“Trace Analysis of Acetaldehyde and Methanol in Polymer Grade Olefins”
Clarence S Wentzel - Arnel Inc., Ray Tuohy - ExxonMobil Chemical Company Arnel Inc.

The authors describe the development of a gas chromatographic method for the analysis of trace levels of acetaldehyde and methanol in polymer grade olefins. Polymer grade propylene and butadiene have demanding purity specifications to ensure catalytic process optimization and product yields. Gas chromatography has been the traditional discipline to separate and quantify these impurities. The application of a single, direct chromatographic solution to enable both acetaldehyde and methanol to be determined in both matrices is very desirable. This paper describes a parallel method development project that included both packed and capillary columns integrated into a PerkinElmer AutoSystem XL gas chromatograph. The use of a PreVentTM adapter with valveless backflush to accelerate the analysis is considered in the capillary work. The development path and virtues of each system are discussed. Sampling considerations, chromatographic application, detector optimization, sample types, and precision are presented.

“Detailed Hydrocarbon Analysis of Heavy Distillation Fractions”
Clarence S Wentzel, Mark R Taylor - Arnel Inc. Arnel Inc.

We describe a high-resolution gas chromatographic analysis of intermediate and heavy distillate fractions employing selective prefractionation. The speciated separations are inclusive to C12 with higher boiling compounds backflushed to vent. Standard methods developed by the ASTM and other organizations are limited in scope due to the inability of long, narrow bore columns to elute high boiling materials. The application of a precolumn and valveless backflush using a PreVentTM adapter permits the analysis of samples through the heavy distillate range. A programmable pneumatic controller and mid-point pressure changes allow the sample to be fractionated and backflushed from the precolumn at selectable intervals. Construction, column selectivity, operational parameters and sample analyses are presented.

“A Rapid NMR method to Determine Additives in Polymers”
Harry Xie, Alison Barrett - Bruker Optics, Inc.

Many polymer plants require a check of the additive content every ten minutes in production to guarantee a quality product. Conventional solvent methods take hours to deliver measurement results. As such people are constantly searching for analytical methods that require no sample preparation, no solvents and a short analysis time. The minispec NMR method for additive determination is an ideal solution for the polymer industry. This paper will cover the essential background knowledge of Time Domain NMR and its industrial applications. The details of the additive determination in polymers will be described. Some result data from QA/QC laboratories will be shown. Instrumentation considerations and analysis procedures will also be discussed.

“Rapid Gas Chromatography Using 100um id Capillary Columns”
Merritt Novack - Analytical Control Services

Procedures have been developed to provide rapid gas chromatography for simulated distillation (2 minute C3-C15, 7 minute C5-C44), and detailed hydrocarbon analysis (32 minute C1-C15). Results obtained with the rapid analysis methods show excellent correlations to ASTM 3710, ASTM 2887, and ASTM 6623 / ASTM 5134 respectively. These methods are at least three to four times faster than conventional ASTM procedures. The results were provided using fairly standard off the shelf components. The Agilent 6850 gas chromatograph was used for simulated distillation and a Hewlett-Packard 5890 SII was used for the fast detailed hydrocarbon analysis. HP Chemstation was used for data acquisition. Using short narrow bore capillary columns resulted in fast and reliable analysis.

“Prediction of the Relative Response of the He-PDPID without the Use of Theoretical Calculations”
W.E. Wentworth and Stanley D. Stearns - Valco Instruments Co., Inc.

The dominant factor in predicting the relative response of the Helium Pulsed Discharge Photoionization Detector (He-PDPID) is the number of valence electrons assigned in the theoretical calculations. For a series of hydrocarbons, including unsaturated as well as saturated, there is a linear correlation between the theoretically predicted response and the number of valence electrons. Based upon this correlation the relative response can be assessed simply by using the number of valence electrons. The number of valence electrons for heteroatoms can be established using a single parameter for each heteroatom. The calculation of a relative response factor can be made in a few minutes and is accurate to 5 - 15%.

“Use of the Ratio of FID/PDPID Responses for GC Peak Identification”
W.E. Wentworth, Sui Shen, and Stanley D. Stearns - Valco Instruments Co., Inc.

The Pulsed Discharge Photoionization Detector (PDPID) is connected in series with a FID. The helium flowrate from the PDPID (~ 30 mL/min) serves as the inert makeup gas for the FID with no loss in sensitivity since the FID response is mass flow dependent. Since the FID does not respond to heteroatoms, the FID/He-PDPID ratio will be a measure of the amount of heteroatom substitution in the compound. Values for this ratio range from 0.05 to > 1.0. If the PDPID is doped with Kr, the Kr-PDPID response will be dependent upon unsaturation and I, Br, and S substituents in the compound. The response ratio Kr-PDPID/FID gives a wide range of values from approximately zero for saturated hydrocarbons to values on the order of 6 - 10 for I containing compounds. The combination of the FID/He-PDPID and Kr-PDPID/FID ratios gives a differentation between certain classes of compounds.

“The Separation of Olefins from Denatured Alcohol”
Jody Clark, Nathan Halls and Dale Felix - Selerity Technologies, Inc.

