Flammability of hydrocarbon and carbon dioxide mixtures

The effect of carbon dioxide (CO₂) concentration on the ignition behaviour of hydrocarbon and CO₂ gas mixtures is examined in both jets and confined explosions. Results from explosion tests are presented using a 20 l explosion sphere and an 8 m long section of 1.04 m diameter pipeline. Experiments to assess the flame stability and ignition probability in free-jets are reported for a range of different release velocities. An empirically-based flammability factor model for free-jets is also presented and results are compared to ignition probability measurements previously reported in the literature and those resulting from the present tests.The results help to understand how CO₂ changes the severity of fires and explosions resulting from hydrocarbon releases. They also demonstrate that it is possible to ignite gas mixtures when the mean concentration is outside the flammable range. This information may be useful for risk assessments of offshore platforms involved in carbon sequestration or enhanced oil recovery, or in assessing the hazards posed by poorly-inerted hydrocarbon processing plant.     

Environmental and eco-costs life cycle assessment of an acrylonitrile process by capacity enlargement in Mexico

Life cycle assessment and marginal prevention costs (eco-costs method) for an acrylonitrile plant were carried out estimating the environmental impact and the eco-costs, due to the increment in the production capacity. This study compares the old plant's operative performance (old design) at 50,000 ton/year where the by-products were incinerated, with the current operation at 60,000 ton/year where those by-products in the waste stream will be treated to take advantage of its substance content, to generate profitable products. In addition, the effect of a wastewater flow rate with cyanide was evaluated on the biological wastewater treatment process.The redesign showed a high reduction percentage in eleven of eighteen midpoint impact categories. The reduction of 36% in the global impacts in the redesign was obtained when these ones were calculated based on the impacts of the year of 2005. The CO₂ emissions equivalents (CO₂eq) had a reduction of 46% (from 6.55 to 3.50 kg CO₂eq/kg of acrylonitrile). The total of marginal prevention costs (eco-costs) are 1.28 USD/kg for acrylonitrile old design and the 0.735 USD/kg for acrylonitrile redesign, i.e. 42.5% lower than the old design. This means that 94.5% are costs for pollution and the use of energy and 5.4% by depletions of material resources.This study proved that the redesign is environmentally most favorable and economically affordable method.Eco-costs method should be incorporated as part of the financial indicators of a project, but with the respective adaptation to the environmental and economic conditions of a region.     

Is biochar or straw-bale construction a better carbon storage from a life cycle perspective?

Biochar has been presented as a key technology for avoiding dangerous climate change. Pyrolysis converts part of the biomass feedstock into a gaseous fraction, which can be used for energy production. The remaining fraction is char, which is highly stable and resistant to biodegradation. When char is added to soil it increases carbon storage, reduces emissions and improves soil quality. Agricultural residues such as straw, stover and hulls are seen as the most accessible raw material. These residues could also be used as insulation in passive energy housing. Straw bale construction is a relatively simple technology, which has been applied for decades. It can store the carbon of the straw material into walls structures and in the process provides energy efficient housing. The climate benefits from improved energy efficiency depend on local conditions and energy production forms. In this study life cycle assessment was used to compare the climate impacts of biochar production and straw bale construction. On a life cycle perspective, straw bale construction results in higher net carbon storage than biochar production (3.3 t CO₂eq vs. 0.9 t CO₂eq/t of straw). However the result was found to be highly dependent on the assumptions on the overall energy efficiency of the replaced building stock.     

Hydrogen sulphide removal from landfill gas

Control of odours should be considered to be a fundamental issue in order to site, design and manage sanitary landfills. With regard to construction and demolition (C&;D) debris, landfilling was the mainly adopted solution in many European Countries; in particular, gypsum drywalls can produce high concentrations of hydrogen sulphide (H₂S) in landfill gas ranging from 7 ppm to 100 ppm. In some cases also dangerous concentrations until to 12,000 ppm were detected. In this paper H₂S removal efficiency in a lab-scale vertical packed scrubber was investigated. Hydrogen sulphide abatement was evaluated for inlet H₂S concentrations of 1000–100–10 ppm, adjusting scrubbing liquid pH in the range 9–12.5 by means of caustic soda (NaOH 2N solution). Moreover, best operating conditions for the system were defined as well as H₂S abatement along the tower and liquid recirculation effectiveness in case of inlet H₂S concentration of 10 ppm (typical odour concentration). Results showed that pH of 11.5 in scrubbing liquid could be considered the best value for removal of different inlet H₂S concentrations, also taking into account parasitical consumption of NaOH due to CO₂ absorption. Moreover, in case of continuous working of the system at H₂S concentration of 10 ppm, strong removal efficiency was already obtained with a packed bed height of about 70 cm. Significant performances were ensured after 1 h of constant activity, consuming about 3 ml of soda per cubic meter of polluted air. Subsequently liquid blowdown was necessary.     

