Evaluation of the performance of various universal and selective detectors for sulfur determination in natural gas

In the present contribution, the performance of a number of commercially available selective and universal detectors that can be used in the analysis of sulfur components in natural gas is evaluated in terms of sensitivity, selectivity, reproducibility, quenching effect, stability, and compound dependence of the sulfur response. Investigated detectors include the sulfur chemiluminescnce, the flame photometric, the electron capture, the mass spectrometric, the thermal conductivity, and the flame ionization detector. The sulfur chemiluminescence detector was found to have the best overall performance, e.g., low picogram amounts of sulfur can be detected accurately and the linear dynamic range is more than five orders of magnitude. After careful optimization, the sulfur response of this detector was found to be almost compound independent. All other detectors, including the flame photometric and the electron capture detector, have more or less compound dependent responses.     

Improved method for the determination of sulfur components in natural gas

Determination of trace concentrations of sulfur components in natural gas is a true analytical challenge. Only analytical procedures based on gas chromatography can meet the sensitivity and accuracy requirements dictated by environmental regulation institutions and modern chemical industry. In the present contribution the sample pretreatment and chromatographic separation steps have been evaluated and optimized based on the use of a flamebased sulfur chemiluminescence detector (SCD) for target compound detection. The proposed instrument consists of a programmed temperature vaporizing (PTV) injector employing a liner packed with Chromosorb 104, a 4 μm thick film apolar column and a flame-based SCD. Using a 13 mL sample loop the detection limit achievable with the new method is 3 μg S/m³. The precision of replicate measure. ments is generally in the range of 5–15% relative standard deviation. Lower detection limits can be achieved by preconcentrating larger sample volumes, e.g. 100 mL.     

Column selection and optimization for sulfur compound analyses by gas chromatography

The analysis of sulfur-containing compounds using fused silica capillary columns and the Sulfur Chemiluminescence Detector has been investigated. This combination of an inert chromatographic system and a high sensitivity, selective detector provides significant advantages for the analysis of low levels of sulfur compounds in complex matrices over existing techniques. Capillary columns coated with thick films (1–4 μm) of methyl silicone stationary phase permit separation of most sulfur containing compounds and, when used with sub-ambient column temperatures, these columns can be used for the separation of sulfur gases. The effects of stationary film thickness, column length, and internal diameter for the measurement of sulfur compounds in hydrocarbon matrices has been determined.     

Determination of the sulfur components of gasoline streams by capillary column gas chromatography with sulfur chemiluminescence detection

A method using a sulfur chemiluminescence detector (SCD) has been developed for the qualitative and quantitative determination of sulfur components in stabilized gasoline-range process streams, including blended gasolines containing between 1 and > 4000 ppm total sulfur. The detection limit per sulfur component was approximately 50 ppb. On-column injection was employed for optimum precision and accuracy. A new probe material was found which did not soften under FID operating conditions. A new method, using a hydrogen sulfide permeation tube, was developed for rapid alignment of the probe in the FID.     

A system consisted of flame ionization detector and sulfur chemiluminescence detector for interference free determination of total sulfur in natural gas

A new detection system consisted of a flame ionization detector (FID) and a sulfur chemiluminescence detector (SCD) was developed for sensitive and interference free determination of total sulfur in natural gas by non-separation gas chromatography. In this system, sulfur containing compounds and hydrocarbons were firstly burned in the FID using oxygen rich flame and converted to SO₂, CO₂ and H₂O, respectively. The products from FID were transported into the SCD with hydrogen rich atmosphere wherein only SO₂ could be reduced to SO and reacted with O₃ to produce characteristic chemiluminescence. Therefore, the chemiluminescence of CO found in conventional SCD were eliminated because CO₂ could not be reduced to CO under these conditions. The experimental parameters were systematically investigated. Limit of detection obtained by the proposed system is better than 0.5 μmol/mol for total sulfur and superior to those previously reported. The proposed method not only retains the advantages of the conventional SCD but also provides several unique advantages including no hydrocarbon interference, better stability, and easier calculation. The utility of this technique was demonstrated by the determination of total sulfur in real samples and two certified reference materials (GBW 06332 and GBW (E) 061320).     

