened E. aerogenes ZJU1 mutant with larger colour circles enhanced the hydrogenase activity from 89.8 of the wild strain to 157.4mLH2/(gDWh). The hereditary stability of the E. aerogenes ZJU1 mutant was certified after over ten generations of cultivation. The hydrogen yield of 301mLH2/gglucose with the mutant was higher by 81.8% than that of 166mL/gglucose with the wild strain. The peak hydrogen production rate of 27.2mL/(L·h) with the mutant was higher by 40.9% compared with that of 19.3mL/(L·h) with the wild strain. The mutant produced more acetate and butyrate but less ethanol compared with the wild strain during hydrogen fermentation.

Enhanced dark hydrogen fermentation by addition of ferric oxide nanoparticles using Enterobacter aerogenes.

Ferric oxide nanoparticles (FONPs) were used to facilitate dark hydrogen fermentation using Enterobacter aerogenes. The hydrogen yield of glucose increased from 164.5±2.29 to 192.4±1.14mL/g when FONPs concentration increased from 0 to 200mg/L. SEM images of E. aerogenes demonstrated the existence of bacterial nanowire among cells, suggesting FONPs served as electron conduits to enhance electron transfer. TEM showed cellular internalization of FONPs, indicating hydrogenase synthesis and activity was potentially promoted due to the released iron element. When further increasing FONPs concentration to 400mg/L, the hydrogen yield of glucose decreased to 147.2±2.54mL/g. Soluble metabolic products revealed FONPs enhanced acetate pathway of hydrogen production, but weakened ethanol pathway. This shift of metabolic pathways allowed more nicotinamide adenine dinucleotide for reducing proton to hydrogen.

Enhanced energy recovery from cassava ethanol wastewater through sequential dark hydrogen, photo hydrogen and methane fermentation combined with ammonium removal.

Cassava ethanol wastewater (CEW) was subjected to sequential dark H2, photo H2 and CH4 fermentation to maximize H2 production and energy yield. A relatively low H2 yield of 23.6mL/g soluble chemical oxygen demand (CODs) was obtained in dark fermentation. To eliminate the inhibition of excessive NH4(+) on sequential photo fermentation, zeolite was used to remove NH4(+) in residual dark solution (86.5% removal efficiency). The treated solution from 5gCODs/L of CEW achieved the highest photo H2 yield of 369.7mL/gCODs, while the solution from 20gCODs/L gave the lowest yield of 259.6mL/gCODs. This can be explained that photo H2 yield was correlated to soluble metabolic products (SMPs) yield in dark fermentation, and specific SMPs yield decreased from 38.0 to 18.1mM/g CODs. The total energy yield significantly increased to 8.39kJ/gCODs by combining methanogenesis with a CH4 yield of 117.9mL/gCODs.

Co-generation of biohydrogen and biomethane through two-stage batch co-fermentation of macro- and micro-algal biomass.

Aquatic micro-algae can be used as feedstocks for gaseous biofuel production via biological fermentation. However, micro-algae usually have low C/N ratios, which are not advantageous for fermentation. In this study, carbon-rich macro-algae (Laminaria digitata) mixed with nitrogen-rich micro-algae (Chlorella pyrenoidosa and Nannochloropsis oceanica) were used to maintain a suitable C/N ratio of 20 for a two-stage process combining hydrogen and methane fermentation. Co-fermentation of L. digitata and micro-algae facilitated hydrolysis and acidogenesis, resulting in hydrogen yields of 94.5-97.0mL/gVS; these values were 15.5-18.5% higher than mono-fermentation using L. digitata. Through the second stage of methane co-fermentation, a large portion of energy remaining in the hydrogenogenic effluents was recovered in the form of biomethane. The two-stage batch co-fermentation markedly increased the energy conversion efficiencies (ECEs) from 4.6-6.6% during the hydrogen fermentation to 57.0-70.9% in the combined hydrogen and methane production.

