2019 Posters

The following posters will be presented in the Exhibit Hall at the 2019 Gulf Coast Conference.

> View the 2018 posters.

Abstract # 103 - Poster - South Lobby

ILSAC GF-6: A New Level of Performance for Engine Oils to Meet Changing Fuel Economy and Emission Standards

Raj Shah - Koehler Instrument Company, Inc.
Cindy Klager - Koehler Instrument Company, Inc.
Christin Abraham - Stony Brook University

With the continued modernization and improvements being made in the automotive industry, a new level of performance is required for engine oils. Engines are being built to be more durable, while also being designed for better fuel economy and to meet higher emission standards. The current GF-5 engine oil standard does not meet all the new requirements, specifically those of the USA Corporate Average Fuel Economy (CAFE) which will require the average fuel economy to be 54.5 MPG by the year 2025. While oils with lower viscosities can meet these fuel economy requirements, the oil must also maintain the engine durability, hence the need for the GF-6 performance levels.

Along with performance needs, the engine testing needs have also undergone a lot of recent changes. Older engine tests have been replaced with updated versions and brand new tests have been developed that will all need to be accounted for in the ILSAC GF-6 specification. Because of the significant number of new tests and requirements the GF-6 standard has seen numerous delays and is not expected to be finalized until Q2 of 2020. This poster will go deeper into the needs for the new GF-6 specifications along with the reasons why it has taken so long to achieve.

Abstract # 104 - Poster - South Lobby

How Oil Companies can use EDXRF Technology to comply with the EPA Tier 3 Standard Requirement of Low Sulfur Fuel and other Key Applications

Raj Shah - Koehler Instrument Company, Inc.
Cindy Klager - Koehler Instrument Company, Inc.

Energy Dispersive X-ray Fluorescence (EDXRF) is a fast, simple, and non-destructive elemental analysis technique for the measurement of liquids, powders, and solids. It is widely applied throughout the petroleum industry: upstream at the well site, mid-stream at pipelines, storage facilities and blending operations, and down-stream at the refinery. In 2017, the US Environmental Protection Agency (EPA) implemented new regulations on the composition of fuel, which included changing the maximum allowable sulfur content from 30 parts per million (ppm) on an annual average basis down to 10 parts per million (ppm). With more stringent requirements, better tools and technology are needed to test the sulfur content of fuels, namely, gasoline and diesel. The EDXRF is the ideal analytical tool to accurately determine the sulfur content in fuel samples, conforming to not only ASTM D7220, but also meeting the requirements for the EPA Tier 3 program.

Furthermore, the EDXRF can be used to determine concentration of some elements such as manganese, lead, zinc, phosphorous, and calcium. The determination of manganese and lead content gives an indication of the anti-knock agent added to motor gasoline and Avgas to improve octane rating.  Whilst the determination of zinc, phosphorous, calcium, and sulfur give an indication of the antioxidant, and anti-wear agents in lubricating oils. This poster discusses the versatile application of the EDXRF which allows end-users to effectively ascertain correct results for this desired use, and conform to international testing standards.

Abstract # 105 - Poster - South Lobby

Recent Improvements for ASTM D86 Distillation Testing including the Development of a New Hydrocarbon Synthetic Standard

Raj Shah - Koehler Instrument Company, Inc.
Cindy Klager - Koehler Instrument Company, Inc.
Gary Lew - Spectrum Standards

ASTM D86 is the Standard Test Method for Distillation of Petroleum Products and Liquid Fuels at Atmospheric Pressure and has been used across the industry for decades. It is one of the oldest test methods under the ASTM D02 Jurisdiction and we are continuously looking for ways to improve the method. This poster will take a look at some of the most recent improvements and work being done to improve the precision, usability and overall robustness of ASTM D86.  

