Desulfurization and upgrade of pyrolytic oil and gas during waste tires pyrolysis: The role of metal oxides.

Pyrolysis can effectively convert waste tires into high-value products. However, the sulfur-containing compounds in pyrolysis oil and gas would significantly reduce the environmental and economic feasibility of this technology. Here, the desulfurization and upgrade of waste tire pyrolysis oil and gas were performed by adding different metal oxides (Fe2O3, CuO, and CaO). Results showed that Fe2O3 exhibited the highest removal efficiency of 87.7 % for the sulfur-containing gas at 600 °C with an outstanding removal efficiency of 99.5 % for H2S. CuO and CaO were slightly inferior to Fe2O3, with desulfurization efficiencies of 75.9 % and 45.2 % in the gas when added at 5 %. Fe2O3 also demonstrated a notable efficacy in eliminating benzothiophene, the most abundant sulfur compound in pyrolysis oil, with a removal efficiency of 78.1 %. Molecular dynamics simulations and experiments showed that the desulfurization mechanism of Fe2O3 involved the bonding of Fe-S, the breakage of C-S, dehydrogenation and oxygen migration process, which promoted the conversion of Fe2O3 to FeO, FeS and Fe2(SO4)3. Meanwhile, Fe2O3 enhanced the cyclization and dehydrogenation reaction, facilitating the upgrade of oil and gas (monocyclic aromatics to 57.4 % and H2 to 22.3 %). This study may be helpful for the clean and high-value conversion of waste tires.

Enhanced Fe(ii)/Fe(iii) cycle by boron enabled efficient Cr(vi) removal with microscale zero-valent iron.

Recently, researchers have been paying much attention to zero-valent iron (ZVI) in the field of pollution remediation. However, the depressed electron transport from the iron reservoir to the iron oxide shell limited the wide application of ZVI. This study was aimed at promoting the performance of microscale ZVI (mZVI) for hexavalent chromium (Cr(vi)) removal by accelerating iron cycle with the addition of boron powder. It was found that the addition of boron powder enhanced the Cr(vi) removal rate by 2.1 times, and the proportion of Cr(iii) generation after Cr(vi) removal process also increased, suggesting that boron could promote the reduction pathway of Cr(vi) to Cr(iii). By further comparing the Cr(vi) removal percentage of Fe(iii) with or without the boron powder, we found that boron powder could promote the percentage removal of Cr(vi) with Fe(iii) from 10.1% to 33.6%. Moreover, the presence of boron powder could decrease the potential gap values (ΔEp) between Fe(iii) reduction and Fe(ii) oxidation from 0.668 V to 0.556 V, further indicating that the added boron powder could act as an electron sacrificial agent to promote the reduction process of Fe(iii) to Fe(ii), and thus enhancing the reduction of Cr(vi) with Fe(ii). This study shed light on the promoted mechanism of Cr(vi) removal with boron powder and provided an environmentally friendly and efficient approach to enhance the reactivity of the mZVI powder, which would benefit the wide application of mZVI technology in the environmental remediation field.

Self-assembled porphyrin-based photosensitizer nanomicelles for enhanced photodynamic therapy.

Preparation of a supermacromolecular photosensitizer that can stay in the tumor site and exhibits high photoconversion efficiency is useful for improving the efficacy of tumor photodynamic therapy (PDT). In this paper, we prepared tetratroxaminobenzene porphyrin (TAPP) loaded biodegradable silk nanospheres (NSs) and characterized their morphology, optical properties and the singlet oxygen-generating capacity. On this basis, the effect of in vitro photodynamic killing efficacy by as-prepared nanometer micelles was evaluated and the tumor retention ability and tumor killing effect of the nanometer micelles were verified by the co-culture of photosensitizer micelle and tumor cells. The results show that tumor cells were killed well under 660 nm laser irradiation even at a lower concentration of as-prepared TAPP NSs. In addition, due to the excellent safety of as-prepared nanomicelle, they exhibit great potential applications in improved tumor PDT.

Electrochemical removal of ammonium nitrogen in high efficiency and N2 selectivity using non-noble single-atomic iron catalyst.

