Enhancing Green Ammonia Electrosynthesis Through Tuning Sn Vacancies in Sn-Based MXene/MAX Hybrids.

Renewable energy driven N2 electroreduction with air as nitrogen source holds great promise for realizing scalable green ammonia production. However, relevant out-lab research is still in its infancy. Herein, a novel Sn-based MXene/MAX hybrid with abundant Sn vacancies, Sn@Ti2CTX/Ti2SnC-V, was synthesized by controlled etching Sn@Ti2SnC MAX phase and demonstrated as an efficient electrocatalyst for electrocatalytic N2 reduction. Due to the synergistic effect of MXene/MAX heterostructure, the existence of Sn vacancies and the highly dispersed Sn active sites, the obtained Sn@Ti2CTX/Ti2SnC-V exhibits an optimal NH3 yield of 28.4 µg h-1 mgcat-1 with an excellent FE of 15.57% at - 0.4 V versus reversible hydrogen electrode in 0.1 M Na2SO4, as well as an ultra-long durability. Noticeably, this catalyst represents a satisfactory NH3 yield rate of 10.53 µg h-1 mg-1 in the home-made simulation device, where commercial electrochemical photovoltaic cell was employed as power source, air and ultrapure water as feed stock. The as-proposed strategy represents great potential toward ammonia production in terms of financial cost according to the systematic technical economic analysis. This work is of significance for large-scale green ammonia production.

Fast microwave assisted pyrolysis of biomass using microwave absorbent.

A novel concept of fast microwave assisted pyrolysis (fMAP) in the presence of microwave absorbents was presented and examined. Wood sawdust and corn stover were pyrolyzed by means of microwave heating and silicon carbide (SiC) as microwave absorbent. The bio-oil was characterized, and the effects of temperature, feedstock loading, particle sizes, and vacuum degree were analyzed. For wood sawdust, a temperature of 480°C, 50 grit SiC, with 2g/min of biomass feeding, were the optimal conditions, with a maximum bio-oil yield of 65 wt.%. For corn stover, temperatures ranging from 490°C to 560°C, biomass particle sizes from 0.9mm to 1.9mm, and vacuum degree lower than 100mmHg obtained a maximum bio-oil yield of 64 wt.%. This study shows that the use of microwave absorbents for fMAP is feasible and a promising technology to improve the practical values and commercial application outlook of microwave based pyrolysis.

Production of aromatic hydrocarbons by catalytic pyrolysis of microalgae with zeolites: catalyst screening in a pyroprobe.

Catalytic pyrolysis of microalgae and egg whites was investigated to evaluate the performance of different zeolites for the production of aromatic hydrocarbons. Three zeolites with different structures (H-Y, H-Beta and H-ZSM5) were used to study the effect of catalyst type on the aromatic yield. All three catalysts significantly increased the aromatic yields from pyrolysis of microalgae and egg whites compared with non-catalytic runs, and H-ZSM5 was most effective with a yield of 18.13%. Three H-ZSM5 with silica-to-alumina ratios of 30, 80 and 280 were used to study the effect of Si/Al ratio on the aromatic yield. The maximum yield was achieved at the Si/Al ratio of 80, which provides moderate acidity to achieve high aromatic production and reduce coke formation simultaneously. Aromatic production increased with the incorporation of copper or gallium to HZSM-5. However, other studied metals either had no significant influence or led to a lower aromatic yield.

Catalytic pyrolysis of microalgae and their three major components: carbohydrates, proteins, and lipids.

To better understand the pyrolysis of microalgae, the different roles of three major components (carbohydrates, proteins, and lipids) were investigated on a pyroprobe. Cellulose, egg whites, and canola oil were employed as the model compounds of the three components, respectively. Non-catalytic pyrolysis was used to identify and quantify some major products and several reaction pathways were proposed for the pyrolysis of each model compound. Catalytic pyrolysis was then carried out with HZSM-5 for the production of aromatic hydrocarbons at different temperatures and catalyst to feed ratios. The aromatic yields of all feedstocks were significantly improved when the catalyst to biomass ratio increased from 1:1 to 5:1. Egg whites had the lowest aromatic yield among the model compounds under all reaction conditions, which suggests that proteins can hardly be converted to aromatics with HZSM-5. Lipids, although only accounted for 12.33% of Chlorella, contributed about 40% of aromatic production from algal biomass.

Production and evaluation of biodiesel and bioethanol from high oil corn using three processing routes.

Six Korea high oil (KHO) corn varieties varying in germ and endosperm size and oil content (4-21%, wet basis) were subjected to three sequential combinations of milling (M), germ separation (S), fermentation (F), and in situ transesterification (T) to produce bioethanol and biodiesel. Production parameters including saccharification, bioethanol yield, biodiesel yield and composition, and conversion rate were evaluated. The effects of the contents of germ, endosperm size, oil, and non-oil solid mass on the production parameters strongly depended on the processing routes, namely M-F-T, M-T-F, and S-T|F. The M-F-T route produced the highest bioethanol yield while the S-T|F route produced the highest biodiesel yield. The in situ transesterification reaction, if proceeded before fermentation, reduced the bioethanol yield while fermentation and/or presence of endosperm reduced the biodiesel yield.

Cultivation of a microalga Chlorella vulgaris using recycled aqueous phase nutrients from hydrothermal carbonization process.