The ASTM D02 subcommittee on Volatility has launched a ruggedness study to begin testing new options for ASTM D86. With this study the committee hopes to eliminate the use of Mercury thermometers, which has been a widely discussed topic across ASTM D02, with Gallium thermometers. Another main goal of this ruggedness study is to test the newly developed Synthetic Reference Fluid. Currently toluene is used as a verification fluid for calibration and hexadecane is used at higher temperatures. The recently developed synthetic hydrocarbon standard will cover a wider range than what is currently being used. It is another goal of ASTM to harmonize standards with comparable international organization standards. In the case of ASTM D86 it is requested to harmonize it with the ISO 3405 test method for distillation. ISO recently conducted a study using higher level biodiesel blends (B30) which offered results that lie within the current precision statement. ISO will be adding distillate fuels containing up to 30% biodiesel to the scope of ISO 3405 which will also have to be taken into account during the study within ASTM in order to harmonize the methods. All of the aforementioned changes will bring overall improvements to the ASTM D86 test method.

Abstract # 107 - Poster - South Lobby

Recent Advances in Instrumentation for Viscosity Testing and a Comparative Analysis with Newly Developed Viscometry Instrumentation

Raj Shah - Koehler Instrument Company, Inc.
Philip Iaccarino - Stony Brook University
Onur Diri - Omnitek B.V.

Many petroleum products are tested for their viscosity, thus making viscosity testing an essential focus in our industry. Therefore, it is important to hold a high standard for the instrumentation used for viscosity testing. Recently, there has been a push to improve the viscosity instrumentation available in the market, to help simplify the testing procedure while maintaining accurate results. These new instruments are easy to use with automatic operations, produce accurate and consistent results, can test many samples per hour, can handle a wide variety of samples, use only a small amount of sample and cleaning solvent, and are manageable to service. Additionally, instrumentation using both Ubbelohde and Houillon tube designs has seen these improvements. These advances as well as recent changes in the ASTM methods are discussed in this paper. When considering ASTM methods, the newly developed instruments can be used for ASTM D445, ASTM D446, ASTM D2170, ASTM D2171, ASTM D2270, and ASTM D7279. Overall, the recent advances in viscosity instrumentation will serve our industry efficiently and effectively for years to come.

Abstract # 108 - Poster - South Lobby

A Review of Biodiesel Testing Specifications and their Use in Middle Distillate Fuels

Raj Shah - Koehler Instrument Company, Inc.
Philip Iaccarino - Stony Brook University
Kareem Mehdi - Stony Brook University

When considering middle distillate fuels, biodiesel is a good alternative as a result of its carbon neutral footprint, sustainability, and economic viability. Recently, there has been improvements in biodiesel quality testing, by developing better test methods. Without sufficient testing, biodiesel can create various issues when used as a fuel, such as engine clogging. One of such test methods is ASTM D6751, the Standard Specification for Biodiesel Fuel (B100) Blend Stock and Distillate Fuel. This specification sets requirements for B100 fuels, which must be tested in accordance with various test methods.

ASTM D6751 is an important method for biodiesel fuels since biodiesel production and consumption is growing in the United States, and the test method ensures that the biodiesel meets the consumer’s standards. With growing concerns of climate change and an increasing demand for fuel sources, biodiesel will be seen as a more tasteful fuel alternative for years to come. This poster will discuss the current state of biodiesel in the fuel market, and will review the significance requirements and recent changes of the various biodiesel test methods referenced in ASTM D6751.

Abstract # 109 - Poster - South Lobby

Vapor Pressure Measurement Technology: Analysis of the effects of Temperature on Vapor Pressure for Various Oil Samples

Raj Shah - Koehler Instrument Company, Inc.
Tom Karis - TEK Data Systems
Philip Iaccarino - Stony Brook University

Vapor pressure is a property that is commonly tested for in the petroleum industry. In recent years, instrumentation to test for vapor pressure has seen some tremendous developments, which greatly improve the testing procedure. These new instruments align with ASTM D5191 and ASTM D6378, utilize automated procedures and only require small amounts of sample. By revolutionizing the vapor pressure testing field, the recently developed instruments have become the new standard for vapor pressure testing.

Making use of the new instrumentation, the effects of temperature on the vapor pressure of a sample can be studied rapidly and accurately. Generally, as the temperature of a sample increases, the vapor pressure also increases. The degree of the vapor pressure increase varies depending on the properties of the sample: its molecular weight and chemical composition are two of these properties. This poster will use one of these recently developed vapor pressure instruments to measure the vapor pressure of various oil samples, and will analyze the changes across a temperature range for those samples. The paper will also discuss thermodynamic characterization of base oil viscosity and vapor pressure.

