Accred Qual Assur (2001) 6 : 815 Q Springer-Verlag 2001

REVIEW PAPER

Kevin David Cleaver

The analysis of process gases: a review

Received: 1 March 2000 Accepted: 31 March 2000 A presentation summarising the key issues highlighted in this paper was first given at the Nederlands Normalisatie-instituut Gas Analysis Symposium & Exhibition, 79 November 1999, Evoluon Eindhoven, The Netherlands. K.D. Cleaver BOC Gases, The Priestley Centre, The Surrey Research Park, Guildford, Surrey, GU2 5XY, UK e-mail: kevin.cleaver6uk.gases.boc.com Tel.: c44-1483 244308 Fax: c44-1483 450741

Abstract A general review of key issues involved in the analysis of process gases is presented. The reasons for such measurements which include safety, quality, environmental and economic factors are considered. The technical issues arising from these measurements are dependent upon a variety of factors, including the overall sampling system, the type of analytical instrumentation, methods of data collection and the specified calibration protocols. The use of gas calibration cylinders as transfer standards is detailed and issues of

stability and traceability to reference material discussed. Keywords Process 7 Gas 7 Analysis 7 Sampling 7 Traceability

Introduction
A process gas may be regarded as any gas produced by a chemical or physical process, or a gas that is used as an integral part of a process. Examples are the steam reformation of a natural gas feedstock to produce hydrogen and carbon monoxide or the distillation of air at cryogenic temperatures to produce nitrogen, oxygen and argon. The use of gases in medicine, such as nitrous oxide in anaesthesia, or the use of gaseous calibration cylinder standards as transfer standards used in environmental or emissions monitoring is also widespread. The need for the analysis of process gases arises primarily from an industrial requirement for: Reliable and accurate data to enable process control and optimisation Materials and product evaluation Quality control. The data obtained allows: Compliance with legislation

Contract specifications International specifications and standards. Examples of analysis performed to ensure regulatory compliance include ambient air quality and stack emission monitoring for pollutants such as higher oxides of nitrogen, sulphur dioxide, carbon monoxide and ozone, automotive exhaust emission monitoring and the calibration and use of analysers for evidential purposes such as ethanol/air breath analysers. Within the natural gas industry fiscal monitoring, i.e. the analysis of oil and gas steams to determine calorific value, is a key part of the quality system requiring traceable gas calibration standards. These analyses have a significant and direct impact upon oil and gas companies profitability and the consumer. Furthermore, there is a widespread need for analysis to monitor occupational exposure levels to gases in the work place. Toxic gases, such as silane, arsine and phosphine, are widely used in the manufacture of semiconductor devices in gas cabinets and containment chambers. The whole operation is, however, conducted under clean

room conditions, with re-circulated air, so gas monitoring is essential. The monitoring of flammable or explosive atmospheres and medical gases, such as anaesthetics or inhaled nitric oxide, is also very important to ensure process safety. Finally, all industrial organisations survive on their ability to compete on the quality, price and the efficient distribution and delivery of their products into the global market-place. The analysis of gases, in the context of quality control, includes the optimisation of output and minimisation of rejects and the reduction of operating costs. All of these factors ensure that customer satisfaction is achieved and that products are fit for purpose.