Experimental investigation of the flow characteristics of jettisoning in a CO2 carrier

This experimental study was performed to investigate the flow characteristics in the jettisoning flow line of a liquid CO₂ carrier. When a pressurized liquid CO₂ container loses mechanical integrity, possibly by material or mechanical defects, the liquid inventory should be drained out rapidly for safety reasons using the so-called jettisoning process. In the course of jettisoning, the liquid CO₂ undergoes two phase change stages, from liquid to liquid + vapor and from liquid + vapor to solid + vapor. Consequently, the jettisoning release rate is affected by the characteristics of these phase changes. In this study, liquid CO₂ was discharged through a small tube, representing a jettisoning flow line. The temperature and pressure were measured along the tube, and the locations of the phase changes were inferred from the measured data. The experimental results showed that active nucleation occurred near the tube tip and that the phase change into solid and vapor occurred just after leaving the pipe, irrespective of the tube length in this study.     

High-level techno-economic assessment of negative emissions technologies

This paper presents results from research conducted to provide a high level techno-economic and performance assessments of various emerging technologies for capturing CO₂ from the air, directly and indirectly, on a life-cycle basis. The technologies assessed include ‘artificial trees’, the soda lime process, augmented ocean disposal, biochar and bio-energy with carbon capture and storage.These technologies are subjected to quantitative and qualitative analyses, based on the most recent peer reviewed data in the literature, to identify their potential performance as well as the technical and non-technical barriers to their adoption and scale up. Key findings for each technology are presented which seek to highlight the state of technological development and research needs, the anticipated life cycle capture cost in $/tCO₂ based on their potential to deliver a 0.1 ppm CO₂ reduction per annum, policy requirements for scale up and, in light of these findings, the likely role that they will play in addressing climate change and broader environmental issues in the medium to long term.The key finding from the work is that the degree of scale-up required for negative emissions technologies to have a material impact on atmospheric emissions (i.e. at a ppm level) is probably unrealistic in less than 20 years. Therefore, emissions prevention efforts should remain the main focus in addressing climate change and the likely role for negative emissions technologies will be in augmenting a suite of mitigation measures targeting economically or practically difficult emissions.     

Corrosion behavior of steels for CO2 injection

The process chain for Carbon Capture and Sequestration (CCS) includes tubing for injection of CO₂ into saline aquifers. The compressed CO₂ is likely to contain specific impurities; small concentrations of SO₂ and NO₂ in combination with oxygen and humidity are most harmful. In addition, CO₂ saturated brine is supposed to rise in the well when the injection process is interrupted. The material selection has to ensure that neither CO₂ nor brine or a combination of both will leak out of the inner tubing. In this comprehensive paper the investigated materials range from low-alloy steels and 13% Cr steels up to high-alloy materials. Electrochemical tests as well as long term exposure tests were performed in CO₂, in brine and combination of both; pressure was up to 100 bar, temperature up to 60 °C. Whereas the CO₂ stream itself can be handled using low alloy steels, combinations of CO₂ and brine require more resistant materials to control the strong tendency to pitting corrosion. The corrosion behavior of heat-treated steels depends on factors such as microstructure and carbon content. For different sections of the injection tube, appropriate materials should be used to guarantee safety and consider cost effectiveness.     

Anaerobic digestion modeling of the main components of organic fraction of municipal solid waste

The organic fraction of municipal solid waste (OFMSW) is composed of several heterogeneous organic and inorganic wastes. The diversity of composition, the high volatile solid content and the biodegradable material that this waste offers make it quite an interesting option for anaerobic digestion (AD). Depending on the substrate composition, the biological degradation and kinetics of the AD could vary. Biochemical methane potential (BMP) tests are used as a tool to evaluate the methane production of several fractions of OFMSW, in order to study the influence of each fraction in the final mixture. The kinetic parameters of methane curves and the prediction of final productions are studied by different approaches to model equations using linear, exponential, logistic and Gaussian models. The analyses of the fractions indicate that organic substrates such as meat/fish which are in a small proportion in the final mixture, obtain major productivities (291 ± 3 mlCH₄/gVS), however others such as paper (217 ± 5 mlCH₄/gVS) could have their productivity enhanced due to their high VS present in the final mixture. Both the Gomperzt and the first order model fit reasonably with all the fractions, although substrates with lag phase adjust only to the Gompertz model explaining 99% of the experimental results.     

