Oxalic Acid as a Hydrogen Donor for the Hydrodesulfurization of Gas Oil and Deoxygenation of Rapeseed Oil Using Phonolite-Based Catalysts.

The use of renewable local raw materials to produce fuels is an important step toward optimal environmentally friendly energy consumption. In addition, the use of these sources together with fossil fuels paves the way to an easier transition from fossil to renewable fuels. The use of simple organic acids as hydrogen donors is another alternative way to produce fuel. The present work reports the use of oxalic acid as a hydrogen donor for the catalytic hydrodesulfurization of atmospheric gas oil and the deoxygenation of rapeseed oil at 350 °C. For this process, one commercial NiW/SiO2-Al2O3 solid and two NiW/modified phonolite catalysts were used, namely Ni (5%) W (10%)/phonolite treated with HCl, and Ni (5%) W (10%)/phonolite treated with oxalic acid. The fresh phonolite catalysts were characterized by Hg porosimetry and N2 physisorption, ammonia temperature programmed desorption (NH3-TPD), X-ray diffraction (XRD), and X-ray fluorescence (XRF). The sulfided metal phonolite catalysts were characterized by XRD and XRF. Hydrodesulfurization led to a decrease in sulfur content from 1 to 0.5 wt% for the phonolite catalysts and to 0.8 wt% when the commercial catalyst was used. Deoxygenation led to the production of 15 and 65 wt% paraffin for phonolite and commercial solids, respectively. The results demonstrate the potential of using oxalic acid as a hydrogen donor in hydrotreating reactions.

Sulfur and nitrogen-containing compounds from the whole bodies of Blaps japanensis.

Pipajiains H-J (1-3), three new phenolic derivatives with an unusual sulfone group, pipajiamides A-C (4-6), three new amide derivatives, pipajiaine A (7), one new imidazole analogue, and pipajiaine B (8), a pair of new pyrrolidine derivatives, along with three known compounds were isolated from the insect Blaps japanensis. Their structures were identified by spectroscopic and computational methods. Chiral HPLC was used to separate the (-)- and (+)-antipodes of 4 and 8. Biological activities of all the new compounds against extracellular matrix in rat renal proximal tubular cells, human cancer cells (A549, Huh-7, and K562), COX-2, ROCK1, and JAK3 were evaluated. The results show that compounds 2, (+)-4, and (-)-4 are active against kidney fibrosis, whereas, compound 9 is active toward human cancer cells, inflammation, and JAK3 kinase.

Biologically enhanced hydrogen sulfide absorption from sour gas under haloalkaline conditions.

We studied a biotechnological desulfurization process for removal of toxic hydrogen sulfide (H2S) from sour gas. The process consists of two steps: i) Selective absorption of H2S into a (bi)carbonate solution in the absorber column and ii) conversion of sulfide to sulfur by sulfide oxidizing bacteria (SOB) in the aerated bioreactor. In previous studies, several physico-chemical factors were assessed to explain the observed enhancement of H2S absorption in the absorber, but a full explanation was not provided. We investigated the relation between the metabolic activity of SOB and the enhancement factor. Two continuous experiments on pilot-scale were performed to determine H2S absorption efficiencies at different temperatures and biomass concentrations. The absorption efficiency improved at increasing temperatures, i.e. H2S concentration in the treated gas decreased from 715 ±â€¯265 ppmv at 25.4 °C to 69 ±â€¯25 ppmv at 39.4 °C. The opposite trend is expected when H2S absorption is solely determined by physico-chemical factors. Furthermore, increasing biomass concentrations to the absorber also resulted in decreased H2S concentrations in the treated gas, from approximately 6000 ppmv without biomass to 1664 ±â€¯126 ppmv at 44 mg N/L. From our studies it can be concluded that SOB activity enhances H2S absorption and leads to increased H2S removal efficiencies in biotechnological gas desulfurization.

Treatment of real flue gas desulfurization wastewater in an autotrophic biocathode in view of elemental sulfur recovery: Microbial communities involved.