This study investigated the feasibility of using recovered nutrients from hydrothermal carbonization (HTC) for cultivation of microalga Chlorella vulgaris. Different dilution multiples of 50, 100 and 200 were applied to the recycled process water from HTC and algal growth was compared among these media and a standard growth medium BG-11. Algae achieved a biomass concentration of 0.79 g/L on 50 × process water after 4 days. Algae removed total nitrogen, total phosphorus and chemical oxygen demand by 45.5-59.9%, 85.8-94.6% and 50.0-60.9%, respectively, on differently diluted process water. The fatty acid methyl ester yields for algae grown on the process water were 11.2% (50 ×), 11.2% (100 ×) and 9.7% (200 ×), which were significantly higher than 4.5% for BG-11. In addition, algae cultivated on process water had 18.9% higher carbon and 7.8% lower nitrogen contents than those on BG-11, indicating that they are very suitable as biofuel feedstocks.

Enhanced mixotrophic growth of microalga Chlorella sp. on pretreated swine manure for simultaneous biofuel feedstock production and nutrient removal.

The objectives were to assess the feasibility of using fermented liquid swine manure (LSM) as nutrient supplement for cultivation of Chlorella sp. UMN271, a locally isolated facultative heterotrophic strain, and to evaluate the nutrient removal efficiencies by alga compared with those from the conventionally decomposed LSM-algae system. The results showed that addition of 0.1% (v/v) acetic, propionic and butyric acids, respectively, could promote algal growth, enhance nutrient removal efficiencies and improve total lipids productivities during a 7-day batch cultivation. Similar results were observed when the acidogenic fermentation was applied to the sterilized and raw digested LSM rich in volatile fatty acids (VFAs). High algal growth rate (0.90 d(-1)) and fatty acid content (10.93% of the dry weight) were observed for the raw VFA-enriched manure sample. Finally, the fatty acid profile analyses showed that Chlorella sp. grown on acidogenically digested manure could be used as a feedstock for high-quality biodiesel production.

Hydrothermal pretreatment of microalgae for production of pyrolytic bio-oil with a low nitrogen content.

Microalgae can be converted to an energy-dense bio-oil via pyrolysis; however, the relatively high nitrogen content of this bio-oil presents a challenge for its direct use as fuels. Therefore, hydrothermal pretreatment was employed to reduce the N content in Nannochloropsis oculata feedstock by removing proteins without requiring significant energy inputs. The effects of reaction conditions on the yield and composition of pretreated algae were investigated by varying the temperature (150-225°C) and reaction time (10-60 min). Compared with untreated algae, pretreated samples had higher carbon contents and enhanced heating values under all reaction conditions and 6-42% lower N contents at 200-225°C for 30-60 min. The pyrolytic bio-oil from pretreated algae contained less N-containing compounds than that from untreated samples and the bio-oil contained mainly (44.9% GC-MS peak area) long-chain fatty acids (C14-C18) which can be more readily converted into hydrocarbon fuels in the presence of simple catalysts.

Mass cultivation of microalgae on animal wastewater: a sequential two-stage cultivation process for energy crop and omega-3-rich animal feed production.

In this study, 97 microalgal strains purchased from algae bank and 50 microalgal strains isolated from local waters in Minnesota were screened for their adaptability growing on a 20-fold diluted digested swine manure wastewater (DSMW). A pool of candidate strains well adapted to the DSMW was established through a high-throughput screening process. Two top-performing facultative heterotrophic strains with high growth rate (0.536 day(-1) for UMN 271 and 0.433 day(-1) for UMN 231) and one strain with high omega-3 unsaturated fatty acid (EPA, 3.75 % of total fatty acids for UMN 231) were selected. Subsequently, a sequential two-stage mixo-photoautotrophic culture strategy was developed for biofuel and animal feed production as well as simultaneous swine wastewater treatment using above two strains. The maximal biomass concentration and lipid content at the first and second stages reached 2.03 g/L and 23.0 %, and 0.83 g/L and 19.0 % for UMN 271 and UMN 231, respectively. The maximal nutrient removals for total phosphorus and ammonia after second-stage cultivation were 100 and 89.46 %, respectively. The experiments showed that this sequential two-stage cultivation process has great potential for economically viable and environmentally friendly production of both renewable biofuel and high-value animal feed and at the same time for animal wastewater treatment.

Microwave-assisted pyrolysis of microalgae for biofuel production.

The pyrolysis of Chlorella sp. was carried out in a microwave oven with char as microwave reception enhancer. The results indicated that the maximum bio-oil yield of 28.6% was achieved under the microwave power of 750 W. The bio-oil properties were characterized with elemental, GC-MS, GPC, FTIR, and thermogravimetric analysis. The algal bio-oil had a density of 0.98 kg/L, a viscosity of 61.2 cSt, and a higher heating value (HHV) of 30.7 MJ/kg. The GC-MS results showed that the bio-oils were mainly composed of aliphatic hydrocarbons, aromatic hydrocarbons, phenols, long chain fatty acids and nitrogenated compounds, among which aliphatic and aromatic hydrocarbons (account for 22.18% of the total GC-MS spectrum area) are highly desirable compounds as those in crude oil, gasoline and diesel. The results in this study indicate that fast growing algae are a promising source of feedstock for advanced renewable fuel production via microwave-assisted pyrolysis (MAP).