The impact of the 2007 graduated driver licensing law in Massachusetts on the rate of citations and licensing in teenage drivers

ObjectiveWe recently demonstrated that the 2007 Massachusetts Graduated Driving Licensing (GDL) law decreased the rate of motor vehicle crashes in teenage drivers. To better understand this decrease, we sought to examine the law's impact on the issuance of driving licenses and traffic citations to teenage drivers.MethodsCitation and license data were obtained from the Massachusetts Department of Transportation. Census data were obtained from the Census Data Center. Two study periods were defined: pre-GDL (2002–2006) and post-GDL (2007–2012). Two populations were defined: the study population (aged 16–17) and the control population (aged 25–29). The rates of licenses per population were compared pre- vs. post-GDL for the study group. The numbers of total, state, and local citations per population were compared pre- vs. post-GDL for both populations. A sensitivity analysis was performed for the rates of citations using licenses issued as a denominator.ResultsWhile licenses per population obtained by the study group decreased over the entire period, there was no change in the rate of decrease per year pre- vs. post-GDL (2.0% vs. 1.4%; p = 0.6392). In the study population, total, state, and local citations decreased post-GDL (17.8% vs. 8.1%, p < 0.0001; 3.7% vs. 2.2%, p < 0.0001; 14.1% vs. 5.8%, p < 0.0001, respectively). In the control group, total and state citations did not change (26.7% vs. 23.9%, p = 0.3606; 9.2% vs. 10.2%, p = 0.3404, respectively), and local citations decreased (17.5% vs. 13.7%, p = 0.0389). The rates of decrease per year for total, state, and local citations were significantly greater in the study population compared with control (p < 0.0001, p = 0.0002, p < 0.0001, respectively).ConclusionsThe 2007 GDL law in Massachusetts was associated with fewer traffic citations without a change in the rate of licenses issued to teenagers. These findings suggest that 2007 GDL may be improving driving habits as opposed to motivating teenagers to delay the issuing of licenses.     

Can boreal afforestation help offset incompressible GHG emissions from Canadian industries?

To mitigate greenhouse gas and comply with cap-and-trade systems, the carbon capture and storage (CCS) is presently unviable for industrials dealing with low concentration of CO₂ emissions. Alternatively, a new offset opportunity is being analysed in Canada: the afforestation of open woodlands (OWs) in the boreal territory. The results obtained from model simulations (with CBM-CFS3) showed that afforestation of boreal OWs can be a low C-intensive mitigation activity, in particular when understory planting is the chosen silvicultural approach, so that only 8–12 years are needed to reach a net positive C balance with the afforestation of OWs. A large-scale afforestation of boreal OWs – scheduled at 20 kha per year during 20 years for a maximum of 400 kha – could provide capped industrials with a significant offset potential, for instance up to nearly 8% offset of all Québec industrial process emissions (2009 data) after 45 years. In spite of a certain number of issues that can contribute to the uncertainty of the real environmental and economical benefits from the afforestation of OWs as a mitigation activity – most of which issues are discussed in this paper – this study presented a first glimpse at the extent to which the afforestation of boreal OWs in Québec can provide large emitters with eventually substantial and efficient GHG offset potential, especially those emitters tied up with incompressible GHG emissions.     

Oxidation of kerosene components in a soil matrix by a dielectric barrier discharge reactor

This paper discusses some aspects of the kerosene components oxidation in a soil matrix by a dielectric barrier discharge reactor at atmospheric pressure. The total kerosene components abatement can reaches 90% for an energy density of 960 J g_soil^?1. The analyses of the discharge cell outlet gas reveals that CO_x and hydrocarbon compounds selectivity is close to 10%. A semi-quantitative approach by GC-FID shows that the carbon content in the oxidized compounds in soil is about 20% of the carbon content in the initial kerosene components. The polar species formed in soil are a mixture of aliphatic and aromatic molecules containing alcohol and carboxylic acid groups. The process of kerosene oxidation in soil matrix is more promoted than kerosene desorption followed by an oxidation in gas phase.     