Abstract # 110 - Poster - South Lobby

Evaluation of a Piston Ring Coating on the Oscillation Wear and Friction with use of Unique Pre-Screening SRV Instrumentation

Raj Shah - Koehler Instrument Company, Inc.
Philip Iaccarino - Stony Brook University
Vincent Colantuoni - Koehler Instrument Company, Inc.

In an engine, the piston group accounts for approximately 50% of frictional losses, contributing to significant fuel inefficiencies. With market demands for higher and higher fuel performances, the piston ring only increases in its load. With the use of a cost-effective Schwing, Reib, Verschleiss (SRV) instrument, the friction, wear, and load carrying capacity can be pre-screened, to determine which components perform better in an engine. By further understanding the piston-cylinder-contact assembly, engineers and scientists can further improve the piston ring and cylinder liner interaction.

The recently advanced SRV laboratory technique can also be used as a tool to study and solve various tribological problems. It is a diverse model for evaluating the friction and wear properties of greases, lubricants, coatings, additives, and other materials. Additionally, the SRV instrument is in compliance with many ASTM, ISO, and DIN testing standards. As a result of its versatile application, the SRV has the ability to be implemented in many practical setups. This paper will dwell into detail of how this technique can be used for evaluating a variety of piston ring coatings.

Abstract # 119 - Poster - South Lobby

Eco-based Lubricants and Greases: A Study that Looks at both Sides of the Coin

Raj Shah - Koehler Instrument Company, Inc.
Henry Takizawa - Koehler Instrument Company, Inc.

The importance of environmentally sustainable products has become paramount in recent years due to the adverse effects of climate change on our environment. As more and more countries push for legislation regulating the use of fossil fuels and their related byproducts, it has become a challenge for companies within these industries to find eco-friendly alternatives to fossil fuels that provide the same quality of product and are also economically viable. The research conducted for this paper will be used to discern the advantages and disadvantages of bio-lubricants and to ultimately determine if they can be used as a viable substitute to conventional mineral based lubricants. While this may seem like a subject that has been well studied, there are always pros and cons related to a sea change and moving to biolubricants and greases in lieu of conventional products is no exception. In this paper we will evaluate both sides of the coin, looking at the real versus perceived environmental benefits, potential applications, and means of production surrounding vegetable oil based lubricants ( and greases ) to see if they are really sustainable processes. We will also study the applicability of these biobased lubricants in the conditions and environments where conventional lubricants are commonly used and see how they perform.

Abstract # 120 - Poster - South Lobby

Gas-to-Liquids: The Future of Fuel Technology or a Mere Pipe Dream

Raj Shah - Koehler Instrument Company, Inc.
Anson Law - Koehler Instrument Company, INC

The process of gas-to-liquids, GTL, converts natural gases into useful hydrocarbon liquids such as diesel and gasoline through catalysis. GTL process is accomplished by first converting natural gas to synthetic gas through partial oxidation, CH­4+½O2→CO+2H2­, and then to liquid hydrocarbons using a catalyst. At first glance, this process is more environmentally friendly and produces superior quality products compared to using crude oil. However, the uncertainty of large-scale production and investment risks due to high estimated capital costs leaves GTL in doubt. In this paper, we will study the pros and cons of the fuel produced by the GTL process compared to using crude oil with regards to their quality, environmental benefits, and viability/profitability. Looking at both sides of the coin, we will discuss in detail whether GTL is a reliable, profitable, and pragmatic method to supply world’s energy needs.

Abstract # 122 - Poster - South Lobby

Development of a screening method using a translatory oscillation tribometer (SRV®) to test extreme pressure and anti-wear properties of gear oils

Raj Shah - Koehler Instrument Company, Inc.
Cindy Klager - Koehler Instrument Company, Inc.

Gear Oils are used in a wide range of applications and depending on the application, different performance factors of the lubricant are important and must be evaluated. For many applications, including industrial machinery and automotive driveline components, it is ideal to have an antiscuff gear lubricant, or an extreme pressure (EP) type of lubricant. These types of lubricants typically have additives to enhance their load-carrying capacity making them ideal for heavy load, slow speed conditions.

