Oil & Gas Application Notebook

Transcription

1 Natural Gas Oil & Gas Application Notebook AOX in Waste Chromatography, Mass Spectrometry, Molecular Spectroscopy,

2 Natural Gas Oil and Gas Production. The Global Challenge. Whether or not the oil and gas industry is in a boom or bust cycle, companies that succeed will be those that have learned to execute at a lower price point, by working with the supply chain in new ways. They will consider new technology that helps achieve higher product purity and improved production efficiencies. Making informed decisions on selecting drill sites, crude oil testing, custody transfer, contaminant analysis, and product purity testing requires appropriately configured, accurate, dependable, and cost effective analytical instrumentation. Thermo Fisher Scientific offers the most complete portfolio of analytical instrument workflow solutions in the industry. We deliver critical information about your upstream, midstream, and downstream production and industrial water preventative maintenance processes with a choice of available technologies and models that maximize instrument uptime. AOX in Waste Upstream Midstream Downstream Exploration Production Custody Transfer Storage Wholesale Marketing Refining Distribution

3 Natural Gas AOX in Waste The oil & gas industry is driven by two workflows, one for petroleum and natural gas processes and one for industrial water processes. The workflows can be described as a matrix that provides a choice of available products according to the process, matrices, application, and analytes of interest. Feed Stock Testing Natural Gas & Condensates Crude Oil Upstream Exploration & Production Biomarkers GC-HRMS CHNS/O and Heat Value OEA SIMDIS GC, GC-MS Midstream Transportation & Custody Transfer The petrolelum and natural gas workflow includes matrices for natural gas, condensates, and crude oil. Both are segmented according to upstream, midstream, and downstream sectors. Analytical instrumentation includes GC, GC-MS, GC-HRAM, ICP-OES, HPLC, organic elemental analyzers (OEA), and combustion IC (CIC). H 2 S, CO 2, NOx GC F, Cl, S Combustion IC Downstream Refining, Petrochemical, Energy Energy Content (BTU), DHA, SIMDIS, H 2 S/Organic Sulfur GC, GC-MS Sulfur, Metals ICP-OES F, Cl, S Combustion IC RGA, DHA GC, GC-MS Oxygenates, Aromatics GC, GC-MS BTEX 3, PAHs GC, GC-MS S, Metals PAH s ICP-OES HPLC, GC QA Products Download the brochure LIMS leverages all process steps

4 The industrial water processes workflow includes matrices for industrial water and scrubber solutions and is segmented according to process monitoring and waste water monitoring. Analytical instrumentation includes IC, ICP-OES, and GC, and GC-MS,. Natural Gas Industrial Process Monitoring Amines, Anions, Organic acids IC, GC TPH 1, HRVOC 2 GC, GC-MS Waste Monitoring Cations, Anions, Ammonium, Alkai & Alkaline Earth Metals IC, ICP-OES Organic Acids IC, GC Metals (e.g., Zn, Cd) ICP-OES BTEX 3, PCB 4 ASE, GC S ICP-OES AOX in Waste Scrubber Solutions 1. Total petroleum hydrocarbons 2. Reactive volatile organic compounds 3. Benzene, toluene, ethyl benzene, xylenes 4. Polychorlinatedbiphenyl Download the brochure Organic Acids, Sulfur Species, Amines, Alkanolamines Polyphosphates, Polyphosphonates IC Cations, Anions, IC, ICP-OES Products LIMS leverages all process steps

5 Natural Gas AOX in Waste Inductively Coupled Plasma Analyzer For ensuring consistent radial ICP-OES performance and accurate results with high matrix tolerance and stable operation Thermo Scientific icap 7000 Plus Series ICP-OES Analyzer Organic Elemental Analyzer For automated characterization of coal, crude, fuels, lubricants, and petrochemical products by determining nitrogen, carbon, hydrogen, sulfur, and oxygen Analytical Thermo Scientific FlashSmart Elemental Analyzer

6 Natural Gas AOX in Waste Natural Gas and Natural Gas Liquid Specifically configured turnkey GC analyzers equipped with the appropriate injectors, detectors, and columns to meet the regulatory requirements for a wide range of GPA, ASTM, ISO, and DIN methods Thermo Scientific TRACE 1310 Natural Gas and Natural Gas Liquid Hydrocarbon Processing A complete suite of gas chromatography solutions from simple single channel gas chromatographs to highly configured multi-channel, multi-valve systems to meet the varied demands of the hydrocarbon processing industry - HPI Analytical Thermo Scientific TRACE 1310 Gas Chromatograph