Optimization and evaluation of an air-recirculated stripping for ammonia removal from the anaerobic digestate of pig manure

An air-recirculated stripping involved two processes and did not require any pretreatment. First, stripping CO₂ decreased the buffer capacity of the anaerobic digestate, thereby reducing the amount of lime used to achieve a high pH. Second, lime was added to increase pH and remove ammonia from the anaerobic digestate of pig manure. pH increased from 8.03 to 8.86 by stripping CO₂ in the first process (gas-to-liquid ratio = 180) and further reached 12.38 in the second process (gas-to-liquid ratio = 300). During process optimization, the maximum ammonia removal efficiency reached 96.78% with a lime dose of 22.13 g. The value was close to 98.25%, which was the optimal result predicted by response surface methodology using the software Design-Expert 8.05b. All these results indicated that air-recirculated stripping coupled with absorption was a promising technology for the removal and recovery of nitrogen in the anaerobic digestate of pig manure.     

pH-conditioning for simultaneous removal of arsenic and iron ions from groundwater

The effects of some commonly used pH conditioners, viz., lime, banana ash, the carbonate and the bicarbonate of sodium and potassium and their binary mixture, on simultaneous removal of arsenic and iron ions from water have been studied. KHCO₃ has been found to be the most suitable pH conditioner for the purpose. About 80 mg/L KHCO₃ can remove both arsenate and iron ions from initial 250 μg/L and 20 mg/L to below their respective guideline values of the WHO for drinking water, retaining the final pH in the acceptable range for drinking. The simultaneous removal of arsenate and iron by the pH-conditioners decreases in the order: Lime > KHCO₃ > NaHCO₃ > K₂CO₃ > Na₂CO₃ > ash. However, lime requires post-treatment correction of highly alkaline pH. The arsenate ion is removed predominantly through goethite or ferrihydrite in the presence of the bicarbonates and through ferric hydroxide in the presence of the more alkaline pH-conditioners. KHCO₃ is more advantageous over the more basic substances including NaHCO₃, because with it, one not only needs the smallest dose but also can avoid careful adjustment of the dose for regulating the initial and the final pH. The paper clearly demonstrates the potential of KHCO₃ to substitute the currently used pH-conditioners, viz., ash, lime and NaHCO₃ for simultaneous removal of arsenate and iron ions.     

An experimental study for H2S and CO2 removal via caustic scrubbing system

In this study, removal of hydrogen sulfide (H₂S) and carbon dioxide (CO₂) from simulated syngas has been studied on one column scrubbing system. Gas flow rate as a measure of gas residence time and superficial gas velocity, gas composition, inlet H₂S load, flow modes (countercurrent and cocurrent) and packing geometry were the parameters in the design and/or operation of an acid gas scrubber system. Better H₂S scrubbing efficiencies have been obtained in countercurrent flow mode than that of cocurrent flow mode. When accordingly designed, static mixer with its superior performance on H₂S removal overweighed to structured packings. The coexistence of CO₂ and H₂S has been shown to increase the sodium hydroxide (NaOH) consumption along the scrubber column thereby decreasing the H₂S removal efficiency at higher H₂S loads. The gas residence time as changing with the gas velocity was found to be more dominant on acid gas removal efficiency than the effect of superficial gas velocity within the experimented range. A gas residence times of equal or above 3 s were seemed to be closer to the optimum point.     

Disintegration of waste activated sludge by different applications of Fenton process

Oxidative disintegration of municipal waste activated sludge (WAS) using conventional Fenton (Fe²⁺ + H₂O₂, CFP) and Fenton type (Fe⁰ + H₂O₂, FTP) processes was investigated and compared in terms of the efficiency of sludge disintegration and enhancement of anaerobic biodegradability. The influences of different operational variables namely sludge pH, initial concentration of Fe²⁺ or Fe⁰, and H₂O₂ were studied in detail. The optimum conditions have been found as catalyst iron dosage = 4 g/kg TS, H₂O₂ dosage = 40 g/kg TS and pH = 3 within 1 h oxidation period for both CFP and FTP. Kinetics studies were performed under optimal conditions. It was determined that the sludge disintegration was happened in two stages by both processes: rapid and subsequent slow disintegration stages and rapid sludge disintegration stage can be described by a zero-order kinetic model. The effects of oxidative sludge disintegration under the optimum conditions on anaerobic digestion were experienced with biochemical methane potential (BMP) assay in batch anaerobic reactors. Total methane production in the CFP and FTP pre-treated reactors increased by 26.9% and 38.0%, relative to the untreated reactor (digested the raw WAS). Furthermore, the total chemical oxygen demand reductions in the pre-treated reactors were improved as well.     