Testing the scuffing load and extreme pressure properties of a gear oil is not a simple test. A test rig was developed by FZG (the Technical Institute for the Study of Gears and Drive Mechanisms of the Technical University in Munich, Germany) to measure the scuffing load capacity of lubricants as per ISO 14635. While this test provides vital information in regards to scuffing load, it is a very expensive and time consuming test to run and is not feasible to test every gear oil formulation that one might need. To help narrow down which gear oils should be tested using the FZG rig, a test was developed using the Translatory Oscillation Tribometer (SRV®) to screen gear oils and in addition, give complementary information by measuring the coefficient of friction, wear scar, and load carrying capacity.

The SRV® Tribometer is an invaluable tool for evaluating friction and wear properties which can now be applied to EP and Anti-wear (AW) testing of gear oils. The method used is based on DIN 51834-4 and is done on a translatory oscillation tester equipped for parallel movement. The results of the EP and AW tests on the SRV test rig are able to help characterize and differentiate gear oils in minimal time. The results are a good indication of how the lubricant will behave and serve as a pre-screener to determine which oils should go on for further bench tests and field use. In addition to the pre-screening results, this method will also yield results of coefficient of friction, wear volume and estimations for the load carrying capacity. This poster will show how the tests were developed, how the results compare to the FZG test and how the SRV can be used to provide a meaningful evaluation of gear oils.

Abstract # 125 - Poster - South Lobby

Study of the ROBO Oxidation Test Technique and Instrumentation: Current and Future Potential for use with Upcoming Oil Specifications

Sarjeel Zaman - Koehler Instrument Company
Raj Shah - Koehler Instrument Company
Vincent Colantuoni - Koehler Instrument Company

With an increasing demand for superior emission and fuel economy standards in modern engines, the automobile industry must be prepared to supplement these changes with the development of higher performance engine oils. Before an engine oil can be introduced to the consumer market, however, the oil must undergo significant testing for several properties, according to standards set by the American Petroleum Institute (API) and International Lubricant Standardization and Approval Committee (ILSAC). One such property is the oil’s viscosity at low temperatures, which may cause catastrophic engine failure from poor pumpability and deposit formation.

The Romaszewski Oil Bench Oxidation (ROBO) test, developed for the API SN and ILSAC GF-5 specification, is a strong alternative to the Sequence IIIGA test that has long been used to evaluate cold-temperature viscosity of an aged oil. The ROBO test is able to duplicate the oil aging mechanism of Sequence IIIGA test results in a fast and cost-effective manner, while allowing for the assessment of oil viscosity with several other test methods. This paper is an attempt to be a comprehensive literature review on the work done on the ROBO test method so far. This paper will therefore take a close analysis into the development and applications of the ROBO test, as well as present a comparison with the Sequence IIIGA test method. We will discuss the various advantages and any possible drawbacks regarding the use of ROBO. We will also discuss the current and future potential of the ROBO test, including its use in the development of future oil specifications such as ILSAC GF-6.

Abstract # 127 - Poster - South Lobby

Development of a New Instrument and Test Technique to Study Low Temperature Mobility of Lubricating Greases

Stefan Lim - Koehler Instrument Company
Raj Shah - Koehler Instrument Company
Vincent Colantuoni - Koehler Instrument Company

Greases are primarily used to increase the mobility of an object against another. The viscosity of grease becomes high enough at low temperatures where it congeals and stops flowing. Currently, a few experimental techniques, such as the US Steel Grease Mobility, the Lincoln Ventmeter, and the Apparent Viscosity of Lubricating Greases (ASTM D1092) Methods are used to study low temperature properties of greases. DIN Method 51805, also called the Kesternich Method, has been used in Europe to gain a better understanding of low temperature properties of greases. In this paper, we study the development of a new instrument and procedure akin to the Kesternich Method. We evaluate a wide range of greases and compare their low temperature properties with the newly developed instrument and attempt to generate a new test procedure along with repeatability for this technique.