7 Natural Gas AOX in Waste Ion Chromatography For meeting your routine ion analysis demands with flexible detector configurations, automated consumables tracking, and the versatility to run under isocratic and gradient conditions Thermo Scientific Dionex Integrion HPIC system Combustion Ion Chromatography For achieving reliable, reproducible analysis of halides and sulfur in matrices such as coal, crude oil, LPG, fuels, and lubricants Analytical Thermo Scientific Combustion Ion Chromatography (CIC) system

8 Analytical Natural Gas and Analysis Integrated informatics, with connectivity between the LIMS and CDS, that enables real-time evaluation of results for process monitoring, ensuring that turnaround is timely and reducing the risk of lost quality or product AOX in Waste

9 Natural Gas AOX in Waste Petrochemical analysis can be challenging due to difficult matrices, a wide range of contaminants, and sensitivity requirements. We offer the broadest portfolio of laboratory GC, GC-MS OEA analytical instrumentation in the industry that work together to enhance your analytical capabilities and streamline your upstream, midstream, and downstream processes. CIC ICP-OES GC-HRMS Upstream Midstream Downstream Exploration Production Custody Transfer Storage Wholesale Marketing Refining Distribution

10 Nitrogen in Crude Oil Samples Data obtained from the analysis of nitrogen in crude by ASTM D5291 fall within the statistical margin of error using Thermo Scientific FlashSmart Elemental Analyzer. Fluoride in LPG Results comparing untreated with treated fluoride sample in LPG demonstrate the sensitivity of Thermo Scientific Mitsubishi combustion IC system. Natural Gas Nitrogen and Fluoride SIMDIS of Crude AOX in Waste Sample* Thermo Scientific ASTM ASTM Reproducibility N% value Robust Mean N% These Test Data *Characterization of lubricants and oils by the Thermo Scientific FlashSmart Elemental Analyzer Combustion Ion Chromatography with a Dionex Integrion HPIC System technical note

11 SIMDIS of Crude Oil Results show the boiling point range distribution of petroleum fractions using a TRACE 1310 Gas Chromatograph. The chromatogram shows analysis of crude oil by ASTM D7169. The report at the right shows the percent of material at specific boiling points Natural Gas Nitrogen and Fluoride SIMDIS of Crude AOX in Waste

12 Natural Gas BTU of NGLs and NGs Refinery Gas Liquid Samples AOX in Waste The midstream process involves the transportation, storage, and custody transfer of crude and refined petroleum products. Pipelines and other transport systems are used to move crude oil from production sites to refineries and deliver the various refined products to downstream distributors. NG, NGL Analyzer Combustion IC ICP-OES

13 Natural Gas BTU of NGLs and NGs Refinery Gas Liquid Samples AOX in Waste 37.5 mv 25.0 Determining BTU Content of NGLs Determination of the calorific value of natural gas liquids (NGL) by a TRACE 1300 Gas Chromatograph with thermal conductivity detection by GPA Method Minutes mv Methane Ethane Propane i-butane n-butane i-pentane n-pentane 2,2-Dimethylbutane 2,3-Dimethylbutane 2-Methylpentane 3-Methylpentane n-hexane Methylcyclopentane Benzene Determining BTU Content of NGs Determination of calorific value of natural gas (NG) by a TRACE 1300 Gas Chromatograph with FID Detection by GPA Method Minutes Natural Gas Analyzer for GPA 2177 Natural Gas Analyzer for GPA 2261 Natural Gas Analyzer for GPA 2186 Natural Gas Analyzer for GPA 2286 n-heptane Toluene n-octane n-nonane n-decane

14 Refinery Gas Analysis Three-channel systems provide a quantitative determination of hydrogen, permanent gases CO2, H 2 S, and hydrocarbons C1-C8 in refinery process gases, LPG gases, and mixtures of propane and propene (excluding high-purity propene in the range of C1-C5) using a TRACE 1310 Gas Chromatograph. Natural Gas BTU of NGLs and NGs Refinery Gas Liquid Samples Representative chromatograms Hydrogen Carbon Dioxide Methane-Porous Polymer Ethane Hydrogen Sulfide Oxygen Nitrogen Methane-MolSieve Carbone Monoxide Hexane Methane Ethane Ethylene Propane Propylene i-butane n-butane t-2-butene Butene Isobutylene c-2-butene i-pentane n-pentane ,3-Butadiene AOX in Waste Hydrogen Channel Permanent Gas Channel with H 2 S Light Hydrocarbon Channel GC for the Hydrocarbon Processing Industry GC Refinery Gas