Sulfur oxide emissions can lead to acidic precipitation and health concerns. Flue gas desulfurization (FGD) systems treat these emissions generating a wastewater with high-sulfate content. This work is the first attempt to treat this effluent with bioelectrochemical systems (BES) in order to recover elemental sulfur, a technology that allows the treatment of several wastewaters that lack of electron donor. The sulfate treatment and elemental sulfur recovery have been studied in a biocathode with simultaneous sulfate reduction to sulfide and partial sulfide oxidation, comparing the performance obtained with synthetic and real wastewater. A decrease of the sulfate removal rate (SRR) from 108 to 73mgS-SO42-L-1d-1 was observed coupled to an increase in the elemental sulfur recovery from 1.4 to 27mgS-S0L-1d-1. This elemental sulfur recovered as a solid from the real wastewater represented a 64% of the theoretical elemental sulfur produced (the elemental sulfur corresponded to a 72% of the solid weight). In addition, microbial communities analysis of the membrane and cathode biofilms and planktonic biomass showed that the real wastewater allowed a higher growth of sulfur oxidizing bacteria (SOB) adapted to more complex waters as Halothiobacillus sp. while decreasing the relative abundance of sulfate reducing bacteria (SRB).

Enhancement of bio-desulfurization capability of a newly isolated thermophilic bacterium using starch/iron nanoparticles in a controlled system.

Due to the increasing application of oil and petroleum products, increased environmental contamination has become a matter of concern. Bio-desulfurization process may be used to eliminate sulfur from fossil fuels in the moderate condition. In this study, a thermophilic bacterium was isolated that was able to desulfurize dibenzothiophene. 16S rRNA sequencing indicated that this strain is related closely to Bacillus thermoamylovorans (97%). This strain grew in Basal salt medium containing DBT (100 mgl-1) as the only sulfur source, at 55°C and showed maximum growth (OD660 = 0.850) following 72 h incubation time. 2­hydroxybiphenyl was produced at the maximal concentration (26.13 ±â€¯0.12 mgl-1) at 72 h. Bio-desulfurization and growth rate factors were optimized using response surface methodology. Starch/Fe3O4 and starch/Fe nanoparticles were used for enhancement of BDS efficiency. The size of starch/Fe3O4 and starch/Fe nanoparticles were 20 and 30-40 nm, respectively, as described by using scanning electron microscope and transmission electron microscope. The results showed that the immobilized cells by starch/Fe3O4 and starch/Fe nanoparticles had higher desulfurization capacity, about 10% and 22% more, respectively. Also, BDS in a bioreactor in the presence of nanoparticles was increased 25% with respect of the process occurred in the flask.

The shift of microbial communities and their roles in sulfur and iron cycling in a copper ore bioleaching system.

Bioleaching has been employed commercially to recover metals from low grade ores, but the production efficiency remains to be improved due to limited understanding of the system. This study examined the shift of microbial communities and S&Fe cycling in three subsystems within a copper ore bioleaching system: leaching heap (LH), leaching solution (LS) and sediment under LS. Results showed that both LH and LS had higher relative abundance of S and Fe oxidizing bacteria, while S and Fe reducing bacteria were more abundant in the Sediment. GeoChip analysis showed a stronger functional potential for S0 oxidation in LH microbial communities. These findings were consistent with measured oxidation activities to S0 and Fe2+, which were highest by microbial communities from LH, lower by those from LS and lowest form Sediment. Moreover, phylogenetic molecular ecological network analysis indicated that these differences might be related to interactions among microbial taxa. Last but not the least, a conceptual model was proposed, linking the S&Fe cycling with responsible microbial populations in the bioleaching systems. Collectively, this study revealed the microbial community and functional structures in all three subsystems of the copper ore, and advanced a holistic understanding of the whole bioleaching system.

Sulfidization of Organic Freshwater Flocs from a Minerotrophic Peatland: Speciation Changes of Iron, Sulfur, and Arsenic.