Abstract # 128 - Poster - South Lobby

Tribological Performance Testing of Industrial Greases

Vincent Colantuoni - Koehler Instrument Company, Inc.
Raj Shah - Koehler Instrument Company, Inc.
Gregor Patzer - Optimol Instruments

The diversity of lubricating grease species, each with their own complexity and philosophy, raises the demand for the diversification of existing screening methods even in model testing. This article presents an overview of existing standard methods as well as application-oriented testing procedures, which can be used for evaluating friction, wear, and extreme pressure properties of lubricating greases in a model tribometer. For lubricant developers, the SRV® technology platform offers not only testing according to the established test methods and relevant standards, but also the possibility of testing new products in application-oriented load situations. The testing according to standards can be used as a screening test for the grease chemistry and the flow properties of the grease sample. However, it reflects the potential real-life operating conditions of a product in only a very limited way. This poster will present test scenarios for such application-oriented friction and wear tests through a few selected examples: (1) effect of wear particles on the lubricity of a lubricating grease; (2) high temperature fretting behavior of industrial greases; and (3) simplified examination of rolling/sliding friction of high performance greases that can be used as a FE8/FE9 rolling bearing prescreening test.

Abstract # 129 - Poster - South Lobby

Quantitation of Biofuel Components in Jet Fuel Using GCxGC-TOFMS with a New Flow-based Modulator

Christina Kelly - LECO Corporation

As the trend toward “greener,” renewable biofuels becomes more prevalent, concerns over pipeline cross-contamination and mixing are addressed through more rigorous analytical testing. For jet fuels, especially, regulated methods like IP585 and ASTM D7974 respectively address the accurate quantitation of fatty acid methyl esters (FAMEs), which impact jet fuel freezing points and can cause fuel gelling to occur, and determination of specific hydrocarbons in synthesized iso-paraffins (SIP) used for blending with jet fuel. Utilizing two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GCxGC-TOFMS), methods for determination of FAMEs and SIP hydrocarbons using a new diverting flow modulator have been developed.

Abstract # 130 - Poster - South Lobby

Petroleum Biomarkers Around the World: Fingerprinting Crude Oils

Christina Kelly - LECO Corporation

The type and concentration of different hopane and sterane structures can provide unique identifiers for specific oil sources. Crude oil samples collected from different continents are compared using a comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry system (GCxGC-TOFMS) equipped with a new, robust, and easy-to-use flow-based modulator. Resolution of multi-ringed hopanes and steranes from straight-chained and branched alkanes is achieved using the power of a second dimension of chromatographic separation. Using TOFMS with better-than-nominal mass resolution allows for more confident differentiation of each biomarker, providing the option for matching full mass range spectra to both commercial and user-generated spectral libraries. 

Abstract # 133 - Poster - South Lobby

Comprehensive two-dimensional gas chromatography with Orbitrap mass spectrometry applied to flavor and fragrance analysis

Xin Zheng - Thermo Fisher Scientific
Jason Cole - Thermo Fisher Scientific
Matthew Edwards - SepSolve

High Resolution/Accurate Mass (HRAM)  mass spectrometry (MS) has become a popular detector for GCxGC as it provides full-scan analysis with high-quality mass spectra and excellent sensitivity and selectivity, especially for trace level detections. Orbitrap mass spectrometry is superior to detect low concentration unknowns and elucidate their chemical formula with sub ppm mass accuracy and extremely wide dynamic range, which dramatically increases confident identification. In this study, an HRAM Orbitrap analyser was coupled with a GCxGC using reversed flow modulation for flavor and fragrance analysis. Different subtypes of lavender oils were analyzed. The complex matrices and coelution are significant challenges for one-dimensional (1D) GC-MS. Diverse structurally similar isomers can be still problematic even HRAM mass spectrometry is applied due to the exact same masses for both molecular and fragment ions. The flow-modulated GCxGC-Orbitrap MS can effectively address this issue and separate multiple chemical classes such as monoterpenes, sesquiterpenes and oxygenated terpenes that co-eluted in one-dimensional separation. Excellent mass accuracy over a wide dynamic range was achieved as well.

Abstract # 134 - Poster - South Lobby

The implementation of the newly devised Analytical Performance Value (APV) methodology to assess the performance capabilities of laboratory instruments, specifically for the petroleum industry

Raj Shah - Koehler Instrument Company, Inc.
George Gonzalez - Agilent Technologies
Philip Iaccarino - Koehler Instrument Company, Inc.

 A need for the simplified review of method performance capability based on precision statement is required for commercial analytical instruments. A simplified applied statistical approach would benefit and assist laboratory managers, process engineers, commercial traders, lab chemists, lab technicians and operators. The numerical expression rating system based on performance relative to two or more points within the operating value of each parameter is defined in any standard method containing full precision, and is defined as repeatability and reproducibility. A process and computational expression is described and defined as analytical performance value (APV).  

