PEFTEC 2015 - Conference Review

Day 1: 'Environmental Monitoring, Process Monitoring and Regulation in and around petroleum and petrochemical plants'

The opening presentation was given by Mike Spence from Concawe, a research organisation working on behalf of the oil industry. During his presentation, Mike explained that Europe's environment is probably better today than at any time since 1900, thanks to the enhanced environmental control measures taken by industry, both voluntarily and in response to the legislation developed in the EU. For example, data collected by Concawe on behalf of EU petroleum refiners since 1969 has demonstrated that Total Petroleum Hydrocarbons (TPH) emissions to water have been considerably reduced despite growth in throughput over the past 40 years. This is because the majority of European refineries are now using the best available technology (3-stage) for water treatment.

To meet environmental challenges Concawe has extended its monitoring of sector performance to include site water usage and 50 effluent quality parameters, including refining Best Available Techniques Associated Emission Levels (BAT-AEL's), reportable substances and other parameters specifically mentioned in operating permits. This factual data collected by Concawe will continue to assist its membership in maintaining past achievements, responding to new scientific and regulatory developments and enabling the management of the further environmental improvements that are required for sustainable water management in a cost efficient manner.

Speaking on behalf of Arcadis and the Energy Institute, Katy Baker then outlined a case study on the measurement of priority substances and priority hazardous substances in discharges from the 8 UK refineries, as required by the Priority Substances Directive (2008/105/EC), a daughter of the Water Framework Directive (WFD, 2000/60/EC). This work indicated that it will not be necessary to lower refinery emission limits further in the future to meet WFD objectives. The methodology and the results of the study were shared, providing a potential framework for undertaking comparable studies in the future.

Steven Van de Broeck from cefic, the European Chemical Industry Council, then gave a presentation outlining the challenges that are created by the growing list of chemical species that have to be monitored for regulatory purposes. For example, he said that the need to measure micro-pollutants such as organic substances and metals at very low levels, means that reliable and reproducible analytical methods with a sufficiently low limit of quantification are necessary.

In a presentation which began with an explanation of the importance of the European petrochemical industry, Prof Philip de Smedt from Petrochemicals Europe emphasised the role of the crackers which transform crude oil and natural gas into valuable building blocks, such as ethylene, for the chemical industry. However, despite growth in ethylene demand of 2-3% worldwide, the EU is the only region where no new cracker has been built since 2001. Philip said the main reasons for this are the competitive disadvantages of the EU with respect to feedstock and energy price, and the additional burden caused by regulations such as REACH, ETS and the Industrial Emissions Directive (IED). He then outlined the potential impact for existing crackers of the IED and the related BREFs (Best Available Techniques Reference Documents) process, including the proposed BAT-AEL (Associated Emission Levels) in the revised BREF LVOC (Large Volume Organic Chemicals). Looking forward, Philip predicted a growing demand for continuous monitoring of the main pollutants and validation checks between spot measurements and continuous monitoring.

Fugitive emissions were a common theme among many of the Conference and Seminar presentations. Rod Robinson from NPL in the UK, described some of the work that NPL is involved with in the development of standard methods for the measurement of fugitive emissions in the petrochemical industry. He began by summarising European regulations, in particular the refining BREF document which requires the monitoring of fugitive emissions, and then provided an update on the status of the European Standardisation activities in CEN TC 264 WG38 which is developing and validating methods for monitoring fugitive emissions. Rod also summarised recent research projects to develop and improve fugitive emission measurements, including the development of Differential Absorption Lidar (DIAL) and remote sensing methods monitoring fugitive Methane emissions (FuME).

Following a similar theme, Dr Charlene Lawson from Concawe, summarised the results from several leak detection and repair field campaigns that compared two methods for the detection of refinery fugitive VOC emissions: Sniffing and Optical Gas Imaging. Both of these methods are described as Best Available Techniques in the BREF document for refining of mineral oil and gas. The comparison of these methods was made quantitative by using a bagging technique to explicitly measure emission rates. It was found that Optical Gas Imaging was very successful in finding the majority of the mass emissions and therefore can be considered as effective as Sniffing and as a standalone leak detection and repair method.

Katy Baker returned to the speakers’ podium to deliver a presentation outlining the lessons learned following the Buncefield Oil Storage Terminal (UK) explosion in December 2005. This included an explanation of the new environmental guidelines for facilities storing bulk quantities of petroleum, petroleum products and other fuels.

