Analysis of in-cylinder hydrocarbons in a multi-cylinder gasoline HCCI engine using gas chromatography

Gasoline Homogeneous Charge Compression Ignition (HCCI) combustion has been studied widely in the past decade. However, in HCCI engines using negative valve overlap (NVO), there is still uncertainty as to whether the effect of pilot injection during NVO on the start of combustion is primarily due to heat release of the pilot fuel during NVO or whether it is due to pilot fuel reformation. This paper presents data taken on a 4-cylinder gasoline direct injection, spark ignition/HCCI engine with a dual cam system, capable of recompressing residual gas. Engine in-cylinder samples are extracted at various points during the engine cycle through a high-speed sampling system and directly analysed with a gas chromatograph and flame ionisation detector. Engine parameter sweeps are performed for different pilot injection timings and quantities at a medium load point. Results show that for lean engine running conditions, earlier pilot injection timing leads to partial oxidation of the injected pilot fuel during NVO, while the fraction of light hydrocarbons remains constant for all parameter variations investigated. The same applies for a variation in pilot fuel amount. Thus there is evidence that in lean conditions, pilot injection-related NVO effects are dominated by heat release rather than fuel reformation. © 2009 SAE International.

Numerical simulation of post-flame oxidation of hydrocarbons in spark ignition engines

About 50-90 percent of the hydrocarbons that escape combustion during flame passage in spark-ignition engine operation are oxidized in the cylinder before leaving the system. The process involves the transport of unreacted fuel from cold walls towards the hotter burned gas regions and subsequent reaction. In order to understand controlling factors in the process, a transient one-dimensional reactive-diffusive model has been formulated for simulating the oxidation processes taking place in the reactive layer between hot burned gases and cold unreacted air/fuel mixture, with initial and boundary conditions provided by the emergence of hydrocarbons from the piston top land crevice. Energy and species conservation equations are solved for the entire process, using a detailed chemical kinetic mechanism for propane. Simulation results show that the post-flame oxidation process takes place within a reactive layer where intermediate hydrocarbon products are formed at temperatures above 1100-1200 K, followed by a carbon monoxide conversion region closer to the hot burned gases. Model results show that most of hydrocarbons leaving the crevice are completely oxidized inside the cylinder. The largest contribution of remaining hydrocarbons are those leaving the crevice at temperatures below 1400 K. The largest fraction of non-fuel (intermediate) hydrocarbons results from hydrocarbons leaving the crevice when core temperatures are around 1400 K Copyright © 1997 Society of Automotive Engineers, Inc.

Development of a time and space resolved sampling probe diagnostic for engine exhaust hydrocarbons

In order to understand how unburned hydrocarbons emerge from SI engines and, in particular, how non-fuel hydrocarbons are formed and oxidized, a new gas sampling technique has been developed. A sampling unit, based on a combination of techniques used in the Fast Flame Ionization Detector (FFID) and wall-mounted sampling valves, was designed and built to capture a sample of exhaust gas during a specific period of the exhaust process and from a specific location within the exhaust port. The sampling unit consists of a transfer tube with one end in the exhaust port and the other connected to a three-way valve that leads, on one side, to a FFID and, on the other, to a vacuum chamber with a high-speed solenoid valve. Exhaust gas, drawn by the pressure drop into the vacuum chamber, impinges on the face of the solenoid valve and flows radially outward. Once per cycle during a specified crank angle interval, the solenoid valve opens and traps exhaust gas in a storage unit, from which gas chromatography (GC) measurements are made. The port end of the transfer tube can be moved to different locations longitudinally or radially, thus allowing spatial resolution and capturing any concentration differences between port walls and the center of the flow stream. Further, the solenoid valve's opening and closing times can be adjusted to allow sampling over a window as small as 0.6 ms during any portion of the cycle, allowing resolution of a crank angle interval as small as 15°CA. Cycle averaged total HC concentration measured by the FFID and that measured by the sampling unit are in good agreement, while the sampling unit goes one step further than the FFID by providing species concentrations. Comparison with previous measurements using wall-mounted sampling valves suggests that this sampling unit is fully capable of providing species concentration information as a function of air/fuel ratio, load, and engine speed at specific crank angles. © Copyright 1996 Society of Automotive Engineers, Inc.

Extent of oxidation of hydrocarbons desorbing from the lubricant oil layer in spark-ignition engines

The extent of oxidation of hydrocarbons desorbing from the oil layer has been measured directly in a hydrogen-fueled, spark-ignited engine in which the lubricant oil was doped with a single component hydrocarbon. The amount of hydrocarbon desorbed and oxidized could be measured simultaneously as the dopant was only source of carbon-containing species. The fraction oxidized was strongly dependent on engine load, hydrogen fuel-air ratio and dopant chemical reactivity, but only modestly dependent on spark timing and nitrogen dilution levels below 20 percent. Fast FID measurements at the cylinder exit showed that the surviving hydrocarbons emerge late in the exhaust stroke. © Copyright 1996 Society of Automotive Engineers, Inc.

A novel, sensitive potentiometric hydrocarbon sensor for high-vacuum applications.