15 GC for Liquid Samples Liquid streams in a refinery process require analysis by gas chromatography. BTEX in Natural Gas BTU of NGLs and NGs Refinery Gas Liquid Samples gasoline, SIMDIS of crude oil and semi-finished products, DHA, and oxygenates are a few examples. ASTM D2/D3 provide numerous methods describing these analyses, like ASTM D7423 oxygenates in light hydrocarbons shown below 100 ppm standard 20 oxygenates in LPG DME DEE AA ETBE MTBE DIPE PA TAME PE IBA BA MeOH Acetone VA MEK Ethanol i-propanol + n-propanol Allyl Alcohol i-butanol + t-butanol n-butanol AOX in Waste GC ASTM D7423 Analyzer

16 Natural Gas SIMDIS and Oxygenates Lubricants TEA in Naphtha Aromatics in Gas Organic acids LIMS AOX in Waste The downstream process refers to the refining of crude oil into petroleum products by distillation according to their boiling points. These products include the following; Light distillates; LPG C3-C4, gasoline (C3-C12), naphtha (C6-14) Middle distillates; kerosene, diesel (C9-C16), jet fuel (C9-C17) Heavy distillates; lubricating oil (C20+) GC, GC-MS ICP-OES IC HPLC

17 SIMDIS of Gasoline with Ethanol SIMDIS is used to determine the boiling point range of refined product. The chromatogram shows the composition of gasoline with ethanol by ASTM D7096 simulated distillation with a TRACE 1310 Gas Chromatograph. Oxygenates in Light HC Samples Analysis of corrosive oxygenates in LPG and other light hydrocarbons samples following ASTM D7423 using a TRACE 1310 Gas Chromatograph. Natural Gas SIMDIS and Oxygenates Lubricants TEA in Naphtha Aromatics in Gas Organic acids LIMS 600 pa ethanol 2,4-dimethylpentane n-c7 iso-pentane 2-methylpentane n-c5 n-c6 toluene n-c8 p-xylene n-propylbenzene n-butylbenzene n-c10 n-c12 n-c13 n-c14 n-c15 n-c16 n-c Minutes 33.1 pa 20.0 Reverse Flow Split/Splitless Injector: Simplification of ASTM D3606 and D4815 Methods DME 2-DEE 3-AA 4-ETBE 5-MTBE 6-DIPE 7-PA 8-TAME 9-PE 10-IBA 11-BA 12-MeOH 13 - Acetone Minutes 16-VA 17 - MEK 18 - Ethanol 19 - i-propanol+n-propanol 20-Allyl Alcohol 21-i-Butanol+t-Butanol 22-n-Butanol AOX in Waste

18 Natural Gas SIMDIS and Oxygenates Lubricants TEA in Naphtha Aromatics in Gas Organic acids LIMS Nitrogen Reproducibility of Lubricants Results from the analysis of nitrogen show excellent reproducibility of lubricants with helium and argon gases by ASTM D5291 with the Thermo Scientific FLASH 2000 Organic Elemental Analyzer. There were no observable matrix effects when changing lubricant samples. Sample Helium Carrier Gas Argon Carrier Gas Number N% Average N% RSD % N% Average N% RSD % AOX in Waste

19 Natural Gas SIMDIS and Oxygenates Lubricants TEA in Naphtha Aromatics in Gas Organic acids LIMS AOX in Waste Trace Element Analysis in Naphtha Results from the analysis of spiked naphtha are within acceptable limits of ±5% of the true values using Thermo Scientific icap 7600 ICP-OES. A cooled spray chamber reduces the volatility of the solvent, providing a more stable plasma for detecting trace elements at single digit ppb levels in complex matrices. Element and Wavelength (nm) Spike Concentration mg kg -1 Measured Spike Concentration mg kg -1 Spike Recovery % RSD on Three Replicates of the Spike % MDL µg kg -1 Ag Al As B Ba Ca Cd Cr Cu Fe Hg Mg Mn Mo Na Ni P Pb Si Sn Ti V Zn

20 Natural Gas SIMDIS and Oxygenates Lubricants TEA in Naphtha Aromatics in Gas Organic acids LIMS Benzene and Toluene in Gasoline Analysis of aromatics (used to boost octane levels in gasoline) is shown with backflush (right) and without backflush (left) using a TRACE 1310 Gas Chromatograph. In the right chromatogram the heavier matrix components are eliminated, leaving the column and detector cleaner. microvolts microvolts Minutes Minutes Simplication of the ASTM D3606 Method for the Determination for Benzene and Toluene in Gasoline AOX in Waste

