Flash Point Determination Research Articles

Investigation of physical and chemical parameters of the raw hydrocarbon material base of Kaliningrad region for the concept development of an oil refinery

The article analyzes the factors that determine the necessity of oil refinery construction in the Kaliningrad region of the Russian Federation. The assessment of the existing and prospective raw material base is performed. The data for the development of the feasibility study for an oil refinery construction are formed and analyzed. Taking into account the outdated data on the parameters of hydrocarbon raw materials produced in the region, as well as significant changes in the raw material base due to the tendency to develop offshore, rather than continental, fields the physical and chemical parameters of the oil fields of the Kaliningrad region are investigated for the possibility of their further use in oil refining in order to obtain high-quality gasoline and diesel fuel. The laboratory studies of oil samples on viscosity, density, fractional composition, content of sulfur, chloride salts, mechanical impurities, water, and flash point determination are carried out on the basis of the Russian state standards. The different variants of the refinery layouts are analyzed, considering the available raw material base. Taking into account the initial data obtained, a preliminary pre-design study of the technological scheme and the refinery mass balance is carried out and presented in the article.

Estimating flashpoints of fuels and chemical compounds using hybrid machine-learning techniques

Flashpoint of organic materials is a crucial physical property in industrial applications and laboratory experiments, which provides information on safety standards and needed precautions in handling various organic materials. Proposed methods to determine the flashpoint of an organic material suffer from dependency on other physical properties of the chemical or demand complicated calculations which are time-consuming. In this work, a direct system model is proposed to anticipate the flashpoints of organic materials for a wide range of chemical compounds. The following models of genetic algorithm-adaptive neuro-fuzzy inference system, the least-squares version of the support vector machine, particle swarm optimisation-adaptive neuro-fuzzy inference system, and artificial neural network were applied to develop the model. This system model can speed up the flashpoint determination process and its accuracy. It can also anticipate the flashpoints of new organic materials. 79 functional groups were gathered to form a group contribution method to estimate the flashpoints of various chemical compounds. The functional groups were correlated with the model, known as the committee machine intelligent system, which performs accurately to prognosticate the flashpoint for every compound. 1,378 chemical compounds of different chemical categories were used to develop the model, making it suitable to estimate the flashpoints. This system model can determine or anticipate the flashpoints of organic materials with high accuracy and provide useful information for safety considerations in laboratory and industrial applications.

Uncertainty Measurement of Closed Flash Point of Organic Heat Carrier

The closed flash point is an important indicator in the detection of organic heat carrier. In this paper, based on the Pensky-Martin flash point (closed) measurement method, the closed flash point of the organic heat carrier is measured with an automatic closed cup flash point meter. The factors that may affect the accuracy of the measurement result during the measurement process are analyzed, and the uncertainty is determined. Through the analysis of the established uncertainty component sources, the repeatability measurement of the organic heat carrier, the temperature sensor, the pressure sensor, and the numerical rounding based on the standard, the results of the closed flash point determination of the organic heat carrier are obtained. The synthetic uncertainty and the relative expanded uncertainty are evaluated to improve the reliability of the measurement results of the closed flash point of the organic heat carrier and provide a reference for the quality control of the organic heat carrier.

Group contribution model based on decision tree algorithm for estimating flash point of pure organic compounds

ABSTRACT One of the well-known chemical properties which has wide applications in the determination of the amount of flammability and combustibility of various compounds is flash point. Due to difficulty and high cost of experimental determination of flash points, computational and modeling studies of this parameter have been highlighted. In this work, a new model based on Ensemble Boosted Trees (EDT Boosted) is used to anticipate flash point of pure organic compounds as a function of normal boiling point and molecular structure. A comprehensive dataset of 1660 flash points is utilized to assess EDT Boosted model visually and mathematically. The mathematical indexes including R-squared, root mean square error, mean squared error, mean relative error, and standard deviations are forecasted 0.997, 4.5469, 20.6743, 0.85729, and 3.7123 respectively. Additionally, the visual comparison of EDT Boosted outputs and real values of flash point shows our proposed algorithm has great capacity in the calculation of flash point. Finally, the comparison of the suggested algorithm and other approaches is carried out to introduce EDT Boosted algorithm as the best predictor tool for flash point determination.

