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A technoeconomic analysis (TEA) and life cycle assessment (LCA) was conducted on the use of landfill gas (LFG) for electricity generation using an internal combustion engine. This study provides insights that can guide LFG waste to energy (WTE) operators on decisions concerning installation of contaminant removal from LFG for electricity generation. Four scenarios were analyzed; the first (Scenario 1) was a facility with a single siloxane removal unit (SREU) sized for 6 months of continuous use, the second (Scenario 2) was a facility with parallel SREUs sized for one month of use, the third (Scenario 3) was a facility with no SREU, and the fourth was a facility that flared all LFG captured. The TEA revealed that the chiller cost was over 50% the total purchase cost of the LFG pre-treatment system. When the complete LFG to electricity process was analyzed, the internal combustion engine had the highest percentage of total capital investment and the total annual cost. For the base case, it became economically beneficial to install a SREU at facilities with LFG flowrates greater than ∼2000 m 3 /h. Sensitivity analysis showed that at a base case of 1700 m 3 /h, LFG (50% CH 4 ), and 50 mg/m 3 D4, the net income of facilities in Scenarios 1 to 3 became positive at an electricity sales price greater than 5.5 cents/kWh. LCA revealed that Scenario 2 had the greatest CO 2 emission reduction. Scenario 3 is observed to save less CO 2 emissions as biogas flowrate increases due to frequent engine shutdowns. Although there are differences in the global warming potential (GWP 100) for Scenarios 1 to 3, with Scenario 2 being the best and Scenario 3 being the worst, the differences are very small. For this reason, economics alone are sufficient in decision making., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Metal oxynitrides show promising activity for photocatalytic solar water splitting and CO 2 reduction under solar irradiance. Precise control of cation ratios in oxynitrides is an inevitable challenge that needs to be overcome for achieving effective band gap tuning. Here we report the density functional theory-based calculations for the intricate structure-function relationships of Zn-Ga based oxynitrides and correlate the results with the experimental parameters. Crucial material property descriptors such as elemental composition, intrinsic lattice strain, and vacancy defects were exploited during the synthesis to achieve stable oxynitride photocatalysts that demonstrated CO 2 conversion to CO under simulated solar light, without any noble metal impregnation. The highest CO production rate surpassed that of TiO 2 under the same conditions. This work inspires future research on oxynitride materials with tailored optical properties and sustainable photocatalytic activity which enables their large scale applications.