Ammonia nitrogen (NH4+-N) is a ubiquitous environmental pollutant, especially in offshore aquaculture systems. Electrochemical oxidation is very promising to remove NH4+-N, but suffers from the use of precious metals anodes. In this work, a robust and cheap electrocatalyst, iron single-atoms distributed in nitrogen-doped carbon (Fe-SAs/N-C), was developed for electrochemical removal of NH4+-N from in wastewater containing chloride. The Fe-SAs/N-C catalyst exhibited superior activity than that of iron nanoparticles loaded carbon (Fe-NPs/N-C), unmodified carbon and conventional Ti/IrO2-TiO2-RuO2 electrodes. And high removal efficiency (> 99%) could be achieved as well as high N2 selectivity (99.5%) at low current density. Further experiments and density functional theory (DFT) calculations demonstrated the indispensable role of single-atom iron in the promoted generation of chloride derived species for efficient removal of NH4+-N. This study provides promising inexpensive catalysts for NH4+-N removal in aquaculture wastewater.

Plasma Exosome miRNAs Profile in Patients With ST-Segment Elevation Myocardial Infarction.

Background: Circulating microRNAs (miRNAs) have been found to have different expressions in different phases of acute myocardial infarction. The profiles of plasma exosome miRNAs in patients with ST-segment elevation myocardial infarction (STEMI) at 3-6 months postinfarction are unknown. Objective: The aim of this study was to assess the profiles of plasma exosome miRNAs in patients with STEMI in comparison with healthy volunteers and to select specific exosome miRNAs related to pathophysiological changes post-STEMI. Methods: Plasma and echocardiography parameters were collected from 30 patients 3-6 months after STEMI and 30 healthy volunteers. Plasma exosome miRNAs were assessed by using high-throughput sequence (Illumina HiSeq 2500) and profile of the plasma exosome miRNAs was established in 10 patients and 6 healthy volunteers. The specific exosome miRNAs related to heart diseases were selected according to the TargetScan database. The specificity of the selected exosome miRNAs was evaluated in additional 20 post-STEMI patients and 24 healthy volunteers by using quantitative PCR (qPCR). Left ventricular remodeling (LVR) was defined using the European Association of Cardiovascular Imaging criteria according to echocardiography examination. Correlations between expression of the specific miRNAs and echocardiography parameters of LVR were assessed using the Spearman correlation analysis. Results: Twenty eight upregulated miRNAs and 49 downregulated miRNAs were found in patients 3-6 months after STEMI (p < 0.01) in comparison with the healthy volunteers. The two least expressed and heart-related exosome miRNAs were hsa-miR-181a-3p (0.64-fold, p < 0.01) and hsa-miR-874-3p (0.50-fold, p < 0.01), which were further confirmed by using qPCR and demonstrated significant specificity in another 20 patients with post-STEMI comparing to 24 healthy volunteers [area under the curve (AUC) = 0.68, p < 0.05; AUC = 0.74, p < 0.05]. The expression of hsa-miR-181a-3p was downregulated in patients with LV adverse remodeling in comparison with patients without LV adverse remodeling and healthy volunteers. Conclusion: Circulating exosome miR-874-3p and miR-181a-3p were downregulated in patients with STEMI postinfarction. Exosome hsa-miR-181a-3p might play a potential role in the development of LVR in patients with post-STEMI.

Sedimentary environment and relative sea level changes revealed by marine biological membrane.

Marine pollution has a deleterious impact, both on the conditions of the ecosystem and the biodiversity of the ocean. Researchers in the field of marine chemistry have been putting effort into the creation of efficient catalysts for the purification of seawater. There has been extensive research done on membrane technology for the activation of peroxymonosulfate, which is an extremely effective therapy for saltwater. The sediment of QX03, which was obtained from the western coast of Bohai, is located very close to the modern coastline. The uppermost 15 m of this sector were thoroughly analyzed in sedimentary petrology, grain size, shell, and sediment chroma dating to reconstruct the sedimentary environment and relative sea-level during the time period of 44.80 ka cal BP. This indicates that a sea-retreating and retreating process has taken place; VI (5.2-0 m), Terrestrial deposition, is separated into swamp wetlands (VI-1) and flood plain (VI-2). The changes in sedimentary levels had a fairly strong correlation with the changes in sea level. Within the scope of this study, we conducted an in-depth investigation of the innovative membrane technology for the treatment of seawater by means of aqueous phase advanced oxidation close to the Bohai. The results of this study present a prospective technique that could make it possible to use membrane technology in the process of environmental restoration in marine settings.