Infrared and Raman spectroscopy Vibrational spectroscopy, particularly infrared spectroscopy, has been used for monitoring the environment. A number of devices have been developed for the analysis of gases. These include a portable FT-IR real time gas analyser [1], an IR imaging volatile organic carbon field sensor [2], an intercavity diode laser near-IR spectrophotometer [3], and a dual-cell extractive FT-IR ambient air monitor [4]. Trace gas analysis has been performed using a FT-IR equipped with a multipass cell and Grams/386 software [5]. FT-IR has been used for the time-resolved air monitoring of methyl bromide concentrations following the fumigation of buildings [6] and the detection of ammonia and hydrogen chloride in flue gases [7]. The determination of consumer exposure to volatile solvents during paint stripping operations [8] has also been determined by FT-IR. FT-IR has been used as a continuous emission monitor for stack gas analysis at an oil refinery [9] and incinerator [10]. Sampling techniques and FT-IR methods for the analysis of non-methane organic gases in automotive exhaust have been detailed [11] and the gases from aircraft engine exhaust analysed by means of an on-board FT-IR spectrophotometer [12]. Four separate analysers are normally used to test vehicle emissions for carbon monoxide, carbon dioxide, oxides of nitrogen (NOX) and total hydrocarbons, the results obtained from an FT-IR analyser have been compared with those obtained from the separate analysers [13]. FT-IR has also been used in a study of the catalytic conversion of NOX [14]. The use of a ground-based FTIR spectrophotometer as a remote-monitoring device for pollutants such as CFCs has been reported [15]. Reviews covering the remote sensing of the Earths atmosphere from space using IR [16], remote monitoring using far-IR [17] and the use of mid-IR tuneable diode lasers for monitoring trace gases in the atmosphere and the remote sensing of exhaust gases [18] have also been reported. In situ FT-IR spectroscopy has been used to monitor the production of air toxics during the pyrolysis and combustion of benzene and o-dichlorobenzene. The effects of temperature and chlorine concentration on the formation of polynuclear aromatic hydrocarbons were discussed [19]. NIR spectroscopy with fibre optics has been used in on-line determinations of hydrocarbon gases at a petrochemical plant in mixtures of ethane, ethene, propane and propene [20]. Raman spectroscopy has been used in some industrial applications; Lipp and Grosse have reported monitoring dichlorosilane distillation by Raman spectroscopy [21] with data acquisition times of only 1030 s required. Chlorosilane monitoring has now moved to at least the pilot plant stage. Gervasio and Pelletier have characterised the use of Raman spectroscopy to moni-

Industry types
A wide range of industries has a need to use and analyse process gases. The breadth of use may be illustrated by listing the key market sectors that either produce, use, or analyse process gases, namely: Chemical and petrochemical Environmental, including both ambient air and stack emission monitoring Scientific and engineering research organisations, including universities and national laboratories Medical institutions, including hospitals The food processing and drinks industries, where gases such as nitrogen are used to enhance the shelf life of products by reducing oxidation and carbon dioxide is widely used in soft drinks and alcoholic beverages The microelectronics industry, which includes semiconductor manufacture and telecommunications Fabrication industries, including the motor, ship and aircraft industries Power generation, particularly the nuclear industry, for example advanced gas reactors (AGRs) Instrument manufacturers (OEMs).

Instrumentation and techniques

It is perhaps unsurprising, given the breadth of applications, that a very wide range of analytical instrumentation is used for process gas analysis. This instrumentation utilises broad based techniques such as mass spectrometry and infrared spectroscopy, etc., chromatography, and also specific sensors used in analysers like paramagnetic and zirconia analysers, fuel and electrolytic cells. The following review, while not exhaustive, indicates the diversity of approach and the continuing developments to be found in this challenging field.

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tor the synthesis of phosphorus trichloride from phosphorus and chlorine [22]. Gas chromatography (GC) General reviews covering aromas [23], environmental samples [24], multiple detector alternatives to multiple columns [25], anaesthetic gases [26], and a book which discusses the theory and practice of headspace sampling with GC [27], have recently appeared in the literature. A review with eleven references has appeared on the use of metal capillary GC columns as an alternative to fused silica columns [28]. Other column developments have included a charcoal-based column capable of resolving light hydrocarbons [29] and a super long open tubular GC column (450 m long, 200 mm id) for the separation of gasoline [30]. This column had 1.3 million effective plates and was built up by connecting 9, 50 m columns in series and was able to resolve up to 970 components in a standard gasoline. A new porous layer open tubular (PLOT) column for the separation of gases and highly volatile compounds has been reported [31]. A comparison has been made between this column and a conventional doped aluminium oxide capillary column, it was not adversely affected by water, carbon dioxide and sulphur gases and appeared to be more inert than the aluminium oxide column since it did not cause decomposition of the most reactive analytes. Also a quartz-lined aluminium capillary GC column coated with graphitised carbon black has been evaluated for the analysis of volatile organic compounds (VOCs) and oil products [32]. The need for rapid and portable analytical measurements has led to the development of GCs with fast separation times [33]. Many portable high-speed gas chromatographs (HSGC) are being used for on-site analysis [34]. A micro-GC coupled with a thermal conductivity detector (TCD) was shown to separate carbon dioxide and C1C6 alkanes within 30 s. Petroleum industry applications included the detection of hydrogen sulphide and carbonyl sulphide impurities [35] and rapid screening for gasoline to diesel range organic compounds [36]. Environmental problems are a major application for portable GC systems due to the complexity of the samples [37]. Recent applications have included air analysis [38] and the detection of polychlorinated biphenyls (PCBs) [39]. An important focus of research and development in field gas chromatography (FGC) during the last few years has been instrument miniaturisation. The ultimate miniature FGC system was designed and developed using silicon micro-machining and integrated circuit processing techniques [40]. The chromatograph consisted of a 10-mm-long sampling loop, a 0.9-m rectangular shaped column, and an injection loop and column each