Flow injection gas chromatography with sulfur chemiluminescence detection for the analysis of total sulfur in complex hydrocarbon matrixes

A fast and reliable analytical technique for the determination of total sulfur levels in complex hydrocarbon matrices is introduced. The method employed flow injection technique using a gas chromatograph as a sample introduction device and a gas phase dual‐plasma sulfur chemiluminescence detector for sulfur quantification. Using the technique described, total sulfur measurement in challenging hydrocarbon matrices can be achieved in less than 10 s with sample‐to‐sample time <2 min. The high degree of selectivity and sensitivity toward sulfur compounds of the detector offers the ability to measure low sulfur levels with a detection limit in the range of 20 ppb w/w S. The equimolar response characteristic of the detector allows the quantitation of unknown sulfur compounds and simplifies the calibration process. Response is linear over a concentration range of five orders of magnitude, with a high degree of repeatability. The detector's lack of response to hydrocarbons enables direct analysis without the need for time‐consuming sample preparation and chromatographic separation processes. This flow injection‐based sulfur chemiluminescence detection technique is ideal for fast analysis or trace sulfur analysis.     

Determination of arsenic and arsenic compounds in natural gas samples

Organic arsenic compounds (trialkylarsines) present in natural gas were extracted by 10 cm³ of concentrated nitric acid from 1 dm³ of gas kept at ambient pressure and temperature. The flask containing the gas and the acid was shaken for 1 h on a platform shaker set at the highest speed. The resulting solution was mixed with concentrated sulfuric acid and heated to convert all arsenic compounds to arsenate. Total arsenic was determined in the mineralized solutions by hydride generation. The arsenic concentrations in natural gas samples from a number of wells in several gas fields were in the range 0.01–63 μ As dm^?3. Replicate determinations of arsenic in a gas sample with an arsenic concentration of 5.9 μ dm^?3 had a relative standard deviation of 1.7%. Because of the high blank values, the lowest arsenic concentration that could be reliably determined was 5 ng As dm^?3 gas. Analysis of nonmineralized extracts by hydride generation identified trimethylarsine as the major arsenic compound in natural gas. Low-temperature gas chromatography-mass spectrometry showed more directly than the hydride generation technique, that trimethylarsine accounts for 55–80% of the total arsenic in several gas samples. Dimethylethylarsine, methyldiethylarsine, and triethylarsine were also identified, in concentrations decreasing with increasing molecular mass of the arsines.     

Element-selective detection using capillary gas chromatography with atomic emission detection

Capillary GC coupled to an atomic emission detector (AED) provides a powerful new hyphenated technique for the separation and characterization of complex mixtures and compounds. The AED provides simultaneous and truly specific multi-element detection. The specificity of detection reduces the need for the complex sample pretreatment procedures which are necessary to reduce the interference from co-eluted substances which is experienced with detectors such as the FID and the ECD. A range of environmentally significant problems has been studied, including PCB analysis, the characterization of the reaction products of a novel waste treatment process, and the profiling of sulfur-containing species formed by the pyrolysis of various types of coal.     

Determination of phosphorus in natural waters: A historical review

The aim of this paper is to introduce a virtual special issue that reviews the development of analytical approaches to the determination of phosphorus species in natural waters. The focus is on sampling and sample treatment, analytical methods and quality assurance of the data. The export of phosphorus from anthropogenic activities (from diffuse and point sources) can result in increased primary production and eutrophication, and potentially the seasonal development of toxic algal blooms, which can significantly impact on water quality. Therefore the quantification of phosphorus species in natural waters provides important baseline data for studying aquatic phosphorus biogeochemistry, assessing ecosystem health and monitoring compliance with legislation.     