Experimental Investigation of Synchronous Grouting Material Prepared with Different Mineral Admixtures.

Waste sediment generated during tunnel construction is applied to prepare synchronous grouting material, where the influences of fly ash, slag powder, and bentonite on the rheological properties (such as consistency, fluidity, setting time, drainage rate, and stone rate) are studied. The results show that adding fly ash content increases the initial consistency, setting time, and fluidity of grouting material, but also increases its drainage rate and decreases its stone rate. The addition of slag powder results in a slight increase in the setting time and fluidity of the grouting material, yet a decrease in the initial consistency value. In contrast, with the addition of bentonite, both the initial consistency and fluidity of the grouting material decrease. Finally, the optimal mix ratio of high-performance and low-cost grouting materials is fixed to be 30% fly ash, 50% slag powder, and 10% bentonite. Therefore, the fluidity of grouting material can be 170 mm, with an initial consistency of 122 mm, setting time of 1050 min, stone rate of 96.2%, drainage rate of 1.5%, and 28-day compressive strength of 8.3 MPa.

Construction of the gene expression subgroups of patients with coronary artery disease through bioinformatics approach.

Coronary artery disease (CAD) is a heterogeneous disease that has placed a heavy burden on public health due to its considerable morbidity, mortality and high costs. Better understanding of the genetic drivers and gene expression clustering behind CAD will be helpful for the development of genetic diagnosis of CAD patients. The transcriptome of 352 CAD patients and 263 normal controls were obtained from the Gene Expression Omnibus (GEO) database. We performed a modified unsupervised machine learning algorithm to group CAD patients. The relationship between gene modules obtained through weighted gene co-expression network analysis (WGCNA) and clinical features was identified by the Pearson correlation analysis. The annotation of gene modules and subgroups was done by the gene ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis. Three gene expression subgroups with the clustering score of greater than 0.75 were constructed. Subgroup I may experience coronary artery disease of an in-creased severity, while subgroup III is milder. Subgroup I was found to be closely related to the upregulation of the mitochondrial autophagy pathway, whereas the genes of subgroup II were shown to be related to the upregulation of the ribosome pathway. The high expression of APOE, NOS1 and NOS3 in the subgroup I suggested that the patients had more severe coronary artery disease. The construction of genetic subgroups of CAD patients has enabled clinicians to improve their understanding of CAD pathogenesis and provides potential tools for disease diagnosis, classification and assessment of prognosis.

Magnetic ZnFe2O4 nanotubes for dispersive micro solid-phase extraction of trace rare earth elements prior to their determination by ICP-MS.

Magnetic ZnFe2O4 nanotubes (ZFONTs) with numerous pores on their walls were synthesized and characterized. They are shown to be a viable sorbent for dispersive micro-solid phase extraction of the trivalent ions of rare earth elements (REEs), specifically of lanthanum, praseodymium, europium, gadolinium, holmium and ytterbium. The specific surface area of ZFONTs is large (57 m2⋅g-1) and much bigger than that of ZnFeO4 nanoparticles (16 m2⋅g-1). It is shown that REEs are quantitatively retained on ZFONTs in the pH range of 7.0-9.0. The separation of the sorbent from the aqueous phase was achieved by an external magnetic field. Following elution with 0.5 mol⋅L-1 HNO3, REEs were quantified by inductively coupled plasma mass spectrometry. The main parameters influencing preconcentration and determination of the REEs were studied. Under optimum conditions, detection limits for REEs range from 0.01 (Ho) to 0.75 (La) pg⋅mL-1. Relative standard deviations are less than 6.5% (for n = 9; at 1.0 ng⋅mL-1). The method was applied to the determination of trace REEs in spiked biological and environmental samples and gave satisfactory results. Graphical abstract Schematic presentation of a new adsorbent for dispersive micro-solid phase extraction (DMSPE) combined with ICP-MS. Magnetic ZnFe2O4 nanotubes with many pores on their walls were used for preconcentration and determination of rare earth elements (REEs) in environmental and biological samples.

Synergistic Effects of Nano-Montmorillonite and Polyethylene Microfiber in Foamed Paste with High Volume Fly Ash Binder.