Increasingly, ethanol is being used as the compound of choice as an oxygenate additive in gasoline formulations within the United States. When denatured alcohol is used, however, environmental issues arise resulting in the requirement to determine the olefin content in the alcohol. In this presentation, we describe the development of an automated, multiple column SFC method for the determination of olefins in ethanol. The method extends the column switching technique developed for ASTM Method D-6550 by which olefins are separated as a class from within gasoline. In this case, the interest is in separating the olefins from an alcohol matrix that may contain small amounts of aromatic and aliphatic compounds. Three columns are used to effect the separation. Two switching valves control flow direction through the columns. A PVA column retains the ethanol, a silica column separates any aromatics and a silver-loaded silica column captures the olefins. Once the olefins are trapped, the solvent flow is reversed and the olefins are backflushed from the column. The effluent passes through a flame ionization detector for quantitation of the olefins. The aromatics can also be eluted and determined as a final step.

“Gaining Speed and Efficiency Through Temperature Programming in HPLC”
Dale Felix and Stephanie Marin - Selerity Technologies

The benefits of using higher temperatures in HPLC, especially in combination with temperature programming, have been observed by a number of investigators during the past two decades. Increasing the temperature in HPLC results in higher efficiencies, faster run times, and selectivity changes; however, most laboratories continue to operate HPLC at near room temperature. Because selectivity can change as a function of temperature, temperature programming becomes a simple way of effecting separation without complex fluid gradients. The recent introduction of columns that can withstand the rigorous high temperature conditions and of column heaters that can effectively execute programmed temperature gradients places the power of temperature programming within any HPLC laboratory. In this paper we discuss the parameters affecting temperature programming in HPLC and the implications on instrument design. Effective temperature programming requires rapid transfer of heat from the column oven to the column such that columns are uniformly heated and that the column tracks the temperature program with negligible delay. At high flow rates through 4.6 mm columns, mobile phase preheating is absolutely essential in order to reduce band broadening related to thermal mismatch across the column. Examples of several test mixtures demonstrate the effectiveness of temperature programming in HPLC.

“A Direct Injection Gas Chromatographic Method for Measuring Light Hydrocarbon Emissions from Cooling Tower Water”
Max Lee, Tim Logan, Kefu Sun, Spance Hurley Jr., and Steve Gluck - Dow Chemical

Due to recent concerns with ozone, there have been increased efforts to understand the potential fugitive losses of hydrocarbons from cooling towers and develop a practical and effective method to measure those losses. Hydrocarbon monitoring of cooling tower water is required by TNRCC for many Dow businesses at Freeport to receive and/or maintain operation permits. Most heavy hydrocarbons (>C6) can be analyzed by EPA standard methods. However, there are no promulgated EPA methods for determining light hydrocarbons (  

Abstract # 085 Paper

“The Determination of the Temperature Dependence of the Response of the Pulsed Discharge Electron Capture Detector (PDECD)”
Edward C. M. Chen and Li Ding - University of Houston Clear Lake

The temperature dependence of the pulsed discharge electron capture (PDECD)detector has been determined for the halomethanes, several chlorobenzenes, hexafluorobenzene, acetophenone, benzaldehyde, carbon disulfide, biacetyl, nd azulene. The kinetic model of the ECD will be applied to these data to illustrate how the temperature dependence can be predicted from fundamental properties such as the electron affinity, the energy for dissociative electron attachment and the activation energies for thermal electron attachemnt. The temperature dependence will be compared with that obtained from radioactive electron capture detectors. With these data, the optimum temperature for analysis can be chosen.

“MSVent - a Multidimentional Interface Designed for GC-MS”
Michael Harter, Andrew Tipler - PerkinElmer

We describe the design of an interface that enhances the performance and application of a GC-MS system. Fused silica restrictor tubing is inserted into the GC-MS transfer line and is connected to the GC column by means of a simple adapter. A programmable pneumatic controller controls the carrier gas pressure within the adapter. The system supports the following techniques: Column backflushing Injector maintenance and column replacement while the MS is active Constant carrier flow rate to the MS Use any column and flow rate Column effluent split to a second detector Match MS retention times to a FID or SCD Enhanced large volume injection Examples are taken from petrochemical applications.

“Dual Channel Gas Chromatographic System for Low Level Sulfur Detection”
Roger Firor, Bruce Quimby, Jim McCurry – Agilent Technologies

Gas Chromatography coupled with sulfur selective detectors is a powerful tool for measuring low-level sulfur in hydrocarbon streams. However, a single column is not available that will separate all important light sulfur compounds from C2 through C4 hydrocarbons. A dual channel GC-FPD system is described that employs both methyl silicone and silica plot columns to achieve separation of light sulfur compounds (including COS and H2S) in C2 through C4 hydrocarbon streams. Simultaneous dual valved injection with automated EPC standard dilution is employed. Since the system uses easy to operate and maintain FPD's, it is suitable for routine and plant application.