with a width of 300 mm and height of 10 mm. The column was coated with a 0.2 mm thickness of copper phthalocyanine as the stationary phase. Detection was based on a dual detection scheme using a coated chemiresistor and thermal conductivity detection. The complete FGC system was packaged in less than 23 cm 3 and was 2.5 mm high. Although limited in scope to the detection of ammonia and nitrogen dioxide, this miniature chromatograph offers exciting possibilities for future field instruments. The most common uses for FGC have hitherto been in the determination of volatile and semi-volatile organic compounds in the atmosphere. Target compounds for on-site screening by FGC include benzene in complex environments at the ppm level [41], dimethyl sulphide and carbon disulphide [42], and polychlorinated biphenyl [43]. Indoor air pollutants such as toluene, a-pinene, and 1,4-dichlorobenzene were determined, with detection limits in the low mg m 31 level [44] and long-lived species were identified in the upper troposphere and lower stratosphere [45]. One major problem of FGC when compared to laboratory based instrumentation is the reduced resolution that most field instruments exhibit. This reduced resolution is partially compensated for by the utilisation of selective detectors. Detectors such as the electron capture detector [46]; the photoionisation detector [47, 48], and a miniature dual flame photometric detector for phosphorus and sulphur compounds [49] have all been interfaced to field gas chromatographs. A versatile selective detector for GC is the ion mobility spectrometer or detector; recently this has been coupled to chromatographs for field use [50, 51]. A hand portable GC-ion mobility spectrometer has been constructed and called the environmental vapour monitor. This monitor has been used to separate and detect chemical warfare agents [52]. Numerous detectors are available for GC, broadly falling into two categories: ionisation detectors and optical detectors. Ionisation detectors include the flame ionisation detector (FID), the helium ionisation detector (HID), the nitrogen phosphorus detector (NPD), the electron capture detector (ECD), the surface ionisation detector (SID), the photo ionisation detector (PID), the ion mobility detector (IMD), and the glow discharge detector (GDD). Other miscellaneous GC detectors include acoustic flame detectors [53], and semiconductor detectors which are possible replacements for FID [54] and for breathalysers [55]. Improvements in the sensitivity of thermal conductivity detectors have also been reported [56] along with the interfacing with capillary column [57, 58]. Increasingly, discharge helium ionisation detectors (DID) are being used in process gas analysis applications. An evaluation of the detector by Cufflin and Smith [59] has shown:

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Detector linearity five orders of magnitude Minimum detection limits for methane of less than 2.5 parts per billion by volume (ppbv), without preconcentration of the sample Standard deviations of less than 200 parts per trillion by volume (pptv). A GC system has been developed for the direct analysis of atmospheric formaldehyde and other oxygenated hydrocarbons [60]. This method utilises the trapping of analytes in a loop cooled with liquid nitrogen, separation by GC and subsequent detection using a pulsed discharge helium ionisation detector (pHID). The detection limit of this instrument is estimated to be 32 pptv for 0.2 l of gas sampled at a flow rate of 30 ml min 1. At-Plant A recent trend with IR spectrophotometers, GCs and other instrumentation, such as mass spectrometers, is to locate them At-Plant. This movement of relatively sophisticated analytical instrumentation out of the laboratory and into the plant allows: Rapid data acquisition and increased operational efficiency, cf. central laboratories Continuous sampling and hence easier plant optimisation The use of statistical process control techniques, trend analysis, etc. Benefits derived from this approach include: Operating cost improvements Increased production The reduction in out of specification product and laboratory costs. The concept of At-Plant instrumentation, with its attendant benefits, is possible largely due to increased automation and PC-based controls, which allow day to day operation of the analysis equipment by plant technicians. Software developments have been of crucial importance, facilitating a simple but flexible approach at the user interface. Specific sensors Specific sensors and techniques for process gas analysis include: Paramagnetic detectors for oxygen purity and high concentration measurements (%) Zirconia, fuel cells and electrolytic cells for trace oxygen measurements (ppmv and ppbv) Chemiluminescence detectors for oxides of nitrogen (NOX) (ppmv and ppbv) UV fluorescence detectors for sulphur dioxide (SO2) (ppbv) determinations.