This newly devised performance value would be contained in any standard method for use as a quantitative evaluation of test method performance. The proposed technique is to define a systematic method which provides for establishing an analytical performance value based on precision criteria relative to parameter measurements. The APV can be expressed as a scaled value percentage, which can then be used to assess acceptability and capability of the instrument or test method. This poster discusses the derivation of the APV methodology and analyzes two examples from the oil and gas industry of a repeatability and reproducibility assessment by applying the APV technique to these two ASTM methods. 

Abstract # 136 - Poster - South Lobby

The Application of Ion-mobility Enabled Mass Spectrometry to Distinguish Between Commercial Lubricant Oils.

Jeff Goshawk - Waters
Eleanor Riches - Waters
Gordon Jones - Waters
Caitlyn Da Costa - Waters

Lubricant oils are used in many commercial settings, from the automotive and aerospace industries, to oil well drilling rigs, to specialist metalworking machinery; in fact, lubricant oils may be present in any application where surfaces might contact one another and friction become a problem.  Many different formulations of lubricant oils are manufactured to address their wide range of uses.

High resolution mass spectrometry enables the accurate mass measurement of ions from which molecular information may be derived. The specificity of the approach is further enhanced by ion-mobility which provides information related to the size, shape and charge of the ions.

A simple workflow, combing ion-mobility with high resolution mass spectrometry followed by statistical analysis of the acquired data, is presented. This technique is used to discover differences between five automotive lubricant oils at the molecular level. This approach could be used to compare similar products, understand the differences between poorly and correctly performing oils, or deformulate competitors’ products.

Abstract # 137 - Poster - South Lobby

Group-Type Analysis of Petroleum Products by GC × GC using Complementary GC Column selectivity

Ramkumar Dhandapani - Phenomenex
Timothy Nelson - Phenomenex
Laura McGregor - SepSolve Analytical
Matthew Edwards - SepSolve Analytical
Aaron Parker - SepSolve Analytical

Precise characterization of petroleum-derived fuels is important for the oil industry and environmental monitoring alike. However, it is a tedious and difficult task to identify each of the thousands of individual components present in these complex samples. Group-type analysis using comprehensive two dimensional gas chromatography (GC×GC) offers significant advantages over conventional chromatography, with its vastly expanded separation space and the added benefit of highly structured groupings of compounds for simple classification of hydrocarbons. To separate complex species by GC×GC, it is essential to have a highly efficient column dimension and a complementary column selectivity. High temperature resistance and flexibility of the GC column tubing are an added advantage for GC×GC. In addition, complementary selectivities like Zebron ZB-1HT Inferno, which is a non-polar 100% dimethypolysiloxane based stationary phase and Zebron ZB-50, which is a higher-polar 50% phenyl phase, offer improved separation for group type analysis. Here we demonstrate the use of reverse fill/flush flow modulation with complementary set of column chemistry for robust, repeatable and affordable GC×GC, combined with simple, yet effective, data processing workflows for group-type analysis

Abstract # 138 - Poster - South Lobby

Cis-Trans FAMEs in Fuels by GC and GCxGC using Zebron® ZB-FAME GC Column

Ramkumar Dhandapani - Phenomenex
Timothy Nelson - Phenomenex
Nicholas Snow - Seton Hall University
Anumeha Muthal - Seton Hall University

 Fatty Acid Methyl Esters (FAMEs) are a big threat in aviation fuels as well as in biofuels. Accurate quantitation and separation of cis-trans in the lower and higher boiling FAMEs is essential from a quality control perspective, as well as from a safety perspective. In this presentation, a Zebron ZB-FAME GC column is utilized to accurately characterize FAMEs in Fuels by GC-MS. Traditional selectivity, like a 100 % polyethylene glycol phase, may only have a few coelutions of FAMEs, while the ZB-FAME GC column coupled with a mass spectrometry based detection will provide an excellent separation of cis and trans FAMEs along with lower level detection. Traditional higher cyano phase selectivities take an hour to separate cis-trans FAMEs, while the ZB-FAME can separate them within 11 minutes. This approach was also extended to a GCxGC using a ZB-FAME in the first dimension and a 5 % phenyl selectivity in the second dimension which together provide a detailed orthogonal separation. Thus, an analysis of fuels by GC-MS and GCxGC using ZB-FAME assures the safety in aviation fuels.