“Dual-Secondary Column Comprehensive Two-Dimensional Gas Chromatography (GC x 2GC) with Differential Flow Modulation”
John V. Seeley and Pedro A. Bueno - Oakland University

A comprehensive two-dimensional gas chromatograph with dual secondary columns (GC x 2GC) has been developed for characterizing mixtures of volatile organic compounds (VOCs). Each GC x 2GC analysis produces a pair of two-dimensional gas chromatograms that provide complementary information due to the unique selectivities of the secondary columns. A wide variety of samples have been analyzed with the GC x 2GC system, including outdoor air, indoor air, and exhaled breath. More than 100 volatile organic compounds can be separated in less than 10 minutes. The enhanced quantitative and qualitative analysis capabilities of this technique will be discussed.

“Real Time Gas Analyzer for Process Monitoring”
Roger Firor, Jim McCurry, Bruce Quimby - Agilent Technologies

Development, characterization, and optimization of petrochemical processes can benefit significantly from fast, accurate on-line chemical measurements. For example, on-line mass spectrometers can give fast response and low detection limits for a wide range of compounds such as would be needed for measuring transient response to instantaneous changes in feed composition or process conditions. Applications of a quadrupole mass spectrometer for real-time gas analysis will be shown. Measurement of percent composition to ppb level impurities is possible. A new specialized two-stage gas interface will be described for sample introduction into the mass spectrometer.

“Volatile Organic Compound Analysis”
Terry Jeffers, Glynda Smith - Tekmar-Dohrmann/Scientific Marketing

The analysis of Volatile Organic Compounds is one of the biggest applications in the GC laboratory. In this workshop attendees will learn about the most popular techniques for analyzing VOCs; Static Headspace and Purge & Trap/GC analysis. We will discuss the theory of both techniques, How to choose the most appropriate technique for your application, instrumentation needed for each method and troubleshooting both methods. The workshop will wind up with a question and answer session.

“Comprehensive Two-Dimensional Gas Chromatography -- A New Frontier in the Characterization of Complex Petroleum Streams”
Frank Cheng-Yu Wang, Frank P. DiSanzo and Frank C. McElroy - ExxonMobil

Comprehensive two-dimensional gas chromatography (GCxGC or 2D-GC), provides unique capabilities in high resolution gas chromatography (GC). GCxGC employs a single GC containing two separation columns of different selectivity connected in series with a modulation unit in between to perform solute focusing and re-injection into a short, high-speed second column. GCxGC may be considered a 'Continuous' heart-cutting form of a conventional single heart-cutting multidimensional GC which has been established for many years. When analyzing a complex mixture, conventional one-dimensional GC most often results in (1) unresolved peaks in a limited time region and (2) limited detection sensitivities. However, with GCxGC compound resolution has been significantly enhanced. In addition, the resulting two-dimensional chromatogram can provide unique component information on a boiling point basis in one dimension as well as on a polarity basis in the second dimension. This means that in the GCxGC chromatogram, unlike conventional GC, the information of compound classes can be clearly observed. This presentation will describe applications of GCxGC to the characterization of petroleum streams such as hydrocarbons using flame ionization detector (FID) and sulfur compound using sulfur chemiluminescence detector (SCD). For example, in the hydrocarbon analysis by FID, paraffins, naphthenes, and aromatics will form distinct two-dimensional separated groups. In the analysis with SCD, sulfur-containing compound classes can be distinguished by boiling point and polarity as distinct different classes. The GCxGC/SCD approach offers significant resolution and identification advantage over conventional GC/FID and GC/SCD analysis.

“Six Degrees of Separation: GCxGC Column Technology from a Practical Perspective”
Jean-Marie D. Dimandja - Spelman College

Comprehensive two-dimensional gas chromatography (GCxGC) is rapidly transitioning from the instrument development to the method development phase. Routine application of GCxGC requires integrated software for data processing and dedicated column technology for quality control. Conventional 1D GC column technology offers discrete choices based on stationary phase type and column dimensions. This paper will present the current state of column technology in GCxGC. A number of distinct operational modes will be presented through the use of a characterization mixture that has been developed specifically for GCxGC and provides feedback on the system in a manner similar to the use of the Grob mix in 1D GC.

“Advances in Burner Technology for Measurement of Nitrogen Compounds by Gas Chromatography and Chemiluminescence Detection”
Randy Shearer - Ionics Instruments and Jim Luong, Ronda Gras, Myron Hawryluk - Dow Chemical

Gas chromatography with nitrogen chemiluminescence detection (NCD) has advantages over other detectors for nitrogen speciation, including high selectivity, linearity, and a stable and equimolar response. Still, more sensitivity is desired to improve detection limits. An advanced catalytic/flame based burner has been developed to address this. Compared to other NCDs, the advanced burner offers markedly improved sensitivity, while maintaining a high degree of selectivity. This burner delivers a sensitivity enhancement of up to 50%. In addition, the advanced reactor is robust, easy to operate and delivers excellent selectivity. System performance data along with common industrial applications will be covered.

“Analysis of Volatile Sulfur Compounds by Microvolume Injection and DR-SCD”
Randy Shearer - Ionics Instruments and Jim Luong and Ronda Gras, - Dow Chemical

The accurate analysis of trace sulfur compounds in hydrocarbons is crucial in the petrochemical industry. With that in mind, a new gas chromatographic technique has been developed to deliver faster sulfur analysis with markedly improved sensitivity. This technique is based on fundamental principles of high-speed gas chromatography and an improved selective detector. The main components are a microvolume injector using a high-speed actuator coupled with an advanced "dual rod" (DR-SCD). In comparison to a currently practiced technique, the new analytical approach is approximately four times faster and five times more sensitive. This approach and its performance will be described.