Different types of chemical sensors have been used for the electrochemical sensing of gases of medical interest [61]. In recent years the use of inhaled nitric oxide in neonates, paediatric and adult patients in intensive care units has become widespread. Of particular importance has been the requirement to monitor the concentration of inhaled nitric oxide [62] and nitrogen dioxide impurities; comparisons of chemiluminescence and electrochemical sensors have been made [63, 64]. A highly sensitive (10 ppb 1 ppm) ozone (O3) sensor using In2O3 as a sensing film has been developed stabilised ZrO2 [65], oxygen sensors based on Y2O3 (YSZ) have demonstrated longer lifetimes [66] and the detection of hydrocarbons in air and purification of exhaust gas under lean-burn conditions using solid electrolytes demonstrated [67]. Odour sensing is in the forefront of analytical interest, and several optical sensors have been used in this application. A chemiluminescence gas sensor made of Al2O3 emits luminescence during the catalytic oxidation of a combustible odour vapour [68]. Novel types of sensor are based on the immobilisation of a chemiluminescent reagent between a miniature photomultiplier tube and a Teflon diffusion membrane [69]. Taste and flavour monitoring has been done using a fluorescent optical probe detecting certain sulphur compounds in the vapours of hams [70]. A wide variety of techniques and sensors are used to measure moisture in gases, including: Capacitive sensors, which include aluminium oxide and other metal oxides, and silicon-based sensors Electrolytic (phosphorus pentoxide) sensors, which consist of a film of the phosphorus pentoxide desiccant which strongly absorbs water vapour from the surrounding gas. Optical dew point hygrometers, where condensation as dew or frost is formed on a mirror within the instrument and the onset of condensation is sensed optically by detecting changes in how the mirror reflects or scatters light. Other non-optical condensation dew point sensors detect condensation electrically, or by other methods such as the change in frequency of a resonating quartz crystal [71].

Sampling systems
Analysers and their associated sampling systems are often complex installations, which require careful design, reliable utilities (water, electricity, carrier and fuel gases), protection against temperature extremes, rain, dusts and corrosion. Ease of access to all of the system components is essential to allow adequate preventive maintenance and efficient operation. The key requirements of a sampling system are that the system design includes all of the components required for a safe and correct operation, e.g. probes,

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valves, filters, coolers, pressure regulators and relief valves, pumps, piping, etc., thus ensuring a sample which is representative of the overall process to be admitted to the analyser for analysis [7274]. An important consideration is sample point location. The sample point should be chosen to: Provide the most accurate information on the composition of the process stream Minimise time lags, particularly important when analyser outputs are used for process control Ensure that temperature, pressure, dryness, particulate loading, etc. are analyser compatible wherever possible to minimise the requirement for coolers, relief valves, filters, etc. Ensure that sample take off points are readily accessible. Design and construction considerations include: Materials selection and compatibility Requirements for purging, by-pass flow Trace heating and insulation, requirements for intrinsic safety and zoning of electrical equipment Equipment location Labelling, tags, etc. Effluent and sample gas disposal Calibration facilities Automatic calibration Requirements for analyser communication, which include signal transmission, cables, alarms and system validation and calibration. The complete analyser system should be designed, installed and operated so that it does not present a hazard to either personnel or plant.

Calibration and traceability

Process gas analysers used for quantitative measurements require calibration. Calibrations are typically performed using: Gas calibration cylinders of known composition, either gravimetrically prepared or certified using comparison methods Static or dynamic volumetric methods for the preparation of standard gas mixtures Permeation tubes and other blending devices such as mass flow controllers, capillary based gas dividers, etc. The key attributes of a gas calibration cylinder are: Stability the calibration standard shall remain at the certified value throughout the specified shelf-life and as the contents are depleted in use. In order to achieve stability, cylinders may require the passivation of the internal surfaces [75]. Accuracy the standard is fit-for-purpose and the measurement uncertainty is consistent with identified requirements for use and customer needs.