Mike Spence then delivered a second presentation in which he provided information on a trial being conducted by Concawe in collaboration with TOTAL looking at dosed refinery effluent and its effect on various organisms. There is increasing recognition by regulators that there are limitations to the substance-specific approach for assessing and controlling the environmental fate and effects of effluents. As the number of compounds of interest increases, this method becomes increasingly time consuming and costly. Consequently, many regulators are seeking more holistic techniques such as whole effluent assessment (WEA) to supplement existing approaches. Using a series of artificial streams, the trial monitors the effect of refinery effluents on simulated aquatic ecosystems, and calibrates the findings against laboratory whole effluent toxicity bioassays and the output of numerical models (PETROTOX). The main objective of the project is to show the real distance between WEA methodology, which is conservative, and in-situ impact measurement for risk assessment. Mike explained that the results suggest that there is a good dose response for a given hydrocarbon blend, and that these results will be used to inform hydrocarbon toxicity models.

Located at the Antwerp Expo, PEFTEC took place very close to the Port of Antwerp, which includes the world’s largest cluster of petrochemical companies outside of the United States. Speaking on behalf of the Port, Eric de Deckere gave a presentation on sustainability reporting. He said the port’s performance in terms of people, planet and prosperity was mapped for the first sustainability report which was produced in 2012. Recently the Port of Antwerp launched its third sustainability report. The report addresses environmental themes such as the emission of sulphur dioxide and fine particles, carbon dioxide emission, energy consumption and water usage. However, mobility, information transfer, research and innovation, safety and security, employment, education and economic performance, are also included.

Following the themes outlined in Rod Robinson’s presentation, Fabrizio Innocenti, also from NPL, gave a presentation describing the Application of Differential Absorption Lidar (DIAL) for Pollutant Emissions Monitoring. He described the DIAL system operated by NPL, and presented a number of case studies which included the emissions measurement of VOCs, methane and benzene from different areas of a site including process areas, storage tanks, water treatment plants, delayed cokers, loading and unloading operations and flares. Comparisons of DIAL measurements with other techniques were also provided including the results of validation studies against known releases.

The measurement of fugitive emissions was also the subject matter of Petroula Kangas’s presentation. Representing the ExxonMobil Research and Engineering Company, Petroula explained that Method 21 uses screening values and empirical relationships developed from field test data to estimate (not measure) the mass rate of fugitive emissions using concentration data measured near the potentially leaking component. She said this method is labour intensive, which means that compliance with Leak Detection and Repair (LDAR) requirements can be costly. However, Optical gas imaging (OGI) technology offers productivity improvements that could significantly reduce the costs for LDAR compliance.

With support from the ExxonMobil Research and Engineering Company and ExxonMobil Upstream Research Company, Providence Photonics, LLC has been developing a quantitative OGI technology, or QOGI, that could become a viable alternative to Method 21. This QOGI technology has been demonstrated using controlled lab and field experiments to determine the volumetric and mass rates of simulated leaks.

In the final presentation of the first day, Mrs Janneke van Wijk, from VSL, the Dutch Metrology Institute, described a project to assess the equivalence of measurement standards maintained by national metrology institutes. This included an update on the status of the reference materials programme and the proficiency testing programme, and the further development of calibration facilities for mercury analysis, stack gas simulation facilities and biogas composition analysis.

Day 2: 'Analytical Techniques, Methods & Laboratory Sustainability in Petroleum and Petrochemical Laboratories'

Since 2008, the University of Rostock and the Helmholtz Zentrum München have been cooperating in the development and application of mass spectrometry-based analytical techniques for the characterisation of complex molecular substance mixtures. Setting the theme for the second day, Prof Ralf Zimmermann from the group said that the analysis of complex petrochemical fractions and oil matrices still represents a challenge for analytical chemistry. His presentation explained the analysis of the chemical signature of complex petrochemical mixtures with thermal analysis coupled to photo ionisation mass spectrometry and gas chromatography-high resolution-mass spectrometry.