Separation of volatile methyl siloxanes from landfill gas using fixed adsorption beds was modeled with the objective of identifying appropriate technology and the economics associated with this purification step. A general adsorption model assuming plug flow and radial symmetry was developed and used to conduct a parametric sweep of 162 unique cases. The varied parameters were adsorbent type (activated carbon and silica gel), bed height (3.05-9.15 m/10-30 ft), inlet siloxane concentration (5-15 mg/m 3 ), moisture content (0-100% relative humidity at STP or RH), and siloxane tolerance limit (0.094-9.4 mg/m 3 ) that correlated to three distinct energy conversion technologies (electricity production using engines or fuels cells or catalytic conversion to liquid hydrocarbon fuels). Due to the detrimental effect of RH on siloxane absorption, the maximum allowable moisture content of LFG before purification is 50% RH and moisture removal processes are also required. The design calculations using a selected case study show that the adsorption bed height required needed for 6 months minimum breakthrough time for catalytic fuel production is twice that for engine applications. Fuel cell applications require 3 times the bed height compared to engine applications. However, the purification costs amounted to 94%, 16% and 52% of recovered product value for engine, liquefaction, and fuel cell applications, respectively indicating the need for a high value product to justify purification costs. The approaches and conclusions can be extended to specific process conditions for landfill gas purification and to other processes that use biogas produced from waste as a feedstock., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Waste-to-energy projects are an increasingly prominent component of future energy portfolios. Landfill gas (LFG)-to-energy (LFGTE) projects are particularly important as they address greenhouse gas emissions. Contaminants in LFG may hamper these projects both from environmental and economic standpoints. The purpose of this review is to highlight key aspects (LFG composition ranges, LFG flowrates, and allowable tolerances for LFGTE technologies, performance and costs for contaminant removal by adsorption). Removal of key contaminants, H 2 S and siloxanes, by adsorption are surveyed in terms of adsorption capacities and regeneration abilities. Based on the open literature, costing analyses are tabulated and discussed. The findings indicate economics of contaminant removal depend heavily on the feed concentrations of contaminants, allowable tolerances for the LFGTE technology, and the current market for the product. Key trends, identification of challenges, and general purification guidelines for purifying LFG for energy projects are also discussed., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Background: We evaluated the incidence and presentations of internal hernias (IH) after laparoscopic antecolic Roux-en-Y gastric bypass (RYGB) at our institution., Methods: We retrospectively reviewed the records of 594 patients who underwent laparoscopic antecolic RYGB at our institution between December 2004 and December 2010., Results: Five hundred ninety-four patients underwent laparoscopic antecolic RYGB with a mean follow-up of 50.5 months. Thirty-six patients developed 37 IH (6.2 %) requiring surgical intervention. Mean age of IH patients was 36.9 years. Thirty-one out of 36 were female. Mean preoperative BMI was 44.3 Kg/m(2). The mean time of presentation after their RYGB was 25.9 months. The mean % excess body weight loss at time of presentation was 54.0 %. Twenty-five out of 37 of IH occurred at Petersen's space; 9/37 IH occurred under the jejunojejunostomy; three patients had hernias at both locations. Mesenteric swirling was the most common CT scan finding in 20/36 (55.6 %). Six out of 36 CT were initially read as normal; however, on retrospective review by a radiologist, abnormalities indicating IH were found in 4/6. Patients presented with different degrees of acuity: 6/37 with chronic abdominal pain and 28/37 with acute abdominal pain. Bowel necrosis was found in 3/37., Conclusion: IH is a serious and potentially fatal complication of RYGB. Presentation can vary from chronic abdominal pain to bowel necrosis. CT is helpful in providing diagnosis; however, careful attention to the specific signs of small bowel volvulus, such as mesenteric swirl sign, should be given. IH should be considered in RYGB patients who present with even vague symptoms.

InVO4/TiO2 composite was synthesized via amalgamation of InVO4 with TiO2 (Degussa P-25) powders. Application of the produced composite was evaluated as a catalyst for visible-light photocatalytic degradation of 2-chlorophenol (2-CP) in synthetic wastewater solutions. The catalyst was characterized by X-ray diffraction (XRD), scanning electron microscopy energy dispersive X-ray microanalyses and nitrogen physisorption. The degradation of 2-CP was affected by solution pH, light intensity, photocatalyst dosage and 2-CP initial concentration. InVO4/TiO2 showed higher photocatalytic degradation of 2-CP as compared with Degussa P-25 TiO2. Complete degradation of 2-CP was achieved with the InVO4/TiO2 catalyst under optimized conditions (1 g/L catalyst with a pollutant concentration of 50 mg/L at solution pH 5 and irradiation time of 180 min). Comparatively, 2-CP degradation efficiency of 50.5% was achieved with the TiO2 (Degussa P-25) at the same experimental conditions. The study confirmed that InVO4/TiO2 has high potential for degradation of 2-CP from wastewater under visible-light irradiation.

Pt nanoparticles/TiO2 catalysts were prepared and evaluated for UV-photocatalytic degradation ofphenol and 2-chlorophenol (2-CP) in synthetic wastewater solutions. The catalysts were synthesized by immobilizing colloidal Pt nanoparticles onto titanium dioxide (rutile TiO2). Analytical techniques, such as standard Brunauer-Emmett-Teller isotherms, X-ray diffraction, transmission electron microscope, were utillized for investigating the specific surface area, structure, and particle size distribution of the catalysts and its components. The photocatalytic activities of both phenol and 2-CP solutions were studied in a 1L batch photoreactor independently, under 450 W UV irradiation. Samples were drawn at regular intervals and residual concentration of phenol and 2-CP in the samples was analysed using an UV-visible spectrophotometer. Parameters controlling the photocatalytic process, including catalyst concentration, solution pH, and initial phenol (2-CP) concentration, were investigated. The obtained results revealed that Pt/TiO2 showed higher photocatalytic degradation for both phenol and 2-CP pollutants in solution (as compared to the rutile TiO2). The degradation efficiencies of 87.7% and 100% were obtained for phenol and 2-CP, respectively, under optimized conditions (0.5 g/L catalyst with a pollutant concentration of 50 mg/L after irradiation time of 180 min).