Experimental Assessment of PAO and PAG Based Oil Performances in a Screw Compressor

The paper presents comparative results of an experimental assessment for behaviour and performances evolution of poly-alpha-olefin (PAO) and poly-alkyl-glycol (PAG) based oil, used in a natural gas screw compressor. Within such compressor type the oil is directly injected and has simultaneous multiple roles: lubrication, coolant, compressing and sealant. Taking into account the gas composition, the oil type used within the screw compressor directly influences its performances and life span. For a known composition of processed the gas, the PAO and PAG oil was used in the same compressor. Each type of oil has been monitored and specifically analyzed: flash point determination, cinematic viscosity measurement, FTIR analysis for contamination and usage determination. The literature highlights that a thorough monitoring and analyze of the oil is, in fact, one of the most important ways to assess the performances and usage of a screw compressor. Thus, many of the compressor maintenance problems can be identified and solved resulting the increase of its lifespan and decrease of the maintenance expenditures. The data have been centralized and a comparative analysis of PAO and PAG has been made, thus resulting the best solution for the specific problem encountered at the natural gas shaft.

Fluorinated Phosphorus-Based Compounds As Multifunctional Additives/Co-Solvents for Advanced Lithium-Ion Battery Electrolytes

In today’s society, the utilization of portable energy sources like lithium-ion batteries (LIBs) is of essential worth. However, LIBs still have certain limitations and bottlenecks addressed to nonaqueous aprotic electrolytes, as inevitable components for the operation of the battery.1 With this in line, state-of-the-art nonaqueous aprotic electrolytes (SOTA) reveal different challenges such as electrolyte decomposition and high flammability. One effective and cost favorable approach refers to the introduction of additives or co-solvents to the SOTA electrolyte.2-3 Hereby, the electrolyte decomposition can be minimized when increasing the cut-off potential (beyond 4.5 V vs. Li/Li+) that prevents the increased capacity fading of the battery. Furthermore, phosphorus (III and V) fluorinated or non-fluorinated compounds have been the subject of an investigation and can be featured as effective flame retardants.2-3 With the advance demand of energy in the last decades, an increase in the energy density, as well as an improvement in safety concerns are highly required for the advanced batteries, tailored for targeted application.2-5 In this work, several fluorinated cyclic phosphorus-based containing compounds were designed, synthesized and investigated as bifunctional - high-voltage and flame retardant – additives/co-solvent as electrolyte components for advanced LIB application. The selected molecules were correlated in respect to their structure-reactivity relationship and characterized by means of carefully selected physicochemical, electrochemical, analytical and structural methods. Furthermore, the influence of the fluorinated cyclic phosphorus-based additives/co-solvents on the overall performance of the graphite/NCM111 cells was studied. In addition, the flammability of electrolyte formulations were investigated. The results obtained from self-extinguishing time test (SET) and flash point determination, as well as TGA and DSC measurements were correlated to theoretical calculations to understand the mechanism of the combustion. This systematical approach allows to understand the structure-reactivity relationship of the selected compounds, their impact on the overall battery chemistry, performance and safety and helps, to further tailor the properties of electrolyte additives/co-solvents for specific application. 1 D. Gao, RSC Adv. (2015), 5, 17566. 2 K. Xu, Chem. Rev. (2004), 104, 4303. 3 K. Xu, Chem. Rev. (2014), 114, 11503. 4 S. S. Zhang, J. Power Sources (2006), 162, 1379. 5 M. Asif, Renew. Sustainable Energy Rev. (2007), 11, 1388.