A potentiometric device based on interfacing a solid electrolyte oxygen ion conductor with a thin platinum film acts as a robust, reproducible sensor for the detection of hydrocarbons in high- or ultrahigh-vacuum environments. Sensitivities in the order of approximately 5 x 10(-10) mbar are achievable under open circuit conditions, with good selectivity for discrimination between n-butane on one hand and toluene, n-octane, n-hexane, and 1-butene on the other hand. The sensor's sensitivity may be tuned by operating under constant current (closed circuit) conditions; injection of anodic current is also a very effective means of restoring a clean sensing surface at any desired point. XPS data and potentiometric measurements confirm the proposed mode of sensing action: the steady-state coverage of Oa, which sets the potential of the Pt sensing electrode, is determined by the partial pressure and dissociative sticking probability of the impinging hydrocarbon. The principles established here provide the basis for a viable, inherently flexible, and promising means for the sensitive and selective detection of hydrocarbons under demanding conditions.

Process envelopes for stabilisation/solidification of contaminated soil using lime-slag blend.

PURPOSE: Stabilisation/solidification (S/S) has emerged as an efficient and cost-effective technology for the treatment of contaminated soils. However, the performance of S/S-treated soils is governed by several intercorrelated variables, which complicates the optimisation of the treatment process design. Therefore, it is desirable to develop process envelopes, which define the range of operating variables that result in acceptable performance. METHODS: In this work, process envelopes were developed for S/S treatment of contaminated soil with a blend of hydrated lime (hlime) and ground granulated blast furnace slag (GGBS) as the binder (hlime/GGBS = 1:4). A sand contaminated with a mixture of heavy metals and petroleum hydrocarbons was treated with 5%, 10% and 20% binder dosages, at different water contents. The effectiveness of the treatment was assessed using unconfined compressive strength (UCS), permeability, acid neutralisation capacity and contaminant leachability with pH, at set periods. RESULTS: The UCS values obtained after 28 days of treatment were up to ∼800 kPa, which is quite low, and permeability was ∼10(-8) m/s, which is higher than might be required. However, these values might be acceptable in some scenarios. The binder significantly reduced the leachability of cadmium and nickel. With the 20% dosage, both metals met the waste acceptance criteria for inert waste landfill and relevant environmental quality standards. CONCLUSIONS: The results show that greater than 20% dosage would be required to achieve a balance of acceptable mechanical and leaching properties. Overall, the process envelopes for different performance criteria depend on the end-use of the treated material.

Comparison of stabilised/solidified mixes of model drill cuttings based on the North Sea and Red Sea Areas

Following the global stringent legislations regulating the wastes generated from the drilling process of oil exploration and production activities, the management of hazardous drill cuttings has become one of the pressing needs confronting the petroleum industry. Most of the prevalent treatment techniques adopted by oil companies are extremely expensive and/or the treated product has to be landfilled without any potential end-use; thereby rendering these solutions unsustainable. The technique of stabilisation/solidification is being investigated in this research to treat drill cuttings prior to landfilling or for potential re-use in construction products. Two case studies were explored namely North Sea and Red Sea. Given the known difficulties with stabilising/solidifying oils and chlorides, this research made use of model drill cutting mixes based on typical drill cutting from the two case studies, which contained 4.2% and 10.95% average concentrations of hydrocarbons; and 2.03% and 2.13% of chlorides, by weight respectively. A number of different binders, including a range of conventional viz. Portland cement (PC) as well as less-conventional viz. zeolite, or waste binders viz. cement kiln dust (CKD), fly ash and compost were tested to assess their ability to treat the North Sea and Red Sea model drill cuttings. The dry binder content by weight was 10%, 20% and 30%. In addition, raw drill cuttings from one of the North Sea offshore rigs were stabilised/solidified using 30% PC. The characteristics of the final stabilised/solidified product were finally compared to those of thermally treated cuttings. The effectiveness of the treatment using the different binder systems was compared in the light of the aforementioned two contaminants only. A set of physical tests (unconfined compressive strength (UCS)), chemical tests (NRA leachability) and micro-structural examinations (using scanning electron microscopy (SEM), and X-ray diffraction (XRD)) were used to evaluate the relative performance of the different binder mixes in treating the drill cuttings. The results showed that the observed UCS covered a wide range of values indicating various feasible end-use scenarios for the treated cuttings within the construction industry. The teachability results showed the reduction of the model drill cuttings to a stable non-reactive hazardous waste, compliant with the UK acceptance criteria for non-hazardous landfills: (a) by most of the 30% and 20% binders for chloride concentrations, and (b) by the 20% and 30% of compost-PC and CKD-PC binders for the Red Sea cuttings. The 20% and 30% compost-PC and CKD-PC binders successfully reduced the leached oil concentration of the North Sea cuttings to inert levels. Copyright 2007, Society of Petroleum Engineers.