“Adjudication of Reported Nitrogen Interference with Respect to Total Sulfur Determination by Oxidative Combustion and Electrochemical Detection”
Herb A. Hernandez, Mike G. Trbovich - AJ APS Technologies, Inc.

It has been reported that unspecified, but large, amounts of chemically-bound nitrogen in hydrocarbon liquids can interfere with the determination of total sulfur content by the oxidative combustion / electrochemical detection method (OCECD). This report will define the history and function of the OCECD technique, investigate possible and probable causes of the reported interference, site practical and analytical investigation of the basic analytical method, and propose viable conclusions and solutions. Also, since the reported interference was observed with liquid hydrocarbon materials, this report will confine its investigation specifically to these matrices.

“Assessing Technical feasibility of Supercritical Extraction Processes Utilizing Benchtop Laboratory Equipment”
Ken Krewson - Surpercritical Fluid Technologies, Rodger Marentis - Supercritical Solutions

The primary goal of Analytical/Laboratory SFE Unit Testing is to assess technical feasibility of a potential supercritical fluid extraction application. Experimental work begins using a supercritical fluid extraction bench top laboratory unit, such as the SFT-150. The Analytical/Laboratory Unit typically has 10ml to 4 liter extraction vessel capacity. Product samples and data from the feasibility testing are used to assess product quality, and to research the following process variables. 1) Preparation of feedstock 2) Extractor conditions 3) Separator conditions. The extract product is analyzed to determine how changes in these parameters change extract yield and concentration. If the results from Analytical/Laboratory Unit Testing are encouraging, the process development protocol is followed by proceeding to the next step. Phase Equilibrium experiments should be carried out on a laboratory phase equilibrium instrument to determine the processing conditions in which the compound of interest solubilizes and/or precipitates from the supercritical fluid. This information can then be utilized to fine tune the operation of the separators of a commercial scale supercritical fluid extraction system. Examples demonstrating the use of both and analytical/laboratory SFE unit and supercritical fluid phase equilibrium instrument will be shown.

“Ionics Instruments SCD/NCD Training Course”
Sue Davis - Trainer - Ionics Instruments Business Group

The SCD/NCD course will cover the following: How to correctly start up and shut down your instrument What the instrument components are and what they do How to run samples and interpret the results How to properly maintain your instrument to increase its performance and lifetime How to troubleshoot your system A few new applications that may be useful to you Course will be offered at 8:30 to 4:30 on September 8 and 9 at the Moody Gardens Hotel. Registration Price $995.00 Lunch is provided. For Registration Contact - Teri Drouillard – 1-800-291-6455 Ex. 228

“A Novel New Technology For Removing Residual Water From Emulsified Solvent Extractions for Environmental Analysis”
Robert Johnson and John A. Hiser – Horizon Technology, Inc.

A critical component of the sample preparation procedure is the removal of residual water from the extracting solvent, prior to introducing the extract into the analytical instrument. For many years, sodium sulfate has been used as the standard drying agent for removing residual water from the final solvent extracts. The conventional drying technique uses large quantities of sodium sulfate, is time consuming, can interfere with recoveries, creates waste issues, and cannot handle emulsified samples. This new product uses an innovative technology using a physical separation vs. a chemical separation to remove the residual water from the final elution solvent. This new product provides many advantages over the conventional sodium sulfate technique including, a cleaner, faster and easier technology, more complete phase separation and the ability to handle dirty and emulsified samples. This presentation will discuss the results from studies using this new drying device for EPA Method 8270, Method 1664A for Oil & Grease and other related methods.

“Optimizing System Parameters for the Analysis of Low Concentration Oxygenates in Environmental Water Samples Using Purge and Trap/Gas Chromatography/Mass Spectrometry”
Allen K. Vickers, Cameron George - Agilent Technologies

Phasing out Methyl tert-butyl ether (MTBE) as the oxygenate additive of choice in gasoline has led to an increased interest in testing for other common additives. These other additives may be ethers other than MTBE but also Methanol or Ethanol may be considered. Traditional techniques used for the analysis of volatile organic compounds in drinking and ground waters frequently employ the use of a purge and trap concentrator interfaced with a gas chromatograph. Extracting extremely polar analytes from an aqueous matrix requires modification and optimization of the purge and trap concentrator from its typical settings. All parameters will be detailed.

“Automatic Dual Column Confirmation of Chlorinated Pesticides and Herbicides Using Capillary Gas Chromatography and Retention Time Locking Software”
Allen K. Vickers, Kai Meng and Cameron George - Agilent Technologies

Achieving fast and effective analyte confirmation in the analysis of chlorinated pesticides, herbicides and PCBs is just one challenge facing environmental laboratories. To obtain a higher level of analyte identification confidence most methodology calls for the use of a confirmation column. The process of compiling and reviewing data from primary and confirmatory columns is tedious and time consuming. Using the Auto Dual Column Confirmation function of Retention Time Locking (RTL) software allows this comparison to take place immediately following sample analysis. When RTL software is used with optimized capillary columns and Auto Dual Column Confirmation sample and reporting throughput is vastly improved.