Determination of flash point and Reid vapor pressure in petroleum from HTGC and DHA associated with chemometrics

Flash point (FP) and Reid vapor pressure (RVP) are physicochemical properties of crude oil that are used as safety and environmental parameters. In this paper, we propose a methodology for estimating the FP and RVP for crude oil by means of detailed hydrocarbon analysis (DHA) and high temperature gas chromatography (HTGC) associated with partial least squares (PLS) regression. These techniques were used due to their direct relationship to FP and RVP. We studied 107 crude oil samples (with an API gravity range of 11.4–54.0) collected from a Brazilian sedimentary basin. The curve data derived from these two techniques were merged to better describe the true boiling point curve. Using fusion information drawn from the two chromatographic techniques (DHA and HTGC), we estimated the flash point with an average error of 5.3 °C and a coefficient of determination of approximately 0.9. While the data fusion represents an information gain in the estimation of the flash point, for to estimate the Reid vapor pressure, the HTGC data are sufficient. The PLS regression generated the best Reid vapor pressure results, with an average error of 0.4 kPa and with a coefficient of determination of above 0.99.

Investigation on the dependence of flash point of diesel on the reduced pressure at high altitudes

The high altitudes of the plateau areas lead to a decreasing flash point temperature of liquid fuels due to the reduced ambient pressure. It indicates that liquid fuels suffer greater fire and explosion hazards at high altitudes. To reveal the dependence of flash point on reduced pressure at high altitudes, a series of field flash point determinations are performed at six different altitudes on the Qinghai–Tibet Plateau. The results show that flash point decreases nonlinearly with the reduced pressure, which is inconsistent with the current standards of flash point determination, where adopt a linear correction for the pressure effect on flash point. Taking diesel as an example, two methods, the Clausius–Clapeyron relation method and the LCR method, are proposed to predict the flash point of diesel under different pressures. The results show that the predictive accuracy of the two methods is similar, and both of the two methods give more accurate predictive flash point than the linear relationship. The Clausius–Clapeyron relation is validated to be able to expound the dependence of flash point of liquid fuels on reduced pressure. These two methods can complement each other. The Clausius–Clapeyron relation method is recommended when the accurate the phase-transition enthalpy is known, the LCR model is an available method when the phase-transition enthalpy is unknown or uncertain, especially for the complicated fuel mixtures.

Illuminating Flash Point: Comprehensive Prediction Models

Flash point is an important property of chemical compounds that is widely used to evaluate flammability hazard. However, there is often a significant gap between the demand for experimental flash point data and their availability. Furthermore, the determination of flash point is difficult and costly, particularly for some toxic, explosive, or radioactive compounds. The development of a reliable and widely applicable method to predict flash point is therefore essential. In this paper, the construction of a quantitative structure - property relationship model with excellent performance and domain of applicability is reported. It uses the largest data set to date of 9399 chemically diverse compounds, with flash point spanning from less than -130 °C to over 900 °C. The model employs only computed parameters, eliminating the need for experimental data that some earlier computational models required. The model allows accurate prediction of flash point for a broad range of compounds that are unavailable or not yet synthesized. This single model with a very broad range of chemical and flash point applicability will allow accurate predictions of this important property to be made for a broad range of new materials.

Determination of flash point and cetane index in diesel using distillation curves and multivariate calibration

Partial least squares regression (PLS) was used to predict flash point and cetane index of diesel using distillation curves (ASTM-D86). The low RMSEP values obtained, compared with other chemometric models based on spectrometric methods described in literature, and high correlation coefficients between reference and predicted values showed that PLS was efficient to determine flash point and cetane index. The model built contains diesel samples of different compositions, thus revealing the variety of fuel in the Brazilian market. Furthermore, the proposed method has two advantages: low cost and easy implementation, as it applies the results of a routine test to evaluate the quality of diesel.