Comparison of combustion sources for sulfur chemiluminescence detection

Three different types of SCD combustion source have been evaluated for use in the chromatographic analysis of atmospheric sulfur compounds. The conventional FID source and the newer inverted burner source were found to be less sensitive and less stable than the flameless design. Overall, the flameless source was superior for use with HRGC-SCD.     

Analysis of sulfur-containing compounds in crude oils by comprehensive two-dimensional gas chromatography with sulfur chemiluminescence detection

This paper reports an analytical method for separating, identifying, and quantifying sulfur-containing compounds in crude oil fraction (IBP-360 degrees C) samples based on comprehensive two-dimensional gas chromatography coupled with a sulfur chemiluminescence detector. Various sulfur-containing compounds and their groups were analyzed with one direct injection. 3620 peaks were detected including 1722 thiols/thioethers/ disulfides/1-ring thiophenes, 953 benzothiophenes, 704 dibenzothiophenes, and 241 benzonaphthothiophenes. The target sulfur compounds and their groups were identified based on the group separation feature and structured retention of comprehensive two-dimensional gas chromatography as well as standard substances. The quantitative analysis of major sulfur-containing compounds and total sulfur was based on the linear response of the sulfur chemiluminescence detector using the internal standard method. The sulfur contents of target sulfur compounds and their groups in 4 crude oil fractions were also determined. The recoveries for standard sulfur-containing compounds were in the range of 90-102%. The quantitative result of total sulfur in the Oman crude oil fraction sample was compared with those from ASTM D 4294 standard method (total S by X-ray fluorescence spectrometry), the relative deviation (RD%) was 4.2% and the precision of the method satisfactory.     

A novel focusing injection technique for chemiluminescent detection of volatile sulfur compounds separated by HRGC

A one meter stainless steel capillary column coated with a 20μm film of polydimethylsiloxane was used to replace the Teflon gas sampling loop of a HRGC – flameless SCD system. This column trap was equilibrated with the gaseous sample and then purged with carrier gas while being sequentially, resistively heated in ten 10 cm sections. The sequential heating of the 10cm sections was timed such that the velocity of the moving heated zone was approximately the same as the velocity of the carrier gas. The thick stationary phase film served to retard the front end of the injection band while the ballistic heating accelerated the back end. The net result was focusing of the injection, which gave rise to a narrower injection profile than that obtained with the original Teflon loop.     

Studies on thermionic ionisation detection in comprehensive two-dimensional gas chromatography

This study explores the application of specific thermionic ionisation detection in comprehensive 2-D GC (GC x GC) and represents the first report of GC x GC with nitrogen phosphorus detection (GC x GC-NPD). Of particular interest is the performance of the NPD with respect to peak parameters of asymmetry and sensitivity. Since GC x GC produces much narrower peaks than obtained with fast GC (e.g. 100 ms vs. <1 s) the effect of detector response time and any lack of symmetry arising from the detection step is important if peak separation (resolution) is to be maintained. It was observed that detector gas flows had a significant impact on peak asymmetry and peak magnitude, and that optimisation of the detector was critical, particularly for complex sample analysis by GC x GC-NPD. Peak asymmetries ranging from As = 1.8 to 8.0 were observed under different conditions of detector gas flows. Comparison of GC x GC-NPD with GC x GC-flame ionisation detection (FID) showed the former to be approximately 20 times more sensitive for the detection of nitrogen-containing methoxypyrazines analytes, and GC x GC-NPD had a larger linear detection range compared to GC x GC-FID. Furthermore, comparison of GC x GC-NPD and GC x GC-TOFMS chromatograms for the analysis of coffee head-space demonstrated the benefits of selective detection, ultimately realised in a comparatively simplified contour plot.     