“Improving Performance for the Analysis of Volatile Organics by Purge and Trap/Gas Chromatography/Mass Spectrometry”
Allen K. Vickers, Philip L. Wylie and Cameron George - Agilent Technologies

The analysis of volatile organic compounds (VOC) in various matrices is a primary concern for most environmental testing laboratories. Recent changes in mass selective detector (MSD) design have resulted in improved sensitivity allowing for potential method improvements. To fully recognize these improvements it is important that all system parameters are optimized, including purge and trap conditions, column choice, detector settings and tune values.

“On Column Solid Phase Capillary Microextraction by Using Pulsed Discharge Detector and Reversing Column Flow During Extraction”
Huamin Cai and Stanley D. Stearns - VICI Valco Instruments Co. Inc.

Solid Phase Microextraction (SPME) has become a popular sample preparation method because it can eliminate tedious solvent extraction procedures and it can avoid huge solvent peaks passing through a GC column and detector. This consequently increases the performance and the lifetime of both column and detector. However, the current SPEM method, which uses a rod coated with solid phase as an extractor, has two drawbacks. First, it makes atomization difficult since the sample vial needs to be shaken during extraction to increase extraction efficiency, and second, it may lose sample or get contaminated when transferring the rod from the sample to the GC injector, since during that time the rod is exposed to air. The On Column Solid Phase Capillary Microextraction (OSPCME) method can overcome these two drawbacks. This method uses a capillary tube coated internally with solid phase as an extractor. The tubing is directly connected to the analytical column. During extraction, the Pulsed Discharge Detector (PDD) is pressurized, so that the column flow is reversed and the solvent will not go into the column and detector. Meanwhile, sample is passing through the extractor tubing and vent in the other direction, leaving interesting compounds on the tubing wall. After extraction, the PDD is depressurized to do the analysis. Because sample can be introduced for extraction by a large volume syringe, it is easy to automate, and because the extractor tubing is never exposed to air, it reduces sample loss and contamination. In addition, this method also has the following advantages: (1) it has higher extraction efficiency since all samples pass through a narrow bore extractor; (2) there is no size limitation for the extractor tube - it can be as short as a few centimeters and as long as a few meters; (3) the temperature of the extraction can be easily controlled, with a low temperature for a higher extraction efficiency and a high temperature for lower interference. The method can be used in many fields, such as residue pesticides analysis, organics in water, residue solvent in drugs, etc. Also, this method can be used for gas samples, especially air samples, such as indoor air quality monitor and trace explosive material monitor.

“Evaluation of Capillary Columns for General Performance Parameters”
Allen K. Vickers and Mitch Hastings - Agilent Technologies

To quantifiably and with scientific rigor compare the performance of a variety of capillary GC columns, all with 5% phenyl 95% dimethylpolysiloxane stationary phases from various manufacturers, to like DB- and HP- brands with the intent of providing information about the performance of these columns that will demonstrate clear technical differences and address competitive claims such as: "Equivalent too..." "Replacement for..." and "The only difference is the price" Research findings will be presented addressing these claims.

“Complete Separation of Fusel Oils by Capillary GC”
Allen K. Vickers, Eberhardt R. Kuhn, Susan E. Ebeler - Agilent Technologies, Inc.

Fusel oils are of great importance in the alcoholic beverages industry, since they affect the flavor and aroma of the beverage. Thus, their accurate quantitation is essential in assuring consistent quality of alcoholic beverages. This paper describes the successful separation of all fusel oils, including other compounds typically found in alcoholic beverages, in a single run on a common stationary phase. In particular, baseline separation of methanol/acetaldehyde and isoamyl/active amyl alcohol was achieved. Examples include chromatograms of standards as well as real samples of fermented and distilled spirits. The results are discussed in terms of fundamental chromatographic principles.

“Use of Retention Time Locking Software to Mitigate Dimensional Differences Related to Capillary Column Tolerances in Gas Chromatographic Analysis Methods”
Allen K. Vickers, Jason Ellis, Mitch Hastings - Agilent Technologies, Inc.

Capillary columns vary slightly from the nominal dimensions in length, diameter, and film thickness, despite column manufacturers' best attempts at controlling these parameters. While tolerances can vary from one manufacturer to the next and are generally quite narrow, these small differences in dimensions can result in differences in retention times that can have a significant impact on some separations. With the trend toward increasingly complex analyte lists, the likelihood increases of a method developed on one column yielding a given separation and the next "identical" column not giving the separation when these minor variations in dimension are not compensated for. Retention Time Locking software can help a user obtain more consistent results. It assists in adjusting column head pressure to match retention times by adjusting gas linear velocities to make up for dimensional differences. Ultimately this produces robust, easy to use methods with extremely reproducible retention times and elution orders from column-to-column and even GC system-to-system.

“Evaluation of Distillation as a Means of Recovering Low-Sulfur Fuels from Pipeline Transmix”
Randall Heald, Chris LaFrancois, George Dorsey - Phillips Petroleum Company

Typically, pipeline companies use distillation to recover gasoline from transmix, which is a blend of different fuel types that results from interfacial mixing during transport. Because of boiling-range overlap, this process does not completely separate the commingled fuels. This fact has raised concerns about processing transmix once the sulfur reductions prescribed in the EPA's Tier II Emission Standards are fully implemented. In this study, blends of various fuels of both low and high sulfur content were distilled and the fractions were analyzed for total sulfur. The results of this study and the implications for recovering low-sulfur fuel from transmix will be discussed.