Following a similar theme, Dr Mark Barrow, from the University of Warwick in the UK, provided an introduction to ultrahigh resolution mass spectrometry (particularly Fourier transform ion cyclotron resonance, FTICR) and petroleomics. This included a range of example applications such as: comparison of naphthenic acid profiles for different crude oils (work from 2000-2003); differentiating origins by ultrahigh resolution profiles in Athabasca oil sands samples; crude oil profile comparisons after exposure to UV and sunlight (simulated); coupling gas chromatography and atmospheric pressure chemical ionisation (GC-APCI) with FTICR mass spectrometry; MS/MS (dissociation) experiments to gain structural insight into petroleum components, and preliminary work with the ionisation of paraffins/saturated alkanes.

In a presentation entitled ‘Novel Technologies for Petroleum Analyses,’ Dr Eleanor Riches from Waters Corporation explained how techniques such as Atmospheric Pressure GC (APGC), Atmospheric Solids Analysis Probe (ASAP) and ion mobility coupled to mass spectrometry along with PetroOrg© software offer additional, complementary information to more widely used techniques. Eleanor demonstrated the utility of several novel techniques, including for example, APGC for petroleum biomarkers discovery and for spill identification and environmental forensics. Using the high specificity of exact mass precursor and fragment ions, hopane and sterane biomarkers can be readily identified, and the soft nature of APGC ionisation means that it is possible to acquire data showing both intact precursor ions and related fragment ions. Eleanor also showed the applicability of ASAP for rapid qualitative analysis of petroleum from different geographical sources.

As a specialist delivering forensic and problem solving/method development capabilities for BP Fuels and Lubricants businesses globally, and with 35 years of experience in the Petroleum industry, Tom Lynch is well placed to comment on challenges in analytical petrochemistry. He prefaced his presentation by reminding the audience that the petroleum and petrochemical industry is highly regulated and the majority of analyses are carried out using industry standard methods such as those published by ASTM, DIN or the Energy Institute. He said these methods are also used to check for product quality excursions when field issues are encountered, but in many cases more sophisticated techniques are required. Tom then described approaches to problem solving field issues using flexible hyphenated chromatographic and mass spectrometry systems, citing examples from a range of typical issues encountered in the petroleum and related industries.

Describing Supercritical Fluid Chromatography - Mass Spectrometry and Petrochemistry as a ‘Perfect Marriage,’ Dr John Langley from the University of Southampton in the UK, gave a presentation in which he highlighted recent instrumental developments that have delivered a robust SFC technique. He said that the solvent compatibility, solvation power, selectivity and peak capacity of modern SFC coupled with mass spectrometry represents the ideal analytical platform for the analysis of many petrochemical species. He also gave a brief introduction to modern UHPSFC-MS followed by examples using Waters Acquity Ultra Performance Convergence Chromatography (UPC2™) mass spectrometers. The application of different ionisation techniques was also discussed in relation to the analysis of a number of different petrochemical applications, including biodiesel and corrosion inhibitors.

Hyphenation was also discussed by the next speaker; Dr Vicente L. Cebolla from the Instituto de Carboquimica in Spain - a public research centre belonging to the Spanish National Research Council (CSIC). Vicente explained that recent instrumental developments in the modularity of High-Performance Thin-Layer Chromatography (HPTLC) have created a high degree of flexibility and reliability. Different hyphenation strategies are now possible according to a particular analytical issue, with the additional possibility of evaluating only selected target zones of a chromatographic plate without the need for conducting a complete experiment. This, together with high sample throughput and low solvent consumption, leads to significant savings in the cost of analysis.

HPTLC has rarely been used for analysing petroleum products and biodiesel. However, Vincente provided two examples to illustrate its potential application. First, a hyphenated procedure (AMD induced fluorescence-ESI/MS, MS-MS and High Resolution, HR-MS) which allows separation, quantification and composition profiling of lipids in biodiesel (BX), from a unique silica gel plate. MS/MS and HR-MS spectra are obtained directly from the plate through the interface, using quadrupole ion-trap and μ-QToF-MS technologies, respectively. The second example concerns SARA analysis of heavy petroleum products. Using AMD is a useful alternative to obtain different separations with increasing levels of complexity for products which include bitumens, refining products, asphaltenes, and base oils. Gradient conditions can be fine-tuned at will for expanding separation in desired zones of the chromatogram.

Alyson Fick from ASTM International described method development and the periodic review process so that methods can be updated to accommodate changing technologies and markets. Dr Larry Tucker from Metrohm USA, then provided case studies to illustrate the standards development process for an ongoing revision to an existing standard and for two proposed new methods: 1) for testing water in ethanol and hydrocarbon blends by Karl Fischer titration and 2) for testing the acid number of crude oils and petroleum products. Reference was also made to the ASTM proficiency test program for petroleum products via the Interlaboratory Cross Check Program (ILCP) for laboratories to monitor their performance in executing test methods.