Abstract # 139 - Poster - South Lobby

Detailed Hydrocarbons Analysis of Fuel by using High Efficient Column Dimensions

Ramkumar Dhandapani - Phenomenex
Timothy Nelson - Phenomenex

There are hundreds of chemical components in spark ignition fuels, and so to make the testing and regulation manageable they are measured in categories by chemical group-type. These category group-types are based on molecular similarities that give them common performance behaviors. These tests are referred to as Detailed Hydrocarbon Analysis (DHA) which includes several test methods that measure different hydrocarbon subset or group-type categories. DHA identifies the important individual components in spark ignition fuels and other refinery light hydrocarbon process streams. Common refinery naphthas are virgin, alkylate, reformate, FCC and Coker, and finished spark ignition fuels. This technique is also referred to as PONA, PIONA, or PIANO analysis since specific test methods are measuring the group-type paraffins, isoparaffins, olefins, naphthenes, aromatics, and oxygenates. The DHA analysis helps optimize the production processes in addition to meeting the regulatory requirements. In this study, ZB-DHA-PONA is utilized for group type separation. It’s unique Engineered Self Cross-linking™(ESC) stationary phase provides low bleed and exceptional column life, extreme deactivation of the fused silica provides sharp peaks for polar and non polar compounds and the stationary phase is a true boiling point based separating phase. All these features provides the benefit of optimal separation of DHA critical pairs with symmetric peaks. Columns are available in high efficient dimension and are designed and Tested for Detailed Hydrocarbon Analysis. They provide excellent response and Peak Symmetry for Polar Oxygenates, suitable for DHA, PONA, PIONA, PIANO, and ASTM Methods (D5134, D5441, D5501, D6729, D6730, D6733).

Abstract # 141 - Poster - South Lobby

Application of GC×GC-VUV and GC×GC-FID for the analysis of common gasoline samples, middle distillates and crude oil distillation cuts

Ramkumar Dhandapani - Phenomenex
Dr. Max Jennerwein - ASG Analytik-Service
Dr. Thomas Wilharm - ASG Analytik-Service
Dr. Markus Eschner - ASG Analytik-Service
Timothy Nelson - Phenomenex

Comprehensive two-dimensional gas chromatography has made its way to lab routine for several years now. One of the most frequent utilizations of this instrumentation is the analysis of middle distillates like diesel fuel, heating oil or jet fuel. In most cases GC×GC technique is achieved by thermal modulation and FID or mass spectrometry for detection. An alternative is provided by flow modulation, a reliable modulation for a broad temperature range without consumption of LN2. This makes it an optimal instrument for the analysis of gasoline samples. The analysis of gasoline is usually accomplished following the European standard DIN EN ISO 22854, ASTM D6839, respectively. Up to now, there is only one manufacturer supplying an analytical instrument that complies with these standards. Moreover, high concentration of e.g. methanol, which is coming up in some countries, is not covered by these standards and there are no precision statements therefore. Deviations from the common composition of gasoline can be problematic or even harmful to the applied instrument (e.g. high amounts of MeOH, EtOH, H2O or high boilers). Therefore a more detailed insight in the composition is not possible. Now, a promising new technique can be reported, which is described by ASTM D8071. This analytical method applies GC-Vacuum Ultraviolet detection (GC-VUV) for the quantitative determination of the content of n-paraffins, iso-paraffins, olefins, naphthenes, aromatics and oxygenates in common gasoline. In addition, it is possible to detect and identify di-olefins with unconjugated and conjugated double bonds. In the presented work, the application of GC×GC –VUV and a possible transition to GC×GC –FID were tested. The hyphenation of both techniques results in a powerful new analytical method. Although, at the current state of the software, it is not possible to exploit the full potential, it is obvious what these techniques provide for the future. For the analysis of gasoline, this technique will overcome the weakness of both instruments. Low concentrated analytes like di-olefins can clearly be identified using VUV detection and the increased sensitivity  can be achieved from the two-dimensional GC separation.