Foamed cement-based materials have attracted much attention as a new type of thermal insulation materials (TIMs) that may offer a sustainable solution to the built environments. This laboratory study explores the combined use of nano-montmorillonite and polyethylene microfiber in foamed paste with high volume fly ash (HVFA) binder. A total of 16 foamed HVFA paste mixtures were fabricated which consisted of 70% Class F fly ash, 30% Portland cement, 2% sodium alpha-olefin sulfonate, 0.38% Na3PO4, and 2% nano-montmorillonite. The dosage and type of polyethylene microfibers (90 µm in diameter) were explored in the present study, with six dosages (0, 0.1%, 0.2%, 0.3%, 0.4%, 0.5% by volume) and three lengths (3 mm, 6 mm, and 9 mm) tested. Based on the experimental results, the highest 28-day rupture strength (1.51 MPa) was achieved with the use of 3-mm long PE microfibers at 0.4 vol.%. Synergistic utilization of nMMT and microfibers exhibited a great influence on the dry density and water absorption of the foamed paste. The SEM micrographs illustrated the multiple mechanisms by which the microfibers serve to reduce shrinkage-induced cracking of the foamed paste. Energy-dispersive X-ray spectroscopy was employed to obtain the contents of Ca, Si, Al, S and mole ratios of Ca/Si, Ca/(Si + Al), S/Ca, and Al/Si in the hardened pastes, which reveal the difference in hydration products near or away from the nMMT-pretreated polyethylene microfibers. The results of microhardness test were also used to elucidate such nano-/micro-synergistic effects, which improved the bonding between microfibers and foamed paste matrix. A mechanism was proposed to explain the role of various admixtures and the balanced performance of such inorganic TIMs.

Synthesis of 5-hydroxymethyl furfural from cellulose via a two-step process in polar aprotic solvent.

The synthesis of 5-hydroxymethyl furfural (HMF) from cellulose via a two-step process was investigated. To optimize reaction conditions, the separate conversion of cellulose and glucose was first performed in tetrahydrofuran (THF) and N, N-dimethylformamide (DMF) via a one-step process using hosphotungstic acid (PHA) as catalyst. The direct conversion of cellulose to HMF was then performed via the two-step process. The first step and the second step were carried out in THF and the mixture solvent composed of THF/DMF, respectively. Cellulose was converted to HMF and glucose in the first step in THF. Both of cellulose and the as-formed glucose were then converted to HMF in the second step. The conversion of cellulose to HMF and glucose were significantly improved by the two-step process, and the total yield of HMF and glucose was elevated from 52.1 to 97.0%. A possible mechanism for the formation of HMF from cellulose via the two-step process was also proposed.

Study on regeneration of waste powder activated carbon through pyrolysis and its adsorption capacity of phosphorus.

The regeneration of WPAC through pyrolysis and its adsorption capacity of phosphorus were studied. The optimum conditions for WPAC regeneration were 650 °C and 2 h which resulted in a recovery of BET surface and total pore volume with a value of 1161.4 m2/g and 1.2176 m3/g. WPAC had a maximum PO43--P adsorption capacity of 9.65 mg/g which was 48.93% of PAC, while RWPAC had a maximum PO43--P adsorption capacity of 15.31 mg/g which was 77.64% of PAC. The kinetic analysis revealed that Langmuir model could well describe the adsorption process of PAC, WPAC and RWPAC on PO43--P and the PO43--P adsorption followed the pseudo-second-order model.

Nutrients removal from the secondary effluents of municipal domestic wastewater by Oscillatoria tenuis and subsequent co-digestion with pig manure.

Batch experiments were carried out to investigate the performance of Oscillatoria tenuis to remove nitrogen, phosphorus and chemical oxygen demand (COD) from secondary effluents of municipal domestic wastewater. Meanwhile the potential of biogas production by collected O. tenuis co-digested with pig manure was also investigated. O. tenuis had a biomass productivity of 150 mg L-1 d-1, a removal rate of [Formula: see text] (96.1%), total phosphorus (82.9%) and COD (92.6%) within 7 d at an aeration rate of 1.0 L/min. The biochemical methane potential (BMP) test for O. tenuis fermented with pig manure was evaluated at three different ratios. The cumulative methane yield was 183 mL CH4/gVSadd at a mixing ratio (MR) of 3.0, 191 mL CH4/gVSadd at a MR of 2.0 and 84 mL CH4/gVSadd at a MR of 1.0. The maximum methane yield appeared at the ratio of 2.0. Meanwhile, acid-, alkali- and thermal-pretreatments were applied to raw microalgae biomass to promote biogas production. The highest methane productivity (256 mL CH4/gVSadd) was achieved by the thermal-pretreatment at 120°C, which was about 1.5 times higher than the non-pretreatment group (191 mL CH4/g VSadd).