Iron-rich organic flocs are frequently observed in surface waters of wetlands and show a high affinity for trace metal(loid)s. Under low-flow stream conditions, flocs may settle, become buried, and eventually be subjected to reducing conditions facilitating trace metal(loid) release. In this study, we reacted freshwater flocs (704-1280 mg As/kg) from a minerotrophic peatland (Gola di Lago, Switzerland) with sulfide (5.2 mM, S(-II)spike/Fe = 0.75-1.62 mol/mol) at neutral pH and studied the speciation changes of Fe, S, and As at 25 ± 1 °C over 1 week through a combination of synchrotron X-ray techniques and wet-chemical analyses. Sulfidization of floc ferrihydrite and nanocrystalline lepidocrocite caused the rapid formation of mackinawite (52-81% of Fesolid at day 7) as well as solid-phase associated S(0) and polysulfides. Ferrihydrite was preferentially reduced over lepidocrocite, although neoformation of lepidocrocite from ferrihydrite could not be excluded. Sulfide-reacted flocs contained primarily arsenate (47-72%) which preferentially adsorbed to Fe(III)-(oxyhydr)oxides, despite abundant mackinawite precipitation. At higher S(-II)spike/Fe molar ratios (≥1.0), the formation of an orpiment-like phase accounted for up to 35% of solid-phase As. Despite Fe and As sulfide precipitation and the presence of residual Fe(III)-(oxyhydr)oxides, mobilization of As was recorded in all samples (Asaq = 0.45-7.0 µM at 7 days). Aqueous As speciation analyses documented the formation of thioarsenates contributing up to 33% of Asaq. Our findings show that freshwater flocs from the Gola di Lago peatland may become a source of As under sulfate-reducing conditions and emphasize the pivotal role Fe-rich organic freshwater flocs play in trace metal(loid) cycling in S-rich wetlands characterized by oscillating redox conditions.

Traceless purification and desulfurization of tau protein ligation products.

We present a novel strategy for the traceless purification and synthetic modification of peptides and proteins obtained by native chemical ligation. The strategy involves immobilization of a photocleavable semisynthetic biotin-protein conjugate on streptavidin-coated agarose beads, which eliminates the need for tedious rebuffering steps and allows the rapid removal of excess peptides and additives. On-bead desulfurization is followed by delivery of the final tag-free protein product. The strategy is demonstrated in the isolation of a tag-free Alzheimer's disease related human tau protein from a complex EPL mixture as well as a triphosphorylated peptide derived from the C-terminus of tau.

Effect of electrokinetics on biodesulfurization of the model oil by Rhodococcus erythropolis PTCC1767 and Bacillus subtilis DSMZ 3256.

Biodesulfurization of the model oil using Rhodococcus erythropolis PTCC1767 (R. erythropolis) and Bacillus subtilis DSMZ 3256 (B. subtilis) strains assisted by applying electrokinetic was investigated as a novel method for desulfurization. The yield of biodesulfurization is low because it takes long time to be completed. Electrokinetic reduces the process time and accelerates degradation of the sulfur compounds. A mixture of normal hexadecane with 10mM dibenzotiophene (DBT) was employed as the model oil. The biodesulfurization experiments were initially performed. The results represented 34% and 62% DBT conversions after 1 and 6 days by R. erythropolis and the biodesulfurization yields were 11% and 36%, respectively. However, the DBT conversions for B. subtilis strain after 1 and 6 days were 31% and 55% and the biodesulfurization yields were 9% and 31%, respectively. The electrokinetic biodesulfurization experiments were studied at different current densities and the optimum current density was selected. According to the results, DBT conversion and biodesulfurization yield for R. erythropolis after 3 days were 76% and 39%, respectively, at the current density of 7.5 mA/cm(2). At the same conditions, the DBT conversion and biodesulfurization yield for B. subtilis were 71% and 37%, respectively. The experimental results indicate that the electrokinetic significantly reduces the biodesulfurization time. The combination of electrokinetic and biodesulfurization has the potential to obtain 'zero sulfur' products.

Biodesulfurization of dibenzothiophene and gas oil using a bioreactor containing a catalytic bed with Rhodococcus rhodochrous immobilized on silica.

Biodesulfurization (BDS) in a bioreactor packed with a catalytic bed of silica containing immobilized Rhodococcus rhodochrous was studied. Various bed lengths and support particle sizes were evaluated for BDS of dibenzothiophene (DBT) and gas oil. The sulfur-containing substrates were introduced separately into the bioreactor at different feed flows. Higher removal of sulfur from DBT and gas oil was achieved with a long bed, lower substrate flow, and larger sizes of immobilization particles. The packed bed bioreactor containing metabolic active cells was recycled and maintained BDS activity.