“Philips Analytical XRF User Group Meeting”
User Group

The meeting will run from 12 noon until 5:00 p.m. Lunch will be held from 12:00 p.m.-1:00 p.m.. The meeting will then follow from 1 p.m.-5:00 p.m.

“Flow Injection Polymer Analysis? A New Method For Process And Quality Control”
Max Haney, Wei Sen Wong, Shawn Welch - Viscotek

The control of polymerization processes requires fast turnaround time for sequential measurements of the extent of reaction. A flow injection analysis method has been developed that measures polymer concentration, molecular weight, and intrinsic viscosity of a solution or emulsion reactor sample in less than 5 minutes from the time the sample is taken. The system consists of an HPLC pump, an injector valve, a GPC-type guard column, and the Viscotek triple detector array (TDA). The TDA is a single detector module with refractometer, light scattering, and viscometer detectors. A single polymer standard is used to calibrate all three detectors simultaneously. The procedure for sample analysis after calibration is: 1. Dilute the sample with an approximate amount of mobile phase solvent. 2. Inject the diluted solution. 3. The polymer is separated from the low molecular constituents (diluent, additives, monomer, oligomers) by the guard column. Typical run time is 3-4 minutes. 4. Software calculates quantities of interest from the three integrated polymer signals: a) Polymer concentration from the refractometer, b) Molecular weight from the light scattering, and c) Intrinsic viscosity from the viscometer. Precision on all three quantities is typically 0.3% RSD, which permits a very fine degree of feedback for control of the process.

“Speciation of Selenium in Refinery Wastewaters”
Charles J. Lord - Phillips Petroleum Co

The selenium concentration in discharged wastewater is becoming an important issue for many refineries. Refineries that process high-sulfur crude oils are particularly sensitive to this problem because in general, the selenium concentration increases along with the sulfur content. Selenium from the crude oil accumulates in the sour water waste streams and is difficult to remove using conventional wastewater treatment systems. In order to design an effective treatment process, it is necessary to know not only the total selenium concentration, but also the chemical forms of selenium that are present in the water. In order to satisfy this need, a selenium speciation technique has been developed that is capable of detecting part per billion levels of the various selenium anions that are found in wastewaters.

“The Sleeping Giants: Cylinder Safety in the Laboratory”
Selome Ayele, Jeffrey J. Werner, Louis D'Agostaro, Jean-François A. Borny - DCG Partnership 1, Ltd

Many industrial and laboratory facilities require the use of compressed gases for a variety of reasons. Compressed gas cylinders present both chemical and physical hazards to those employees in the lab as well as to people in other parts of the building. These hazards are easily overlooked and cylinder safety taken for granted. We believe it is important to keep our facility safe and to ensure that all of our employees conduct themselves in a manner which presents no hazard to themselves, other employees, or guests. This presentation contains basic safety precautions to ensure safe handling and storage of cylinders as well as cylinder labeling, and transportation for a variety of cylinders used in the standard industry.

“Sulfur Standards- From Fear to Ecstasy”
Monica Cathriner, Jean-François Borny, Jeff Werner, Louis D'Agostaro - DCG Partnership 1, Ltd.

In the analytical world, sulfur conjures up not only smelly, stinky images, but sends shivers of cold sweat down the backs of even the most stoic analytical chemists. This fear factor arises from the perception that sulfur analyses are impossible - from dependable, accurate standards to reliable results.From years of research and development, DCG has established a proprietary method for the passivation of cylinders to insure reliability, dependability and accuracy from all our world class sulfur calibration standards.This presentation will highlight the rigorous steps we take to guarantee sulfur calibration. We will also give a general overview, from sample grabbing to column choices to detector choices to accurate results, of some of the most stubborn sulfur analysis.

“Calibration Standards: Getting What You Want, When You Want It!”
Chavaun Harper, Jeffrey J. Werner, Louis D'Agostaro, Jean-François A. Borny - DCG Partnership 1, Ltd

Precise calibration of analytical instruments is imperative in today's competitive markets. DCG has emerged as a global leader in gas and liquid standards for the hydrocarbon, natural gas, and refining industries All standards are made gravimetrically. To ensure that the standards meet the customer's stringent specifications and requirements, analytical instrumentation is used to verify the gravimetric results. This presentation will illuminate the exacting techniques used to attain the highest quality standards. From the customer order to final preparation for shipment, from raw product analysis to final verification, every standard and instrument must be handled properly to ensure accuracy and reliability.

“Two-Dimensional Gas Chromatography (GCxGC) with Pulsed Flow Modulation”
Huamin Cai and Stanley D. Stearns - VICI Valco Instruments Co. Inc.