Ethylenediaminetetraacetic acid (EDTA) functionalized silica adsorbent has been synthesized using (3-aminopropyl) triethoxylsilane (APTES) as a bridging link between silanol groups (SiOH) of silica and carboxylic group of EDTA. Fourier transform infrared spectroscopy (FTIR) and Temperature-programmed oxidation (TPO) analysis confirmed the grafting of EDTA onto the silica. The synthesized EDTA-silica was investigated as an adsorbent for removal of Cu(II), Zn(II) and Ni(II) from aqueous solution. The effect of solution pH, initial solution concentration, and contact time were studied. The removal of metal ions increased with the increase in solution pH, contact time and concentration. The maximum equilibrium time was found to be 45min for all three metal ions. Kinetics studies revealed that the adsorption of Cu(II), Zn(II) and Ni(II) onto EDTA-silica followed the pseudo-second order kinetics and film diffusion and intra-particle diffusion mechanism were involved. Adsorption equilibrium data were well fitted to Langmuir isotherm model and maximum monolayer adsorption capacity for Cu(II), Zn(II) and Ni(II) was 79.36, 74.07 and 67.56mg g(-1), respectively. Thermodynamic results reveal that the removal of metals onto EDTA-silica was endothermic and spontaneous in nature., (Copyright © 2013 Elsevier Inc. All rights reserved.)

Photocatalytic process has shown recently a great potential as an environmental friendly and clean remediation technology for organic pollutants in wastewater. This work described the synthesis of silver-based bimetallic nanoparticles using colloid chemistry and the subsequent immobilization onto titania to form composite photocatalytic materials (titania-supported Ag-Pt nanoparticles). The photocatalysts were characterized by X-ray diffraction, electron microscopy, and nitrogen physisorption. The catalytic activity of the photocatalysts was evaluated by photocatalytic degradation of phenol and 2-chlorophenol (2-CP) in synthetic wastewater solutions. The photocatalytic processes were conducted in a batch photoreactor containing appropriate solutions of phenol and 2-CP with UV irradiation of 450 W. UV-visible spectrophotometer was used for analyzing the concentration of phenol and 2-CP in solutions. Parameters affecting the photocatalytic process such as the solution pH, phenol and 2-CP concentrations, and catalyst concentration were investigated. The results obtained revealed that TiO(2)-supported Ag/Pt nanoparticles showed a higher activity for UV-photocatalytic degradation of both phenol and 2-CP pollutants in the solution (as compared to the plain rutile TiO(2)). The photodegradation processes were optimized by the 0.5-g/L catalyst with a pollutant concentration of 50 mg/L for all the samples. Complete degradation for both phenol and 2-CP was achieved after 120 min.

Generation 4 polyamidoamine (PAMAM) dendrimers with ethylenediamine cores (G4-OH) were immobilized on titania (TiO(2)) and examined as novel metal chelation materials. Characterization results indicate both the effective immobilization of dendrimers onto titania and retention of the dendrimer on titania following remediation. The effective remediation of Cu(II), Ni(II), and Cr(III), which are model pollutants commonly found in industrial electroplating wastewater, is demonstrated in this work. Important parameters that influence the efficiency of metal ion removal were investigated; e.g. solution pH, retention time, metal ion concentration, and composite material dosage. Metal ion removal was achieved over a wide metal concentration range within a 1 h equilibration time. Maximum metal ion removal was achieved at pH ≥7 for both Cu(II) and Cr(III), and pH ≥9 for Ni(II). Further, the dendrimer/titania composite materials were even more effective when metal ion mixtures were tested. Specifically, a dramatic increase was observed for Ni(II) chelation when in a mixture was compared to a pure nickel solution. These findings suggest new strategies for improving metal ion removal from industrial wastewater., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