Gas cleaning and hydrogen sulfide removal for COREX coal gas by sorption enhanced catalytic oxidation over recyclable activated carbon desulfurizer.

This paper proposes a novel self-developed JTS-01 desulfurizer and JZC-80 alkaline adsorbent for H2S removal and gas cleaning of the COREX coal gas in small-scale and commercial desulfurizing devices. JTS-01 desulfurizer was loaded with metal oxide (i.e., ferric oxides) catalysts on the surface of activated carbons (AC), and the catalyst capacity was improved dramatically by means of ultrasonically assisted impregnation. Consequently, the sulfur saturation capacity and sulfur capacity breakthrough increased by 30.3% and 27.9%, respectively. The whole desulfurizing process combined selective adsorption with catalytic oxidation. Moreover, JZC-80 adsorbent can effectively remove impurities such as HCl, HF, HCN, and ash in the COREX coal gas, stabilizing the system pressure drop. The JTS-01 desulfurizer and JZC-80 adsorbent have been successfully applied for the COREX coal gas cleaning in the commercial plant at Baosteel, Shanghai. The sulfur capacity of JTS-01 desulfurizer can reach more than 50% in industrial applications. Compared with the conventional dry desulfurization process, the modified AC desulfurizers have more merit, especially in terms of the JTS-01 desulfurizer with higher sulfur capacity and low pressure drop. Thus, this sorption enhanced catalytic desulfurization has promising prospects for H2S removal and other gas cleaning.

Rate-limiting step analysis of the microbial desulfurization of dibenzothiophene in a model oil system.

A mechanistic analysis of the various mass transport and kinetic steps in the microbial desulfurization of dibenzothiophene (DBT) by Rhodococcus erythropolis IGTS8 in a model biphasic (oil-water), small-scale system was performed. The biocatalyst was distributed into three populations, free cells in the aqueous phase, cell aggregates and oil-adhered cells, and the fraction of cells in each population was measured. The power input per volume (P/V) and the impeller tip speed (vtip ) were identified as key operating parameters in determining whether the system is mass transport controlled or kinetically controlled. Oil-water DBT mass transport was found to not be limiting under the conditions tested. Experimental results at both the 100 mL and 4 L (bioreactor) scales suggest that agitation leading to P/V greater than 10,000 W/ m(3) and/or vtip greater than 0.67 m/s is sufficient to overcome the major mass transport limitation in the system, which was the diffusion of DBT within the biocatalyst aggregates.

Photocatalytic process of simultaneous desulfurization and denitrification of flue gas by TiO2-polyacrylonitrile nanofibers.

TiO2 nanoparticles were successfully fabricated on electrospun polyacrylonitrile (PAN) nanofibers via the coupling of electrospinning and hydrothermal pathway. A straightforward photocatalysis oxidation process has been developed for simultaneous desulfurization and denitrification of flue gas using the TiO2-PAN photocatalyst. Also, the influences of some important operating parameters, such as titanium loading content of catalyst, flue gas humidity, flue gas flow, and inlet flue gas temperature on removal efficiencies of SO2 and NO were investigated. The results demonstrated that removal efficiencies of 99.3% for SO2 and 71.2% for NO were attained under the following optimal experiment conditions: titanium loading content, 6.78 At %; gas flow rate, 200 mL/min; flue gas humidity, 5%; inlet flue gas temperature, 40 °C. Furthermore, the presumed reaction mechanism of SO2 and NO removal using TiO2-PAN photocatalyst under UV light was proposed.

Effect of byproducts of flue gas desulfurization on the soluble salts composition and chemical properties of sodic soils.