PH-dependent leaching behaviour and other performance properties of cement-treated mixed contaminated soil

Portland cement has been widely used for stabilisation/solidification (S/S) treatment of contaminated soils. However, there is a dearth of literature on pH-dependent leaching of contaminants from cement-treated soils. This study investigates the leachability of Cu, Pb, Ni, Zn and total petroleum hydrocarbons (TPH) from a mixed contaminated soil. A sandy soil was spiked with 3000 mg/kg each of Cd, Cu, Pb, Ni and Zn, and 10,000 mg/kg of diesel, and treated with ordinary Portland cement (CEM I). Four different binder dosages, 5%, 10%, 15% and 20% (m/m) and different water contents ranging from 13%-19% dry weight were used in order to find a safe operating envelope for the treatment process. The pH-dependent leaching behaviour of the treated soil was monitored over an 84-day period using a 3-point acid neutralisation capacity (ANC) test. The monolithic leaching test was also conducted. Geotechnical properties such as unconfined compressive strength (UCS), hydraulic conductivity and porosity were assessed over time. The treated soils recorded lower leachate concentrations of Ni and Zn compared to the untreated soil at the same pH depending on binder dosage. The binder had problems with Pb stabilisation and TPH leachability was independent of pH and binder dosage. The hydraulic conductivity of the mixes was generally of the order, 10-8 m/sec, while the porosity ranged from 26%-44%. The results of selected performance properties are compared with regulatory limits and the range of operating variables that lead to acceptable performance described. © 2012 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences.

On the photoluminescence of a-C:H films

a-C:H films deposited from methane and helium mixture in a capacitively coupled rf plasma were found to show photoluminescence (PL) with peak intensities at energies far above the Taue gap of these films. Apart from the PL the films were investigated with respect to their IR and UV/VIS absorption properties as well as their Raman spectra were examined. The ultraviolet (UV) and blue luminescence from hard a-C:H thin films are explained by incorporation of polycyclic hydrocarbons from gas-phase reactions in the methane helium plasma into the film.

Cement-fly ash stabilisation/solidification of contaminated soil: Performance properties and initiation of operating envelopes

This study was aimed at evaluating the mechanical and pH-dependent leaching performance of a mixed contaminated soil treated with a mixture of Portland cement (CEMI) and pulverised fuel ash (PFA). It also sought to develop operating envelopes, which define the range(s) of operating variables that result in acceptable performance. A real site soil with low contaminant concentrations, spiked with 3000mg/kg each of Cd, Cu, Pb, Ni and Zn, and 10,000mg/kg of diesel, was treated with one part CEMI and four parts PFA (CEMI:PFA=1:4) using different binder and water contents. The performance was assessed over time using unconfined compressive strength (UCS), hydraulic conductivity, acid neutralisation capacity (ANC) and pH-dependent leachability of contaminants. With binder dosages ranging from 5% to 20% and water contents ranging from 14% to 21% dry weight, the 28-day UCS was up to 500kPa and hydraulic conductivity was around 10-8m/s. With leachant pH extremes of 7.2 and 0.85, leachability of the contaminants was in the range: 0.02-3500mg/kg for Cd, 0.35-1550mg/kg for Cu, 0.03-92mg/kg for Pb, 0.01-3300mg/kg for Ni, 0.02-4010mg/kg for Zn, and 7-4884mg/kg for total petroleum hydrocarbons (TPHs), over time. Design charts were produced from the results of the study, which show the water and/or binder proportions that could be used to achieve relevant performance criteria. The charts would be useful for the scale-up and design of stabilisation/solidification (S/S) treatment of similar soil types impacted with the same types of contaminants. © 2013 Elsevier Ltd.

Investigation of the dilution process for measurement of particulate matter from spark-ignition engines

Measurements of particulate matter (PM) from spark ignition (SI) engine exhaust using dilution tunnels will become more prevalent as emission standards are tightened. Hence, a study of the dilution process was undertaken in order to understand how various dilution related parameters affect the accuracy with which PM sizes and concentrations can be determined. A SI and a compression ignition (CI) engine were separately used to examine parameters of the dilution process; the present work discusses the results in the context of SI exhaust dilution. A Scanning Mobility Particle Sizer (SMPS) was used to measure the size distribution, number density, and volume fraction of PM. Temperature measurements in the exhaust pipe and dilution tunnel reveal the degree of mixing between exhaust and dilution air, the effect of flowrate on heat transfer from undiluted and diluted exhaust to the environment, and the minimum permissible dilution ratio for a maximum sample temperature of 52°C. Measurements of PM concentrations as a function of dilution ratio show the competing effects of temperature and particle/vapor concentrations on particle growth dynamics, which result in a range of dilution ratios-from 13 to 18-where the effect of dilution ratio, independent of flowrate, is kept to a minimum. This range of dilution ratios is therefore optimal in order to achieve repeatable PM concentration measurements. Particle dynamics during transit through the tunnel operating at the optimal dilution ratio was found statistically insignificant compared to data scatter. Such small differences in number concentration may be qualitatively representative of particle losses for SI exhaust, but small increases in PM volume fraction during transit through the tunnel may significantly underestimate accretion of mass due to unburned hydrocarbons (HCs) emitted by SI engines. The fraction of SI-derived PM mass due to adsorbed/absorbed vapor, estimated from these data, is consistent with previous chemical analyses of PM. © 1998 Society of Automotive Engineers, Inc.