This study presents a kinetic model of the chelation of iron ions by generation 4 hydroxyl-terminated polyamidoamine (PAMAM) with ethylenediamine core (G4-OH). The coordination processes of iron ions from ferric chloride, FeCl(3), and ferrous bromide, FeBr(2), to G4-OH dendrimers were analyzed using ultraviolet-visible (UV-vis) spectroscopy, proton nuclear magnetic resonance ((1)H NMR) spectroscopy, and liquid chromatography-mass spectrometry (LC-MS). In the visible region, a charge-transfer was observed when the dendrimer was added to a ferric chloride solution. This phenomenon is a ligand-to-metal charge-transfer (LMCT) between the free electron group of the dendrimer's internal amines and the dehalogenated iron ion that takes 2 h to complete at room temperature. Analysis of potential rate laws and diffusion effects led to a second-order kinetic model for this reaction. By measuring the rate coefficients as a function of temperature (22-37 °C), an apparent activation energy of 41.5 kJ/mol was obtained using the Arrhenius method. The results of this study will fuel research of PAMAM dendrimers for environmental, pharmaceutical, and materials applications., (© 2011 American Chemical Society)

Deactivation mechanisms of alumina-supported, Ni-based catalysts for tar reforming in biomass-derived syngas were evaluated using extended X-ray absorption fine structure (EXAFS) spectroscopy. Catalysts were characterized before and after catalytic reaction cycles and regeneration procedures, which included oxidation by a mixture of steam and air, and reduction in hydrogen. Qualitative analysis of the EXAFS spectra revealed that oxidation of a portion of the Ni in the catalysts to form an oxide phase and/or a sulfide phase were likely scenarios that led to catalyst deactivation with time-on-stream and with increased reaction cycles. Deactivation through carbon deposition, phosphorus poisoning, or changes in particle size were deemed as unlikely causes. Quantitative analysis of the EXAFS spectra indicated sulfur poisoning occurred with time-on-stream, and the contaminating species could not be completely removed during the regeneration protocols. The results also verified that Ni-containing oxide phases (most likely a spinel also containing Mg and Al) formed and contributed to the deactivation. This study validates the need for developing catalyst systems that will protect Ni from sulfur poisoning and oxide formation at elevated reaction and regeneration temperatures.

A continuing goal in catalysis is to unite the advantages of homogeneous and heterogeneous catalytic processes. To this end, nanoparticles represent a new frontier in heterogeneous catalysis, where this unification can also be supplemented by the ability to obtain new or divergent reactivity and selectivity. We report a novel method for applying heterogeneous catalysts to known homogeneous catalytic reactions through the design and synthesis of electrophilic platinum nanoparticles. These nanoparticles are selectively oxidized by the hypervalent iodine species PhICl(2), and catalyse a range of π-bond activation reactions previously only catalysed through homogeneous processes. Multiple experimental methods are used to unambiguously verify the heterogeneity of the catalytic process. The discovery of treatments for nanoparticles that induce the desired homogeneous catalytic activity should lead to the further development of reactions previously inaccessible in heterogeneous catalysis. Furthermore, a size and capping agent study revealed that Pt PAMAM dendrimer-capped nanoparticles demonstrate superior activity and recyclability compared with larger, polymer-capped analogues.

Platinum nanocubes and nanopolyhedra with tunable size from 5 to 9 nm were synthesized by controlling the reducing rate of metal precursor ions in a one-pot polyol synthesis. A two-stage process is proposed for the simultaneous control of size and shape. In the first stage, the oxidation state of the metal ion precursors determined the nucleation rate and consequently the number of nuclei. The reaction temperature controlled the shape in the second stage by regulation of the growth kinetics. These well-defined nanocrystals were loaded into MCF-17 mesoporous silica for examination of catalytic properties. Pt loadings and dispersions of the supported catalysts were determined by elemental analysis (ICP-MS) and H(2) chemisorption isotherms, respectively. Ethylene hydrogenation rates over the Pt nanocrystals were independent of both size and shape and comparable to Pt single crystals. For pyrrole hydrogenation, the nanocubes enhanced ring-opening ability and thus showed a higher selectivity to n-butylamine as compared to nanopolyhedra.