Sodium borohydride removes aldehyde inhibitors for enhancing biohydrogen fermentation.

To enhance biohydrogen production from glucose and xylose in the presence of aldehyde inhibitors, reducing agent (i.e., sodium borohydride) was in situ added for effective detoxification. The detoxification efficiencies of furfural (96.7%) and 5-hydroxymethylfurfural (5-HMF, 91.7%) with 30mM NaBH4 were much higher than those of vanillin (77.3%) and syringaldehyde (69.3%). Biohydrogen fermentation was completely inhibited without detoxification, probably because of the consumption of nicotinamide adenine dinucleotide (NADH) by inhibitors reduction (R-CHO+2NADH→R-CH2OH+2NAD(+)). Addition of 30mM NaBH4 provided the reducing power necessary for inhibitors reduction (4R-CHO+NaBH4+2H2O→4R-CH2OH+NaBO2). The recovered reducing power in fermentation resulted in 99.3% recovery of the hydrogen yield and 64.6% recovery of peak production rate. Metabolite production and carbon conversion after detoxification significantly increased to 63.7mM and 81.9%, respectively.

Inhibitory effects of furan derivatives and phenolic compounds on dark hydrogen fermentation.

The inhibitory effects of furan derivatives [i.e. furfural and 5-hydroxymethylfurfural (5-HMF)] and phenolic compounds (i.e. vanillin and syringaldehyde) on dark hydrogen fermentation from glucose were comparatively evaluated. Phenolic compounds exhibited stronger inhibition on hydrogen production and glucose consumption than furan derivatives under the same 15mM concentration. Furan derivatives were completely degraded after 72h fermentation, while over 55% of phenolic compounds remained unconverted after 108h fermentation. The inhibition coefficients of vanillin (14.05) and syringaldehyde (11.21) were higher than those of 5-HMF (4.35) and furfural (0.64). Vanillin exhibited the maximum decrease of hydrogen yield (17%). The consumed reducing power by inhibitors reduction from R-CHO to RCH2OH was a possible reason contributed to the decreased hydrogen yield. Vanillin exhibited the maximum delay of peak times of hydrogen production rate and glucose consumption. Soluble metabolites and carbon conversion efficiency decreased with inhibitors addition, which were consistent with hydrogen production.

Hydrogen production using amino acids obtained by protein degradation in waste biomass by combined dark- and photo-fermentation.

The biological hydrogen production from amino acids obtained by protein degradation was comprehensively investigated to increase heating value conversion efficiency. The five amino acids (i.e., alanine, serine, aspartic acid, arginine, and leucine) produced limited hydrogen (0.2-16.2 mL/g) but abundant soluble metabolic products (40.1-84.0 mM) during dark-fermentation. The carbon conversion efficiencies of alanine (85.3%) and serine (94.1%) during dark-fermentation were significantly higher than those of other amino acids. Residual dark-fermentation solutions treated with zeolite for NH4(+) removal were inoculated with photosynthetic bacteria to further produce hydrogen during photo-fermentation. The hydrogen yields of alanine and serine through combined dark- and photo-fermentation were 418.6 and 270.2 mL/g, respectively. The heating value conversion efficiency of alanine to hydrogen was 25.1%, which was higher than that of serine (21.2%).

Fermentative hydrogen and methane cogeneration from cassava residues: effect of pretreatment on structural characterization and fermentation performance.