Determination of diesel quality parameters using support vector regression and near infrared spectroscopy for an in-line blending optimizer system

This work demonstrates the application of support vector regression (SVR) applied to near infrared spectroscopy (NIR) data to solve regression problems associated to determination of quality parameters of diesel oil for an in-line blending optimizer system in a petroleum refinery. The determination of flash point and cetane number was performed using SVR and the results were compared with those obtained by using the PLS algorithm. A parametric optimization using a genetic algorithm was carried out for choice of the parameters in the SVR regression models. The best models using SVR presented a RBF kernel and spectra preprocessed with baseline correction and mean centered data. The obtained values of RMSEP with the SVR models are 1.98°C and 0.453 for flash point and cetane number, respectively. The SVR provided significantly better results when compared with PLS and in agreement with the specification of the ASTM reference method for both quality parameter determinations.

Thermal stability of UNEX/HCCD-PEG diluent FS-13

Phenyl trifluoromethyl sulfone (FS-13) is an inert diluent used in HCCD/PEG process for isolation and recovery of cesium and strontium from highly radioactive raffinate waste. There is no experimental data available in open literature describing pressurization due to the thermal decomposition of FS-13 at elevated temperatures. Experiments were conducted for determination of flash point and heating of FS-13 under pressurized closed-vent conditions in an adiabatic calorimeter. During adiabatic experiments, negligible pressurization was observed.

Experimental investigations of the effect of biodiesel utilization on lubricating oil tribology in diesel engines

Biodiesel is an alternative fuel derived from vegetable oils by modifying their molecular structure through a transesterification process. Linseed oil methyl ester (LOME) was prepared using methanol in the presence of potassium hydroxide as a catalyst. The use of LOME in compression ignition engines was found to develop a very compatible engine-fuel system with lower emission characteristics. Two identical engines were subjected to long-term endurance tests, fuelled by an optimum biodiesel blend (20 per cent LOME) and diesel oil, respectively. Various tribological studies on lubricating oil samples drawn at regular intervals from both engines were conducted in order to correlate the comparative performance of the two fuels and the effect of fuel chemistry on lubricating oil performance and life. A number of tests were conducted in order to evaluate the comparative performances of the two fuels such as density measurement, viscosity measurements, Flashpoint determination, moisture content determination, pentane and benzene insolubles, thin layer chromatography, differential scanning calorimetry, etc. All these tests were used for an indirect interpretation of the comparative performance of these fuels. The performance of biodiesel fuel is found to be superior to that of diesel oil and the lubricating oil life is found to be longer while operating the engine on biodiesel

Determination of flash point in air and pure oxygen using an equilibrium closed bomb apparatus

The standard closed testers for flash point measurements may not be feasible for measuring flash point in special atmospheres like oxygen because the test atmosphere cannot be maintained due to leakage and the laboratory safety can be compromised. To address these limitations we developed a new “equilibrium closed bomb” (ECB). The ECB generally gives lower flash point values than standard closed cup testers as shown by the results of six flammable liquids. The present results are generally in good agreement with the values calculated from the reported lower flammability limits and the vapor pressures. Our measurements show that increased oxygen concentration had little effect on the flash points of the tested flammable liquids. While generally regarded as non-flammable because of the lack of observed flash point in standard closed cup flash point testers, dichloromethane is known to form flammable mixtures. The flash point of dichloromethane in oxygen measured in the ECB is −7.1 °C. The flash point of dichloromethane in air is dependent on the type and energy of the ignition source. Further research is being carried out to establish the relationship between the flash point of dichloromethane and the energy of the ignition source.