Background: This study aimed to define perceptions of the need and the value of new simulation devices for laparoscopic and robot-assisted surgery. The initial experience of surgeons using both robotic and nonrobotic laparoscopic simulators to perform an advanced laparoscopic skill was evaluated., Methods: At the 2006 Society of American Gastroesophageal Surgeons (SAGES) meeting, 63 Learning Center attendees used a new virtual reality robotic surgery simulator (SEP Robot) and either a computer-enhanced laparoscopic simulator (ProMIS) or a virtual reality simulator (SurgicalSIM). Demographic and training data were collected by an intake survey. Subjects then were assessed during one iteration of laparoscopic suturing and knot-tying on the SEP Robot and either the ProMIS or the SurgicalSIM. A posttask survey determined users' impressions of task realism, interface quality, and educational value. Performance data were collected and comparisons made between user-defined groups, different simulation platforms, and posttask survey responses., Results: The task completion rate was significantly greater for experts than for nonexperts on the virtual reality platforms (SurgicalSIM: 100% vs 36%; SEP Robot: 93% vs 63%; p < 0.05). Prior robot use was predictive of task completion on the SEP Robot, and nonexperts were more likely to complete the virtual reality task on the SEP Robot than on the SurgicalSIM. Experts performed better than nonexperts for all performance measures on the ProMIS. All the survey scores pertaining to realism except image quality were higher for the ProMIS than for either virtual reality trainer., Conclusion: The task completion rate was the best discriminant of expert performance on both virtual reality platforms, whereas simulator metrics best discriminated expertise for the videoscopic platform. Similar comparisons for the virtual reality platforms were not feasible because of the low task completion rate for nonexperts. The added degrees of freedom associated with the robotic surgical simulator instruments facilitated completion of the task by nonexperts. All platforms were perceived as effective training tools.

Well-defined platinum nanoparticles between 0.8 and 5.0 nm were prepared using dendrimer and polymer capping agents and supported onto mesoporous SBA-15 silica. Using these model catalysts, pyrrole hydrogenation was demonstrated to be structure sensitive because ring opening occurred more easily over larger particles compared to smaller ones. The phenomenon is caused by surface roughness or electronic effects that change with particle size.

Monodisperse rhodium (Rh) and platinum (Pt) nanoparticles as small as approximately 1 nm were synthesized within a fourth generation polyaminoamide (PAMAM) dendrimer, a hyperbranched polymer, in aqueous solution and immobilized by depositing onto a high-surface-area SBA-15 mesoporous support. X-ray photoelectron spectroscopy indicated that the as-synthesized Rh and Pt nanoparticles were mostly oxidized. Catalytic activity of the SBA-15 supported Rh and Pt nanoparticles was studied with ethylene hydrogenation at 273 and 293 K in 10 torr of ethylene and 100 torr of H 2 after reduction (76 torr of H 2 mixed with 690 torr of He) at different temperatures. Catalysts were active without removing the dendrimer capping but reached their highest activity after hydrogen reduction at a moderate temperature (423 K). When treated at a higher temperature (473, 573, and 673 K) in hydrogen, catalytic activity decreased. By using the same treatment that led to maximum ethylene hydrogenation activity, catalytic activity was also evaluated for pyrrole hydrogenation.

Monodisperse sub-10 nm Rh nanocubes were synthesized with high selectivity (>85%) by a seedless polyol method. The {100} faces of the Rh NCs were effectively stabilized by chemically adsorbed Br- ions from trimethyl(tetradecyl)ammonium bromide (TTAB). This simple one-step polyol route can be readily applied to the preparation of Pt and Pd nanocubes. Moreover, the organic molecules of PVP and TTAB that encapsulated the Rh nanocubes did not prevent catalytic activity for pyrrole hydrogenation and CO oxidation.