Two-Dimensional Gas Chromatography (GCxGC) is effective in analyzing complex samples because it has high separation power and it can get more information by using orthogonal primary and secondary columns. The devices currently used for GCxGC separation can be roughly divided into two types - (1) different flow modulator using a sample valve to deliver primary column effluent to the secondary column, and (2) cryogenic modulator using a cryogen to hold primary column effluent during the second column separation. A third type is pulsed flow modulation. This modulator allows the primary column effluent and a small flow of modulating gas flow directly into the secondary column. The modulating gas is a blank carrier gas and is modulated by an on/off valve in such way that it has a pulsed flow. Therefore, the signal output from the modulator is an additive signal. The signal can be easily separated by mathematic methods into the primary column signal and the secondary column signal, so it will not lose primary column signal during second column separation like other modulations do. The pulsed flow modulation method also has the following advantages: (1) the device is simple, inexpensive, and durable, so all that is needed is an on/off valve and a T connector and it could be used in a portable GC; (2) since it can use fast on/off valves, the peak width in the secondary column is very narrow; (3) it is easy to convert from two dimensional GC to one dimensional GC or vice versa by turning on/off modulator, even in the middle of a GC run; and (4) sample does not pass through any valves between column connection, eliminating the problems of carry over, condensation, and peak broadening.

“A Comparison of the PFPD and Chemiluminescent Detectors for Analysis of Low Level Sulfur Components”
Robert Benesch, Bruce Talbert & Tracey Jacksier - Air Liquide

Two of the most popular detectors used in conjunction with gas chromatography for the analysis of sulfur components below 1 ppm are the sulfur chemiluminescent and pulsed flame photometric detectors. However, it is often difficult to determine which detector is most appropriate for a specific application without first considering the figures of merit for each detector. This presentation will compare the figures of merit for each detector type using H2S, COS and SO2 as model compounds. Sensitivity, limit of detection, short and long term detector stability, and linear dynamic range will be presented.

“Fast and Accurate Analysis of Gases using a New Platform Portable Gas Chromatograph based on Miniaturized Chip Injection and Detection Technologies”
ames Pachlhofer, Varian, Inc., Walnut Crfeek, CA and Jaap de Zeeuw, Renaat van Hove, Jos Curvers and Luci Verhoeven, Varian BV, Middelburg, The Netherlands

Varian's exciting NEW CP-4900 Micro GC will be featured. Application results generated on the new instrument will be presented.

“Oil and Grease Determination in Waste Water by Solid Phase Extraction”
S. J. Johnson, K. Harden, T. D. Dickson, C. L. Johlman, and S. G. Gharfeh - Phillips Petroleum Company

Regulations in the Clean Water Act require that an industrial facility that discharges process water obtain an NPDES (National Pollutant Discharge Elimination System) permit. These permits contain standard and site-specific compliance monitoring and reporting requirements. One of the NPDES provisions requires that oil and grease concentration in the water be measured and reported to the US EPA. The US EPA, under the Montreal Protocol on Substances that deplete the Ozone Layer, agreed to regulate and phase out the use of chlorofluorocarbons (CFCs) and other ozone-depleting chemicals. As a result, the US EPA worked to develop Method 1664 (a gravimetric procedure using n-Hexane that is applicable to aqueous samples for the determination of oil and grease) to replace Method 413.1 and Standard Method 5520B, both of which use the Class 1 CFC Freon as the extraction solvent for the determination of oil and grease. Significant changes in Method 1664 relative to these older methods include: 1) the replacement of Freon as the extraction solvent with n-Hexane, 2) quality control, and 3) provision for the use of solid-phase extraction as a direct equivalent to liquid-liquid extraction. Solid phase extraction can offer operational advantages in monitoring waste water streams. This presentation will describe a procedure for determining the Hexane Extractable Material in refinery waste water using solid phase extraction in an automated procedure. Results of data comparisons among EPA 413.1(Freon gravimetric procedure), EPA 1664 (n-Hexane gravimetric procedure), and this automated solid phase extraction method will be presented.

“Cetane Number Analysis Using the Constant Volume Combustion Chamber Method: Fueltech's Fuel Ignition Tester (FIT)”
Michael Croudace (PAC) and Jan Paulsen (Fueltech)

The FIT (Fuel Ignition Tester) allows fuel suppliers, oil companies, and analytical laboratories to evaluate ignition properties of any liquid diesel fuel, providing results faster, at a lower cost, and for more fuel types than possible with conventional laboratory methods.The FIT establishes ignition quality based upon ignition delay; this measurement is then converted to an equivalent derived Cetane Number (DCN). With FIT, the ignition quality of any liquid fuel for diesel engines can be tested efficiently and in a matter of minutes. This includes fuels ranging from low viscosity distillates (Gasoil) to high viscosity marine heavy fuel oil (HFO), as well as unconventional fuels such as biofuels. In addition, the effects on the ignition quality from fuel additives or chemical contaminants can also be established.During this session, we will present an overview of the FIT including round robin data comparisons of FIT and engine test results. An on-site operational unit will provide attendees hands-on opportunity to see how easily and effectively the instrument works.

“LABWORKS User Meeting”
Gary Gostecnik

This annual Gulf Coast Conference meeting will be open to all Users of LABWORKS to learn and share the latest ideas, programs, and techniques relating to the product. For further information, please contact Gary Gostecnik.

“Sulfur Analysis Using ASTM D 2622 at Refinery Laboratories”
Keith F. Dahnke, Robert L. Morton - Phillips Petroleum Co.