Precision and Equivalence of Automatic and Manual Flash Point Apparatus

Abstract The flash point of a liquid material is used to classify whether the material is flammable or combustible. Historically, flash point determination has been done using manual flash point apparatus. However, the advent of automatic flash point apparatus, especially in the petroleum and related industries, brought about improved testing efficiency such that manual flash point determination is becoming the less preferred way of determining flash point. Three ASTM standard test methods, namely, D 56 “Flash Point by Tag Closed Cup Tester,” D 92 “Flash and Fire Points by Cleveland Open Cup,” and D 93 “Flash Point by Pensky-Martens Closed Cup Testers” are the most common test methods used in the various specifications and regulatory requirements for determining the flash point of materials. Three interlaboratory studies were conducted in 1991 to determine new precision values for the ASTM D 56, D 92, and D 93 flash point test methods, and to determine if the flash points obtained by the automatic apparatus are statistically equivalent to the flash points obtained by the manual apparatus in each of these three standard test methods. The pooled repeatability at a 95% confidence level for the D 56 flash point was found to be 1.1°C (manual) and 1.2°C (automatic) for flash points below 60°C; and 1.4°C (manual) and 1.6°C (automatic) for flash points at or above 60°C. The pooled reproducibility for D 56 at a 95% confidence level was found to be 4.1°C (manual) and 4.3°C (automatic) for flash points below 60°C; and 5.8°C (manual) and 5.1°C (automatic) for flash points at or above 60°C. For D 92, a repeatability at a 95% confidence level of 4°C (manual) and 8°C (automatic); and a reproducibility at a 95% confidence level of 13°C (manual) and 18°C (automatic), were obtained. The precision for D 93 was shown to be dependent on the flash point value, with a repeatability at a 95% confidence level of 0.032 X °C (manual) and 0.035 X °C (automatic), and a reproducibility at a 95% confidence level of 0.073 X °C (manual) and 0.078 X °C (automatic). Standard statistical evaluation tests were performed on the data for the three test methods. Essentially, no statistically significant differences were found between automatic and manual D 56, automatic and manual D 92, and automatic and manual D 93 flash point results. Thus, the interlaboratory studies of the three flash point test methods indicated that automatic flash point results are equivalent to manual flash point results.

Reference Verification Fluids for Flash Point Determination

Abstract The flash point of a liquid material is used to classify whether the material is flammable or combustible. 1,4-dimethylbenzene (p-xylene) has been used historically to verify the proper operation of different flash point test equipment. Because of the toxicity and low flash point value of 1,4-dimethylbenzene, an interlaboratory study was conducted to determine alternate flash point reference standards. This study reports the flash points of n-decane, n-undecane, n-tetradecane, and n-hexadecane using various flash point test methods. The flash points of these materials were found to be testmethod dependent because of the inherent differences in the various flash point test methods. The reported reference flash point values of these materials are now used to verify the proper operation of flash point test equipment in place of 1,4-dimethylbenzene.

A model for the calculation and the verification of closed cup flash points for multicomponent mixtures

AbstractRegulatory issues related to material safety have made the accurate measurement and/or prediction of flash points essential. The flash point is one of the major physical properties used to determine the fire and explosion hazards of a liquid. Flash points are used by virtually all governmental entities worldwide to define “flammable” and “combustible” materials for shipping and safety regulations.A model is described here for the calculation of closed cup flash points for multicomponent, single liquid phase, mixtures. The model is based upon rigorous vapor/liquid equilibrium calculations supplemented with information about the lower flammable limits (LFL's) and heats of combustion (ΔHc's) for the mixture's constituent components. The closed cup flash points predicted with this model are typically within ± 5°C of the experimentally reported values. Such a model is useful as a means of verifying experimental data and as a tool for screening product formulations prior to experimental flash point determination. The model should considerably enhance the safety evaluation portion of the product development cycle, thus leading to shortened product time‐to‐market cycles. While flash points calculated with this model are in excellent agreement with experiment, experimental determination is still encouraged for critìcal safety applications.

Standardized methods of testing flammability of plastics

AbstractThe paper is giving a survey of the most important standardized methods for testing flammability and relative parameters of plastics. The items described are dealing with the determination of flash point, heat resistance, burning behaviour. Some new drafts and projects of international standards are also mentioned.

Determination of flash point of petroleum fuel blends

This article presents empirical equations for the calculation of the lowest temperature at which vapors from a petroleum product will ignite momentarily upon the application of a small flame under specified conditions. Blending leads to a considerable decrease in the flash point of the blended fuel in comparison with the original residual fuel oil. The saturated vapor pressure of blends of the two types of fuel is determined by the compatibility of the fuels being blended. It is determined that for calculations, it is more convenient to use the difference between the flash points of the fuels being blended rather than the saturated vapor pressure.