Abstract # 143 - Poster - South Lobby

Orthogonal Selectivity for Separation of oxygenated compounds and hydrocarbons in alternative fuels by 2D GC using Zebron® ZB-1701™ and ZB-1™ GC Columns

Ramkumar Dhandapani - Phenomenex
Timothy Nelson - Phenomenex
Badaoui Omasi - Phenomenex

The need to diversify energy sources in the transportation field has sparked great interest in direct coal liquefaction products. Before processing, these liquids properties and compositions are far from fuel specifications and upgrading must be applied to the gas oil cuts. In fact, they consist mainly of aromatic hydrocarbons, cyclic alkanes (naphthenes), and heteroatomic compounds, especially oxygenated species. To consider their co-refining with petroleum cuts, it is crucial to study their chemical and physical properties. Apart from the hydrocarbons, the requirements in terms of molecular characterization improvement concern oxygenated compounds which belong to many different chemical families and are present in relatively high concentrations before hydrodeoxygenation (HDO).  Multidimensional Gas Chromatography has never been at stake to surmount this challenge. Yet, this powerful tool allows the analysis of complex samples and offers a high peak capacity by combining two different stationary phases with different separation mechanisms. Results obtained using GC×GC-FID enabled to unravel molecular structures of oxygenated compounds in a coal-derived middle distillate. It shows that oxygenated structures mainly consist in phenolic compounds. Compared to conventional configurations, a reversed configuration involving a highly polar column in the first dimension and a non-polar one in the second enables the separation of oxygenates but also hydrocarbons in one single run. In fact, 2D contour plots obtained in these conditions exhibit good resolution and high space occupation. Nevertheless, nitrogenates elute in the same zone as oxygenates and a proper quantification is therefore hardly reachable. Limitations of GC×GC can also be overcome by using a multi-technical analytical approach involving sample preparation or fractionation.

Abstract # 150 - Poster - South Lobby

Carbon, Hydrogen and Nitrogen in Petroleum Products and Lubricants according to ASTM 5291 by an automatic elemental analyzer

Liliana Krotz - Thermo Fisher Scientific

Elemental analysis is fundamental in petroleum chemistry. The official method for carbon, hydrogen and nitrogen analysis in petroleum products and lubricants, based on combustion, is described in ASTM D5291.  Using the Test Method D levels of 0.01 N% in lubricants can be determined. The FlashSmart Elemental Analyzer permits the simultaneous determination of CHN. The analyzer is equipped with two independent furnaces allowing the installation of two analytical circuits which are used alternatively and automatic through the Multi Valve Control Module. This paper presents CHN data of petroleum products and lubricants to evaluate the accuracy, precision and repeatability of the data.

Abstract # 169 - Poster - South Lobby

Enhanced Stability performance test of Total Sulfur Content in Diesel Fuel Samples According ASTM D5453

Anne Jurek - EST Analytical

ASTM Method D5453 is commonly used to determine total sulfur in liquid hydrocarbons.  The boiling range of these hydrocarbons can vary from 25 to 400ºC.  This method calls for the sample to be directly injected or placed in a sample boat and then inserted into a high temperature tube for combustion where the sample is oxidized into sulfur dioxide (SO2).  The sample is exposed to ultraviolet light and detected by a photomultiplier.  This application will examine the total sulfur content of diesel fuel samples using the NexiS Total Nitrogen/Total Sulfur combustion analyzer.

Abstract # 186 - Poster - South Lobby

Determination of Low Level Nitrogen and Sulfur In Light Aromatic Hydrocarbons

Anne Jurek - EST Analytical
Kelly Cravenor - EST Analytical
Doug Meece - EST Analytical

In 2000, the EPA implemented the Tier 2 Gasoline Sulfur program.  This program reduced the allowable sulfur content in gasoline to 15ppm and NOx content to 0.07g/mile.  The Tier 2 program was initiated out of the Clean Air Act requirement of the Environmental Protection Agency.  In 2017, a Tier 3 program was applied requiring even lower sulfur and nitrogen content in gasoline and diesel.    The new emission standards combined with the lowered sulfur content will reduce much of the toxic emissions including nitrogen oxides from motor vehicles.  Due to these new regulations there is a need for better analysis of low level Nitrogen and Sulfur.