A series of 11 gravimetrically prepared standards containing 10-500 ppm sulfur were analyzed at 7 Phillips refinery laboratories as well as the Phillips R&D x-ray laboratory. Also, a sample of unleaded gasoline containing ethanol was included. Triplicate results were obtained from each of the seven laboratories on each sample. An ASTM E 691 analysis was performed on the database, to statistically evaluate each laboratory's performance. Results clearly showed that those laboratories having higher-power x-ray tube instruments (3,000 Watts) were able to measure all of the samples acceptably according to the limitations specified in ASTM D-2622. Laboratories equipped with instruments with low-power x-ray sources (200 Watts) were not acceptable for analyzing samples containing less than about 40 ppm sulfur. Specific recommendations for improvement were made to each participating laboratory based on their results.

“Petroleomics: The Search for Relationships Between Chemical Composition and Properties of Petroleum and Its Products by FT-ICR High Resolution Mass Spectrometry”
Ryan P. Rodgers, Chris L. Hendrickson, Mark R. Emmett, Christine A. Hughey, Alan G. Marshall - Florida State University – NHMFL

The number of distinct chemical components of petroleum is already approaching tens of thousands, and is thus becoming roughly comparable to the number of genes (genome) or proteins (proteome) in a given biological species. For example, we recently resolved almost 20,000 different elemental compositions in a single positive-ion electrospray FT-ICR mass spectrum of a heavy crude oil. The focus of this presentation will be to outline the recent advances and applications of FT-ICR mass spectrometry in the petroleum field and discuss how increased compositional knowledge of crude oil and refined products can provide a chemical basis for properties of petroleum.

“Elimination of Neutral Noise from a GC/MS Quadrupole Mass Spectrometer”
Don Clay, Brody Guckenberger, Scott Quarmby, Ed McCauley, and Alan Schoen - Thermo Finnigan

One of the limiting factors of sensitivity in quadrupole mass spectrometers is background noise in the detector signal. Signal to noise measurements confirm much of this background noise is due to Helium ions and energetic neutrals reaching the detector. A new quadrupole mass spectrometer design is described utilizing an off-axis source to eliminate virtually all this neutral noise. This new instrument achieves significantly lower signal to noise measurements, resulting in increased linearity and lower detection limits.

“Comparison between Thermospray and Liquid Band Formation techniques in Split and Splitless Injections”
Don Clay, Paulo Magni, Thomas Porzano - Thermo Finnigan

A transparent injector was constructed to investigate the physical behavior of liquid sample injections into a hot inlet. Dependent on the injection parameters, aerosol formation or liquid droplet formation could be observed. The performance of a new autosampler designed to achieve appropriate selection of the operating conditions for cold needle and hot needle SSL techniques are illustrated and discussed. These techniques involve independent mechanisms of sample vaporization, liquid band formation and thermospray respectively

“Optimised Injection Systems for Fast Screening of Complex Mixtures of Organic Compounds Using Narrow Bore Capillary GC With GC Detectors and Time of Flight MS”
Don Clay, Fausto Munari, Stefano Pelagatti, Daniela Cavagnino - Thermo Finnigan

Short capillary columns with small diameters are becoming more popular in gas chromatography due to their ability to yield separation power in a short time and to lower the minimum amount of detection. They can be successfully used with Split injection systems, but present difficulties in Splitless injections systems due to the difficulty of sample transfer and to adverse solvent effects. Specifically designed injection systems, such as PTV equipped with Backflush capabilities and Large Volume option, may be used with these columns for the successful analysis of traces in different matrices. Detection is also greatly enhanced by the large volume capability and the favorable peak signal to noise ratio.In addition, Time of Flight Mass Spectrometry is becoming the optimum MS detector for Fast GC, thanks to its fast scanning speed. The poster describes the best injection systems for the correct screening of various mixtures such as: Pesticides, PAH's, PCB's, Semi- volatiles and Volatiles , into narrow bore capillary columns for trace analysis in combination with suitable GC detectors and TOFMS to detect and identify compounds in fast chromatography analysis.

"Applicability of Comprehensive Two-Dimensional Gas Chromatography to Industrial Analysis"
Philip Marriott and Robert Shellie - RMIT University

Comprehensive two-dimensional gas chromatography (GCxGC) is a relatively new, however still not very widespread method of ultra high resolution GC analysis. It employs two serially-coupled capillary GC columns of different stationary phase; the first is a normal dimension column, and the second is a very fast analysis column (often about 1m long or less). Between the columns, a 'modulator' device provides a means of pulsing solute from column 1 to column 2, and this achieves a full two-dimensional analysis of the sample. There is a strong enthusiasm within the few groups developing GCxGC methods for the opportunities that are offered to general complex sample analysis, but this needs to be translated to the broader user-base of GC. Perhaps the 'radical' way GCxGC is implemented is partly responsible for this situation.

"SimDis Expert 7' Training"
Joaquin A. Lubkowitz, Roberto I Meneghini - Separation Systems, Inc

This course is intended for persons who are currently responsible for performing simulated distillation analysis and need to learn more about the use of simulated distillation in the laboratory and the use and handling of the SimDis Expert 7 Software.