Enhancement of CO2 capture performance of aqueous MEA by mixing with [NH2e-mim][BF4].

Alcohol amine solutions have a high absorption capacity and rate for CO2 capture, however, there are some shortcomings such as high energy-consumption and low stability. To enhance CO2 capture performance of aqueous MEA, a functional ionic liquid ([NH2e-mim][BF4]) was introduced based on the advantages for CO2 capture. Absorbents were prepared with the molar concentration ratio of [NH2e-mim][BF4] to the 30 vol% aqueous MEA of 0 : 10, 1 : 9, 2 : 8, 3 : 7, 4 : 6 and 6 : 4. The density and the viscosity of the investigated absorbents were measured and the effects of the molar fraction of [NH2e-mim][BF4] (n I) and temperature on CO2 absorption performance were investigated. CO2 desorption performance of the solvent at different temperatures was discussed. The stability performance of the absorbent with n I of 2 : 8 (I/M2:8) was examined by five consecutive cyclic tests. The results showed that for pure CO2, the I/M2:8 displayed the highest absorption performance at 303 K under 1 bar: a comparable CO2 absorption capacity of the 30 vol% aqueous MEA and a higher CO2 absorption rate at the later absorption stage. Moreover, with the increase of temperature, CO2 absorption capacity and rate decreased, while CO2 desorption efficiency and rate increased. 393 K was chosen as the optimum desorption temperature with the desorption efficiency of 99.31%. The introducing of IL contributed to CO2 desorption performance of the absorbents significantly. The properties (CO2 absorption capacity, mass loss, density and viscosity) of the I/M2:8 during the cycles suggested that the IL-MEA mixture had an excellent stability performance.

Study on the adsorption of nitrogen and phosphorus from biogas slurry by NaCl-modified zeolite.

A NaCl-modified zeolite was used to simultaneously remove nitrogen and phosphate from biogas slurry. The effect of pH, contact time and dosage of absorbants on the removal efficiency of nitrogen and phosphate were studied. The results showed that the highest removal efficiency of NH4+-N (92.13%) and PO43--P (90.3%) were achieved at pH 8. While the zeolite doses ranged from 0.5 to 5 g/100 ml, NH4+-N and PO43--P removal efficiencies ranged from 5.19% to 94.94% and 72.16% to 91.63% respectively. The adsorption isotherms of N and P removal with NaCl-modified zeolite were well described by Langmuir models, suggesting the homogeneous sorption mechanisms. While through intra-particle diffusion model to analyze the influence of contact time, it showed that the adsorption process of NH4+-N and PO43--P followed the second step of intra-particle diffusion model. The surface diffusion adsorption step was very fast which was finished in a short time.

Dual extraction based on solid phase extraction and solidified floating organic drop microextraction for speciation of arsenic and its distribution in tea leaves and tea infusion by electrothermal vaporization ICP-MS.

A dual extraction based on solid phase extraction (SPE) and solidified floating organic drop microextraction (SFODME) was developed for As species in tea leaves and tea infusion by electrothermal vaporization inductively coupled plasma mass spectrometry, including total, suspended, soluble, organic and inorganic As as well as As(III) and As(V). In SPE step, titanium dioxide nanotubes were used for preconcentration of analytes and removal of sample matrix. Elution solution from SPE was employed for further preconcentration and separation of analytes with SFODME. Under optimal conditions, detection limits of this method were 0.046 and 0.072pgmL(-1) with relative standard deviations of 6.3% and 5.8% for As(III) and As(V) (n=9, c=1.0ngmL(-1)), respectively. A preconcentration factor of 500-fold was achieved for As(III) and As(V). This method was successfully applied for analysis of speciation of arsenic and its distribution in tea leaves, tea infusion and certified reference material of tea leaves.