Selective detection of volatile nickel,vanadium, and iron porphyrins in crude oils by gas chromatography-atomic emission spectroscopy

This report describes the selective detection of volatile nickel, vanadium, and iron metalloporphyrins in crude oil samples. An atomic emission detector (AED) was used for simultaneous detection of these metals using the Ni 301.2 nm, V 292.4 nm, and Fe 302.1 nm emission lines. Detection limits for these metals range from 0.05 to 5 pg/sec. The presence of volatile forms of these metals in several crude oil samples has been confirmed.     

Formation and decomposition of gas hydrates of natural gas components

Based on our theoretical and experimental work carried out during the last decade, our understanding of the thermodynamics and the kinetics of formation and decomposition of gas hydrates is presented. Hydrate formation is modelled as a crystallization process where two distinct processes (nucleation and growth) are involved. Prior to the nucleation the concentration of the gas in the liquid water exceeds that corresponding to the vapor-liquid equilibrium. This supersaturation is attributed to the extensive structural orientation in the liquid water and is necessary for the phase change to occur. The growth of the hydrate nuclei or the decomposition of a hydrate particle are modelled as two-step procedures. Only one adjustable parameter for each hydrate forming gas is required for the intrinsic rate of formation or decomposition. In addition the inhibiting effects of electrolytes or methanol on hydrate formation are discussed and experimental data on methane gas hydrate formation in the presence of aqueous solutions of 3% NaCl and 3% NaCl + 3% KCI, are presented along with the predicted values. Finally, the relevence of the ideas to the technological implications of gas hydrates as well as areas where future research is needed are discussed.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena.     

Accuracy and precision of natural gas analysis

Summary Calculations of natural gas properties from chromatographic analysis is increasingly popular. An application of the significance of the various sources of error allows the overall uncertainty of the analytical procedure to be evaluated. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

Determination of ethers and alcohols in reformulated gasolines by gas chromatography/atomic emission detection

A GC method for the determination of oxygenated additives in reformulated gasolines (RFG) is described. The method uses on-column injection and atomic emission selective detection of oxygenates using the 777 nm NIR emission line. Detection limits are approximately 10 ppm oxygen. Results compared well with other techniques, such as GC/FTIR.     

Evaluation of comprehensive two-dimensional gas chromatography with flame photometric detection: Potential application for sulfur speciation in shale oil

Flame photometric detection in the sulfur channel has been evaluated for sulfur speciation and quantification in comprehensive two-dimensional gas chromatography [GC × GC-FPD(S)] for S-compound speciation in shale extracts. Signal non-linearity and potential quenching effects were reportedly major limitations of this detector for analysis of sulfur in complex matrices. However, reliable linear relationships with correlation coefficient >0.99 can be obtained if the sum of the square root of each modulation slice in GC × GC is plotted vs. sulfur concentration. Furthermore, the quenching effects are reduced due to essentially complete separation of S-containing components from the hydrocarbon matrix. An increase of S/N of up to 150 times has been recorded for benzothiophene and dibenzothiophene in GC × GC-FPD when compared to GC-FPD due to the modulation process. As a consequence, 10 times lower detection limits were observed in the former mode. The applicability of the method was demonstrated using shale oil sample extracts. Three sulfur classes were completely separated and the target class (thiophenes) was successfully quantified after the rest of the sample was diverted to the second detector by using a heart-cut strategy. Based on the proposed method, 70% of the sulfur in the shale oil was assigned to the thiophenes, 24% to benzothiophenes, and 5% to dibenzothiophene compounds.     

Supercritical fluid chromatography of petroleum products using flameless sulfur chemiluminescence detection

Supercritical fluid chromatography using flameless sulfur chemiluminescence detection has been investigated for the analysis of sulfur compounds in petroleum products. The chromatography and detection system was easy to implement and exhibited good precision, linearity, selectivity, and sensitivity. A minimum detectable limit of 0.3 pg sulfur/s was obtained, and response to sulfur in different sulfur species was nearly equimolar.