21 Natural Gas SIMDIS and Oxygenates Lubricants TEA in Naphtha Aromatics in Gas Organic acids LIMS AOX in Waste Acetic Acid and Formic Acid in Diesel Motor Oil Results from a new IC method shows determination of acetic acid and formic acid in diesel containing 2% motor oil. (A) original sample (B) sample spiked with 10 mg/l of each organic acid (an offset of 20% was applied). Mixtures with up to 10% oil content, compatible with the Dionex Integrion HPIC system, showed no impact on the analytical performance, or method stability. κ (µs/cm) Acetic Acid Formic Acid t (min) CAN 72204: Determination of Formic and Acetic Acids in Petroleum Products (B) (A)

22 , Analysis, and Reporting LIMS can be integrated across the organization including lab instruments and applications as well as enterprise systems and systems Natural Gas SIMDIS and Oxygenates Lubricants TEA in Naphtha Aromatics in Gas Organic acids LIMS AOX in Waste SampleManager LIMS Solutions Implementation of Thermo Scientific SampleManager LIMS at Sinopec Guangzhou The Real Benefits of Standardizing on a Single LIMS in the Gas and Petroleum Industry Thermo Scientific Integrated Information Informatics Solutions for the Oil and Gas Industry

23 es Natural Gas AOX in Waste, Analysis, and Reporting Industrial water processes refer to preventative maintenance applications that keep a refinery operational. Alkaline scrubber solutions are used to neutralize corrosive acids such as H 2 S formed during distillation that left untreated can damage equipment and release toxic gases into the air. Boiler and cooling water, used to control the distillation temperature, are treated with amines to neutralize acidic steam condensate. IC GC, GC-MS ICP-OES

24 Natural Gas AOX in Waste Heat Stable Salts (HSS) in Scrubber Solutions Gradient separation of an aged refinery scrubber solution at a 1:1000 dilution. Resutls show clear resolution of corrosive anions, organic acids, thiosulfate, and thiocyanate using a Thermo Scientific Dionex IonPac AS25A column and Dionex Integrion IC system in less than 30 minutes µs new AS25A column #100 [manually integrated] CD_1_Total min es Peak Peak Name 1 Fluoride 2 Propionate 3 Formate 4 Chloride 5 Nitrite 6 Bromide 7 Nitrate 8 Carbonate 9 Sulfite 10 Sulfate 11 Oxalate 12 Iodide 13 Thiosulfate 14 Phosphate 15 Thiocyanate Separation of HSS in MDEA Solutions Using HPIC Using ion chromatography with electrospray ionization mass spectrometry for the determination of cations and amines in alkanolamine scrubbing solutions

25 es by IC Separation of a simulated solution of common cations and protonated amines used to neutralize the build-up of acidic byproducts and prevent expensive equipment damage using an Dionex Integrion IC System. Natural Gas 2 µs Peaks: 1. Lithium 2. Sodium 3. Ammonium 4. Ethanolamine 5. Potassium 6. Diethanolamine 7. Triethanolamine 8. N-Methyldiethanolamine mg/l AOX in Waste Minutes Determination of Diethanolamine and Triethanolamine in Surface Finishing, Wastewater and Scrubber Solutions

26 Natural Gas AOX in Waste Determination of inorganic anions in A) industrial wastewater and B) spiked industrial wastewater using a Dionex IonPac AS4A-SC column. 30 S 0 30 S 0 A B 1 2 Column: Dionex IonPac AG4A-SC, Dionex IonPac AS4A-SC Eluent: 1.8 mm Sodium carbonate/ 1.7 mm Sodium bicarbonate Flow Rate: 2.0 ml/min Injection: 50 µl Detection: Suppressed conductivity Dionex ASRS ULTRA suppressor, AutoSuppression recycle mode Peaks: A B 1. Fluoride mg/l (ppm) 2. Chloride Nitrite Bromide Nitrate o-phosphate Sulfate Minutes es Determination of Inorganic Anions in Wastewater by Ion Chromatography

27 es Natural Gas AOX in Waste Adsorbable Organic Halogen (AOX) in Waste An overlay of chromatograms of unspiked and spiked wastewater containing AOX by CIC using a Thermo Scientific Dionex IonPac AS18-4µm column and a Dionex Integrion IC System. Peaks (A): 1. Fluoride mg/l 2. Chloride Bromide Peaks (B): 1. Fluoride mg/l 2. Chloride Bromide µs B A Minutes Determination of Adsorbable Organic Halogen in Wastewater Using a Combustion IC

28 Additional Resources Oil and Gas Products Oil and Gas Information Oil and Gas Analyte Blogs Natural Gas AOX in Waste Find out more at For Research Use Only. Not for use in diagnostic procedures. AI72824-EN 0818S