[Molluscicidal effect of simple black film mulching in mountainous areas of Yunnan Province].

OBJECTIVE: To evaluate the molluscicidal effect of black plastic mulching in mountainous areas of Yunnan Province. METHODS: In Leqiu Village, Nanjian County, Yunnan Province, the terraced fields with Oncomelania hupensis snails were divided into A, B, C, D, E groups, and of which, A, B, C, D groups, as the experimental groups, were administered with simple black plastic mulching for 30 days, 60 days, 90 days and 120 days respectively; Group E, as the control group, was administered with 50% niclosamide ethanolamine salt wettable powder spraying. RESULTS: In Group C and D (simple black film mulching for 90 days and 120 days), no snails were found after the administration, the average density of living snails decreased by 100%, and the cost of one year was similar to that of the control group. CONCLUSION: The molluscicidal effect of black plastic mulching is good in mountainous areas.

Isolation of cellulose from rice straw and its conversion into cellulose acetate catalyzed by phosphotungstic acid.

Cellulose was isolated from rice straw by pretreatment with dilute alkaline and acid solutions successively, and it was further transferred into cellulose acetate in the presence of acetic anhydride and phosphotungstic acid (H3PW12O40·6H2O). The removal of hemicellulose and lignin was affected by the concentration of KOH and the immersion time in acetic acid solution, and 83wt.% content of cellulose in the treated rice straw was obtained after pretreatment with 4% KOH and immersion in acetic acid for 5h. Phosphotungstic acid was found to be an effective catalyst for the acetylation of the cellulose derived from rice straw. The degree of substitution (DS) values revealed a significant effect for the solubility of cellulose acetate, and the acetone-soluble cellulose acetate with DS values around 2.2 can be obtained by changing the amount of phosphotungstic acid and the time of acetylation. Both the structure of cellulose separated from rice straw and cellulose acetate were confirmed by FTIR and XRD.

Development of a supported tri-metallic catalyst and evaluation of the catalytic activity in biomass steam gasification.

A supported tri-metallic catalyst (nano-Ni-La-Fe/gamma-Al(2)O(3)) was developed for tar reduction and enhanced hydrogen production in biomass steam gasification, with focuses on preventing coke deposition and sintering effects to lengthen the lifetime of developed catalysts. The catalyst was prepared by deposition-precipitation method and characterized by various analytical approaches. Following that, the activity of catalysts in biomass steam gasification was investigated in a bench-scale combined fixed bed reactor. With presence of the catalyst, the content of hydrogen in gas products was increased to over 10 vol.%, the tar removal efficiency reached 99% at 1073 K, and more importantly the coke deposition on the catalyst surfaces and sintering effects were avoided, leading to a long lifetime of catalysts.

Development of nano-niO/Al2O3 catalyst to be used for tar removal in biomass gasification.

The objective of this study isto develop a novel supported nano-NiO catalyst for tar removal in biomass gasification/pyrolysis, to significantly enhance the quality of the produced gases. For this purpose, the supported nano-NiO/gamma-Al2O3 catalyst was prepared by deposition-precipitation (DP) method. Different analytical approaches such as XRD, BET, TEM and SEM/EDX were used to characterize the synthesized catalysts. The results showed thatthe prepared nano-NiO/gamma-Al2O3 catalysts had a coated structure with a loading of NiO in catalysts over 12 wt %, and they had also a higher BET surface area over commercial nickel based catalysts. The active components of catalyst were spherical NiO nanoparticles coated on the surface of supports with a size range of 12-18 nm. Furthermore, the activity of the catalysts to remove tar in the process of biomass pyrolysis was also investigated using a bench-scale combined fixed bed reactor. The experiments demonstrated that the tar yield after addition of the catalyst was reduced significantly; the tar removal efficiency reached to 99% for catalytic pyrolysis at 800 degrees C, and the gas yield after addition of the catalyst increased markedly. The compositions of gas products before and after addition of the catalyst in the process also changed significantly. The percentages of CO2 and CH4 in the product gas after addition of the catalysts were obviously reduced, while those of the valuable H2 and CO strongly increased. Therefore, using the prepared NiO/gamma-Al2O3 catalyst in biomass gasification/pyrolysis can significantly improve the quality of the produced gas and meanwhile efficiently eliminate the tar generation.