The byproducts of flue gas desulfurization (BFGD) are a useful external source of Ca(2+) for the reclamation of sodic soils because they are comparatively cheap, generally available and have high gypsum content. The ion solution composition of sodic soils also plays an important role in the reclamation process. The effect of BFGD on the soluble salts composition and chemical properties of sodic soils were studied in a soil column experiment. The experiment consisted of four treatments using two different sodic soils (sodic soil I and sodic soil II) and two BFGD rates. After the application of BFGD and leaching, the soil soluble salts were transformed from sodic salts containing Na2CO3 and NaHCO3 to neutral salts containing NaCl and Na2SO4. The sodium adsorption ratio (SAR), pH and electrical conductivity (EC) decreased at all soil depths, and more significantly in the top soil depth. At a depth of 0-40 cm in both sodic soil I and sodic soil II, the SAR, EC and pH were less than 13, 4 dS m(-1) and 8.5, respectively. The changes in the chemical properties of the sodic soils reflected the changes in the ion composition of soluble salts. Leaching played a key role in the reclamation process and the reclamation effect was positively associated with the amount of leaching. The soil salts did not accumulate in the top soil layer, but there was a slight increase in the middle and bottom soil depths. The results demonstrate that the reclamation of sodic soils using BFGD is promising.

[Isolation, identification and oxidizing characterization of an iron-sulfur oxidizing bacterium LY01 from acid mine drainage].

An acidophilic iron-sulfur oxidizing bacterium LY01 was isolated from acid mine drainage of coal in Guizhou Province, China. Strain LY01 was identified as Acidithiobacillusferrooxidans by morphological and physiological characteristics, and phylogenetic analysis of its 16S rRNA gene sequence. Strain LY01 was able to grow using ferrous ion (Fe2+), elemental sulfur (S0) and pyrite as sole energy source, respectively, but significant differences in oxidation efficiency and bacterial growth were observed when different energy source was used. When strain LY01 was cultured in 9K medium with 44.2 g x L(-1) FeSO4.7H2O as the substrate, the oxidation efficiency of Fe2+ was 100% in 30 h and the cell number of strain LY01 reached to 4.2 x 10(7) cell x mL(-1). When LY01 was cultured in 9K medium with 10 g x L(-1) S0 as the substrate, 6.7% S0 oxidation efficiency, 2001 mg x L(-1) SO4(2-) concentration and 8.9 x 10(7) cell x mL(-1) cell number were observed in 21 d respectively. When LY01 was cultured with 30 g x L(-1) pyrite as the substrate, the oxidation efficiency of pyrite, SO4(2-) concentration and cell number reached 10%, 4443 mg x L(-1) and 3.4 x 10(8) cell x mL(-1) respectively in 20 d. The effects of different heavy metals (Ni2+, Pb2+) on oxidation activity of strain LY01 cultured with pyrite were investigated. Results showed that the oxidation activity of strain LY01 was inhibited to a certain extent with the addition of Ni2+ at 10-100 mg x L(-1) to the medium, but the addition of 10-100 mg x L(-1) Pb2+ had no effect on LY01 activity.

Bio-desulfurization and denitrification by anaerobic-anoxic process for the treatment of wastewater from flue gas washing.

For amine-based carbon dioxide capture, nitrogen oxides and sulfur oxides were the main pollutants that had a negative effect on the regeneration of solvent. Before carbon dioxide capture, the sulfur oxides in flue gas should be removed by the method of calcium salt, and then washed by alkaline solution to eliminate the residual nitrogen oxides and sulfur oxides. The washing wastewater containing sulfate and nitrate needs to be treated. In this study, a novel anaerobic-anoxic process was built up for the treatment of this washing wastewater. Nitrate was reduced to nitrogen by denitrifying bacteria. Sulfate was firstly reduced to sulfide by sulfate reducing bacteria, and then selectively oxidized to element sulfur by sulfide oxidizing bacteria. The treated liquid could be reused as absorption after the adjustment of pH value. The performances of this bioprocess were investigated under various pH values and S/N ratios. It was found that the optimal pH value of influent was 6.0, the percentages of denitrification and sulfate reducing could reach 90 and 89%, respectively. Seventy-six percent of sulfate was transformed into element sulfur. Nitrate significantly had a negative effect on sulfate reduction above 10 mM. As 20 mM nitrate, the sulfate reducing percentage would drop to 67%. These results showed that the anaerobic-anoxic process was feasible for the treatment of flue gas washing wastewater. It would be prospectively applied to other wastewater with the higher ratio of SO4(2-)/NO3(-).

The etymological role of the main atmosphere pollutants in development of human diseases.