Traceability traceability depends upon a chain of standards linked back to an international primary standard through a series of calibrations, i.e. intercomparisons between two standards in the chain. The value of each standard in the chain must have a defined measurement uncertainty. Therefore, to ensure measurement accuracy, stability, traceable calibration and defined measurement uncertainty are required. See Fig. 1 : A traceability model. The Guide to the Expression of Uncertainty in Measurement [76], Quantifying Uncertainty in Analytical Measurement [77] and The Expression of Uncertainty and Confidence in Measurement [78] are all documents which give detailed guidance to enable the calculation of expanded uncertainties. The International Organisation for Standardisation (ISO) has defined measurement uncertainty as [79]: A parameter associated with the result of a measurement, that characterises the dispersion of the values that could reasonably be attributed to the measurand. The stages in the evaluation of measurement uncertainty are illustrated in Fig. 2. Sources of uncertainty in analytical procedures include: Sampling homogeneity, the number of replicate samples taken, variations in temperature and pressure during sampling Sample preparation the presence of dilution errors or contamination The presentation of certified reference material (CRM) to the measuring system the uncertainty of the CRM Calibration of the instrument Analysis and data acquisition Data processing, for example control of the rounding of results and the use of statistical treatments to derive results The presentation and interpretation of results.

Fig. 1 A traceability model

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indirect observation of a property is the objective for reasons of speed, simplicity and economy. Texts on the use of chemometrics in environmental chemistry have been published [81] and experimental design [82] and method validation [83], particularly in the pharmaceutical industry, are important to the analytical scientist. Procedures for chromatographic method validation have been reviewed by Jenke [8486] and the importance of method validation as a part of total quality management is discussed by Christensen et al. [87], who have illustrated the importance of correcting measurement errors by the use of reference materials. The Analytical Methods Committee [88] of the Royal Society of Chemistry has reviewed the concepts and practices of data quality in analytical chemistry in relation to measurement uncertainty. The use of statistics for the assessment of laboratory performance during interlaboratory testing has been reported and Schrantz et al. [89] have noted that the testing laboratories generally perform well in interlaboratory comparisons when reference materials are used to validate their analytical procedures. A review of the statistical methods used to analyse data from interlaboratory comparisons has been made by Feinberg [90].
Fig. 2 The uncertainty estimation process [80]

Conclusions
In summary, the analysis of process gases is necessary to monitor and control processes, thus enabling compliance with legislation and international standards. It also ensures operational safety and enables the production of a wide variety of items of consistent product quality in a cost-effective manner. In short, the analysis of process gases impinges upon virtually every type of industrial, medical and environmental activity and the accurate quantification of components present in a process stream, including trace constituents present as impurities, is essential and, in certain cases, this knowledge leads to competitive advantage. Future technical developments in process gas analysis are likely to focus on: The increased miniaturisation of equipment, with further developments in HSGC The wider use of broad-based techniques, such as mass spectrometry and IR spectroscopy, allowing the rapid acquisition of data from process streams via a single analyser system The continuation of the trend of locating instrumentation At-Plant with further software developments simplifying the user interface and allowing a greater use of statistical packages to control and optimise processes A greater emphasis on the benefits of accreditation and traceability with respect to gas calibration cylinders used to quantify components in process streams,

Data collection and processing

Commercially produced software is widely available for chemometrics, experimental design and statistical process control. Software is typically used to control: Instrument set up and optimisation Calibration and sampling, including external timed events such as valve switching, column switching, etc. Collection and quantification of analytical data The statistical treatment of results. As with other aspects of method development and process gas analysis the use of software requires validation. Chemometrics Chemometrics is an approach to analytical and measurement science based on the idea of indirect observation. Measurements related to the chemical composition of a substance are taken, and the value of a property of interest is inferred from them through a mathematical relation. Chemometrics works because the properties of substances, such as, say, gasoline, are uniquely defined by their chemical composition. The

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driven by requirements for robust data to enable cost savings and compliance with legislation, etc. In order to achieve these objectives consistently it is essential that a formal quality system is adopted. There are a variety of quality standards to which organisations and laboratories may become accredited. These include ISO EN 9000, ISO Guide 25 and ISO EN 45000. A new standard ISO/IEC 17025 : 1999(E), General requirements for the competence of testing and calibration laboratories will shortly replace the ISO Guide 25 and EN 45000. The accreditation to an external quality standard ensures that, in addition to the purely technical issues of method development and selection, instrument selection, sampling and calibration organisations also consider and document their approach to: The quality management system The organisation and responsibilities for quality The qualifications and training of staff

System review The use of calibration, testing equipment and reference materials Measurement traceability and calibration Record keeping, document and data control Handling complaints, anomalies and departures from documented procedures The participation in internal and external audit programmes, which may also include proficiency testing schemes and correlation exercises. The adoption of a formalised quality system and external accreditation to a quality standard by an independent agency will ensure a consistent approach to process gas analysis and importantly should therefore lead to comparability of measurements and hence results, which is a vital attribute in industrial, medical and commercial areas.

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