The physicochemical properties of cassava residues subjected to microwave (or steam)-heated acid pretreatment (MHAP or SHAP) were comparatively investigated to improve fermentative hydrogen and methane cogeneration. The hydrogen yield from cassava residues with MHAP and enzymolysis was higher (106.2 mL/g TVS) than that with SHAP and enzymolysis (102.1 mL/g TVS), whereas the subsequent methane yields showed opposite results (75.4 and 93.2 mL/g TVS). Total energy conversion efficiency increased to 24.7%. Scanning electron microscopy images revealed MHAP generated numerous regular micropores (∼6 µm) and SHAP generated irregular fragments (∼23 µm) in the destroyed lignocellulose matrix. Transmission electron microscopy images showed SHAP generated wider cracks (∼0.2 µm) in delaminated cell walls than MHAP (∼0.1 µm). X-ray diffraction patterns indicated MHAP caused a higher crystallinity index (33.00) than SHAP (25.88), due to the deconstruction of amorphous cellulose. Fourier transform infrared spectroscopy indicated MHAP caused a higher crystallinity coefficient (1.20) than SHAP (1.12).

Characterisation of water hyacinth with microwave-heated alkali pretreatment for enhanced enzymatic digestibility and hydrogen/methane fermentation.

Microwave-heated alkali pretreatment (MAP) was investigated to improve enzymatic digestibility and H2/CH4 production from water hyacinth. SEM revealed that MAP deconstructed the lignocellulose matrix and swelled the surfaces of water hyacinth. XRD indicated that MAP decreased the crystallinity index from 16.0 to 13.0 because of cellulose amorphisation. FTIR indicated that MAP effectively destroyed the lignin structure and disrupted the crystalline cellulose to reduce crystallinity. The reducing sugar yield of 0.296 g/gTVS was achieved at optimal hydrolysis conditions (microwave temperature = 190°C, time = 10 min, and cellulase dosage = 5 wt%). The sequentially fermentative hydrogen and methane yields from water hyacinth with MAP and enzymatic hydrolysis were increased to 63.9 and 172.5 mL/gTVS, respectively. The energy conversion efficiency (40.0%) in the two-stage hydrogen and methane cogeneration was lower than that (49.5%) in the one-stage methane production (237.4 mL/gTVS) from water hyacinth with MAP and enzymatic hydrolysis.

Subcritical water hydrolysis of rice straw for reducing sugar production with focus on degradation by-products and kinetic analysis.

The competitive reactions of reducing sugar production and degradation in the subcritical water hydrolysis of rice straw were investigated to optimise reducing sugar yield. The optimised conditions (280°C, 20 MPa, rice straw concentration of 5 wt.% and agitation speed of 200 rpm) resulted in a reducing sugar yield of 0.346 g/g rice straw because of the enhanced reducing sugar production and decreased sugar degradation. The sugar yield increased when the temperature increased from 250°C to 280°C, but it decreased when the temperature further increased to 300°C because of the degradation of monosaccharides (e.g. glucose and xylose) into by-products (e.g. 2-methyltetrahydrofuran and acetic acid). A first-order reaction model was developed to elucidate the competitive reaction kinetics of sugar production and degradation at various temperatures. The highest reducing sugar yield based on the model was achieved at 280°C with the highest production and lowest degradation rates.

Improvement of the energy conversion efficiency of Chlorella pyrenoidosa biomass by a three-stage process comprising dark fermentation, photofermentation, and methanogenesis.

The effects of pre-treatment methods on saccharification and hydrogen fermentation of Chlorella pyrenoidosa biomass were investigated. When raw biomass and biomass pre-treated by steam heating, by microwave heating, and by ultrasonication were used as feedstock, the hydrogen yields were only 8.8-12.7 ml/g total volatile solids (TVS) during dark fermentation. When biomass was pre-treated by steam heating with diluted acid and by microwave heating with diluted acid, the dark hydrogen yields significantly increased to 75.6 ml/g TVS and 83.3 ml/g TVS, respectively. Steam heating with diluted acid is the preferred pre-treatment method of C. pyrenoidosa biomass to improve hydrogen yield during dark fermentation and photofermentation, which is followed by methanogenesis to increase energy conversion efficiency (ECE). A total hydrogen yield of 198.3 ml/g TVS and a methane yield of 186.2 ml/g TVS corresponding to an overall ECE of 34.0% were obtained through the three-stage process (dark fermentation, photofermentation, and methanogenesis).