The aim of research was monitoring of the main atmospheric air pollutants concentration on Adjara Autonomous Republic territory in order to determine their role in causing different diseases. The following atmospheric air pollutants have been determined in Batumi: dust, carbon monoxide, sulfur and nitrogen dioxide. The number of diseases registered in Adjara Autonomous Republic, which may be linked to the air pollution, has been studied. These are the following: chronic and nonspecific bronchitis, asthma and asthma status diseases, allergic rhinitis, trachea-, bronchi- and lung malignant tumor. In order to reduce the number of risk-factors significant attention should be paid to the proper functionality of the vehicles and systematic observations should continue on the chemical pollution of the air to make proper decisions to reduce the number of diseases.

The interaction of CuS and Halothiobacillus HT1 biofilm in microscale using synchrotron radiation-based techniques.

In order to investigate the microbe-mineral interaction in the micro scale, spatial distribution and speciation of Cu and S in Halothiobacillus HT1 biofilm formed on a CuS surface was examined using synchrotron-based X-ray techniques. Confocal laser scanning microscope (CLSM) results indicated that Halothiobacillus HT1 biofilm formation gave rise to distinct chemical and redox gradients, leading to diverse niches in the biofilm. Live cells were distributed at the air-biofilm and membrane-biofilm interface. CuS was oxidized by Halothiobacillus HT1 biofilm, and copper penetrated into the biofilm. Sulfide was oxidized to cysteine (77.3%), sulfite (3.8%) and sulfonate (18.9%). Cu-cysteine-like species were involved in the copper homeostasis. These results significantly improve our understanding of the interfacial properties of the biofilm-mineral interface.

Pilot-scale demonstration of the hybrid zero-valent iron process for treating flue-gas-desulfurization wastewater: part II.

The hybrid zero-valent-iron (hZVI) process is a novel chemical treatment process that has shown promise for removing heavy metals and nutrients from industrial wastewaters. In this study, a pilot-scale demonstration was conducted to continuously treat 3.8-7.6 L/min (1-2 gpm) of the flue-gas-desulfurization (FGD) wastewater at a coal-fired power plant for 5 months. In this paper, a spike test was conducted to evaluate performance of the hZVI process for removing selected toxic metals at artificially elevated concentrations. The results showed that a multiple-stage hZVI process could decrease selenate-Se from 22 mg/L to ~10 µg/L and dissolved Hg(2+) from 1.15 mg/L to ~10 ng/L. In addition, the process simultaneously removed a broad spectrum of heavy metals such as As(III), As(V), Cr(VI), Cd(II), Pb(II) and Cu(II) from mg/L to near or sub-ppb (µg/L) level after a single-stage treatment. The process consumed about 0.3 kg ZVI per 1 m(3) FGD wastewater treated at a cost of about US$0.6/m(3). Solid waste production and energy consumption were reasonably low. The successful pilot study demonstrated that the hZVI technology can be a low-cost, high-performance treatment platform for solving some of the toughest heavy metal water problems.

Hydroprocessing of sunflower oil-gas oil blends over sulfided Ni-Mo-Al-zeolite beta composites.

Mixtures of sunflower oil and a straight run gas oil in the diesel fuel range were hydroprocessed over sulfided NiO(3%)-MoO3(12%)-γ-Al2O3 incorporating 0, 15 or 30 wt.% zeolite beta (BEA). The studies were carried out at 320-350 °C; 30-60 bars, and weight hourly space velocities (WHSV), 1-4 h(-1). Catalyst containing 30% BEA achieved nearly 100 % conversion of the vegetable oil into hydrocarbons at 330 °C, 60 bars and a WHSV of 2 h(-1) compared to 95.5% by the Ni-Mo-γ-alumina catalyst without BEA. Hydroprocessing with blends containing oleic acid revealed that the catalysts were able to transform the acid into hydrocarbons. An analysis of the ratios of the n-C18 and n-C17 paraffins formed from the vegetable oil at different process conditions revealed that the catalyst containing 15% BEA was most active for hydrodeoxygenation. The gas oil-hydrodesulfurization activity of the Ni-Mo-Al2O3 was enhanced by the addition of BEA by more than 10%.