In a presentation addressing the chemical fingerprinting of crude oils, Dr Laura McGregor from Markes International explained the advantages of two-dimensional gas chromatography with time-of-flight mass spectrometry (GCxGC-TOF MS). Despite this enhanced separation, the identification of individual compounds in complex samples may become complicated when similar mass spectral characteristics are evident across entire chemical classes. Branched alkanes are a prime example, with weak molecular ions that further complicate the process. Spectral similarity can be addressed by the use of soft ionisation to reduce the degree of ion fragmentation, but this approach has been cumbersome to implement until now. Select-eV ion-source technology addresses this problem through the ability to switch effortlessly between hard and soft electron ionisation without loss in sensitivity. The novel ion source provides enhanced molecular ions whilst retaining structurally-significant fragment ions, thus simplifying the identification of isomeric compounds. The enhanced sensitivity and selectivity stemming from the dramatic reduction in fragmentation at low energies also greatly increases the number of compounds confidently identified, permitting the robust statistical comparisons that are essential for successful chemical fingerprinting.

Recent developments in capillary flow technology (CFT) were outlined by Bart Tienpont from the Research Institute for Chromatography in Belgium. He explained that the latest CFT devices enable flexible configurations that can be applied to various petrochemical applications covering a wide boiling and polarity range of solutes. CFT interfaces are non-moving inert in-oven capillary connections that have low thermal mass and low dead volumes. As these interfaces can also be connected to an electronic pressure/flow controller, they allow smart column configurations that permit column coupling, back-flushing, flow splitting and flow selection or heart-cutting.

Helium is often used as a carrier gas in gas chromatography. However, Dr Jaap De Zeeuw from Restek Corporation gave a presentation demonstrating that Nitrogen can be employed successfully, maintaining the same separation efficiency, retention times and peak elution order, without changing the oven temperature conditions. Besides guaranteed availability, using nitrogen, he explained, lowers costs and carrier gas consumption. However, there is a loss in loadability, so this concept is not ideal for every application.

Fast response times are necessary in some elemental analysis applications, and Prof Gerhard Wiegleb from the University of Applied Sciences Dortmund, Germany, gave a presentation on the combined NDIR- and NDUV-technology that has been developed for the measurement of SO2 and CO2. In this application, solid samples (e.g. steel, ores, finished metals and other inorganic materials) are combusted in a RF-furnace.

The new gas sensor design is based on a photometer principle using multiple channels for SO2/CO2 for ppm-levels and vol.-% levels. The measuring range varies between 2000 ppm and 10 Vol.-% with a detection limit of 3.σ = 100ppb for SO2 (UV-Detection) and 3.σ = 500ppb for CO2 (IR-Detection) using a 10 cm gold plated sample cell, with a cell volume of less than 5ccm. The response time ranged between t=100ms and t=800ms at different detection limits. For typical applications the trade-off between response time and detection limit was 600ms.

The main gas detectors employed in chromatography applications include Flame Ionisation Detectors (FID), Electron Capture Detectors (ECD), Thermal Conductivity Detectors (ECD), Photoionisation Detectors (PID) and Mass spectrometers (MS). A Multimode Plasma Emission Detector can also be utilised and Yves Gamache from Analytical Flow Products explained how this technology can be employed for the measurement of many different chemical compounds over a large dynamic range.

In the final Conference presentation of PEFTEC 2015, Dr Frank David, also from the Belgian Research Institute for Chromatography, provided an overview of some recent developments in GC-MS hardware and their application in petrochemical analysis. This included the use of high resolution accurate mass spectrometers for speciation of contaminants in hydrocarbon fractions and for the analysis of petroleum biomarkers. Soft ionisation techniques that can be applied as an alternative to or complementary with electron ionisation, were also discussed. This includes chemical ionisation, atmospheric pressure chemical ionisation (APCI) and supersonic molecular beam cold EI. The potential of these techniques was illustrated with a number of applications, including the analysis of phthalates, wax fractions and petroleum derivatives. Multidimensional techniques, including heart-cutting GC-GC and comprehensive GCxGC in combination with MS techniques were also discussed