Feasibility of honeycomb monolith supported sugar catalyst to produce biodiesel from palm fatty acid distillate (PFAD)

Carbon coated monolith was prepared by sucrose solution 65 wt.% via dip-coating method. Sulfonation of incomplete carbonized carbon coated monolith was carried out in order to synthesize solid acid catalyst. The textural structure characteristics of the solid acid catalyst demonstrated a low surface area and pore volume. Palm fatty acid distillate (PFAD), a by-product of palm oil refineries, was utilized as oil source in biodiesel production. The esterification reaction subjected to different reaction conditions was performed by using the sulfonated carbon coated monolith as heterogeneous catalyst. The sulfonation process had been performed by using vapour of concentrated H₂SO₄ that was much easier and efficient than liquid phase sulfonation. Total acidity value of carbon coated monolith was measured for unsulfonated sample (0.5 mmol/g) and sulfonated sample (4.2 mmol/g). The effect of methanol/oil ratio, catalyst amount and reaction time were examined. The maximum methyl ester content was 89% at the optimum condition, i.e. methanol/oil molar ratio (15:1), catalyst amount (2.5 wt.% with respect to PFAD), reaction time (240 min) and temperature 80 °C. The sugar catalyst supported on the honeycomb monolith showed comparable reactivity compared with the sugar catalyst powder. However, the catalyst reusability studies showed decrease in FFA% conversion from 95.3% to 68.8% after four cycles as well as the total acidity of catalyst dropped from the value 4.2 to 3.1 mmol/g during these cycles. This might be likely due to the leaching out of SO₃H group from the sulfonated carbon coated monolith surface. The leaching of active species reached a plateau state after fourth cycle.     

Modelling three-phase releases of carbon dioxide from high-pressure pipelines

This paper describes the development and experimental validation of a three-phase flow model for predicting the transient outflow following the failure of pressurised CO₂ pipelines and vessels. The choked flow parameters at the rupture plane, spanning the dense-phase and saturated conditions to below the triple point, are modelled by maximisation of the mass flowrate with respect to pressure and solids mass fraction at the triple point. The pertinent solid/vapour/liquid phase equilibrium data are predicted using an extended Peng–Robinson equation of state.The proposed outflow model is successfully validated against experimental data obtained from high-pressure CO₂ releases performed as part of the FP7 CO2PipeHaz project (www.co2pipehaz.eu).The formation of solid phase CO₂ at the triple point is marked by a stabilisation in pressure as confirmed by both theory and experimental observation. For a fixed diameter hypothetical pipeline at 100 bar and 20 °C, the flow model is used to determine the impact of the pipeline length on the time taken to commence solid CO₂ discharge following its rupture.     

Use of advance oxidation process to improve the biodegradability of olive oil mill effluents

In this study, recalcitrant total phenol (TPh) and organic matter removal were investigated at olive mill wastewater (OMW) in sequential Coagulation and Fenton system. This study focused on different operational parameters such as pH, H₂O₂, and Fe²⁺ dosages, and [Fe²⁺]/[H₂O₂] ratios. The optimum conditions were determined as; pH = 3; [Fe²⁺] = 2.5 g/L; [Fe²⁺]/[H₂O₂] = 2.5. A higher treatment efficiency was achieved at sequential Coagulation and Fenton system (COD, 65.5%) and TPh, 87.2%), compared to coagulation process (COD, 51.4%; total organic carbon (TOC), 38.6% and total nitrogen (TN) 52.1%). This study demonstrated that the Coagulation and Fenton process has a potential for efficient removal of phenolic pollutants from wastewater.     

Optimization of Innovative Ethanol Production from Wheat by Response Surface Methodology

A soft wheat variety has been tested as the raw material for fuel ethanol production via a novel processing route. The bran stream produced by the break section of a Buhler mill was used as the sole nutrient source in solid-state fermentation for the production of hydrolytic enzymes by two fungal strains, Aspergillus awamori and Aspergillus oryzae. Co-fermentation of the two fungi was largely problematic because of a significant difference between their growth rates. A mixture of the two enzyme solutions produced by separate cultivation of the two strains was effective for simultaneous starch and protein hydrolyses. Response surface methodology was used to design ethanol production trials using the flour hydrolysate as the only nutrient source by Saccharomyces cerevisiae. In a medium containing 150 g l⁻¹ glucose and 310 mg l⁻¹ free amino nitrogen, ethanol yield on glucose reached 50.7%, i.e., 99.2% of the theoretical conversion ratio, in 72 h. The yield of CO₂ from glucose was approximated as slightly higher than its theoretical yield due possibly to the availability of O₂ in the early fermentation stage. The overall production of 2-methyl-1-butanol, 1-propanol, 2-methyl-1-propanol and 3-methyl-butanol in all trials of yeast fermentation remained below 1000 ppm. Mass balance calculation concluded conversion ratios of 29.61% (w/w) ethanol and 23.74% (w/w) CO₂ from the wheat.