MEASURE. BIOFUEL PARAMETERS When and Where You Need To. Coen Duvekot Product Marketing Manager, MicroGC

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1 MEASURE BIOFUEL PARAMETERS When and Where You Need To Coen Duvekot Product Marketing Manager, MicroGC Frank Higgins Applications Development Specialist Mobile Spectroscopy

2 Fast and Efficient Solutions with Click to edit Master Agilent title 490 style Micro GC A closer look the Biogas Analyzers Coen Duvekot Product Manager Micro GC March 2013

3 Mobile Measurement Portfolio Micro GC (PL9C) Mobile FTIR (PLMA) Mobile HPLC (PL29) Transportable GC-MS (PLCA) 3

4 Agenda Micro GC General Introduction Micro GC Biogas Analyzer

5 The Agilent 490 Micro GC Family 490 Micro GC Family Basic cabinets, 19 rack and Field Case 490 Micro GC Basic cabinets 2-Channel and 4-channel The field case provides on-the-go measurements 5

6 490 Micro GC: a portfolio of Lab and Mobile Applications Click to edit Master title style Refinery Gas On-/at line and lab measurements of saturated and unsaturated hydrocarbons Biogas Analysis of Gases produced by fermentation of biodegradable materials Permanent gases Oxygen, Argon, Nitrogen Reaction Monitoring Research of renewable energy (biomass gasification) and catalists Natural Gas On-/at line analysis of permanent gases, hydrocarbons and odorants Mud Logging Fuel Cells Analysis of fuel cell fuels and reaction product Mine Safety Monitoring Mine atmosphere, potential for gas explosion, early warning of spontaneous combustion Solvent analysis BTEX, Solvents, Halogenated Hydrocarbons Mobile labs on drilling rigs analyzing hydrocarbons in mud gases

7 490 Micro GC Analyzers Easy to Order Easy to Install Fast to deliver Single part number, easy to quote and order Application Note, Data Sheet and Solutions web site Factory Tested with Check-Out sample (delivered with the Analyzer) Analytical method parameters, Data files, User manual and Reports included * Made-tostock, available for shipment from the LCs worldwide

8 Biogas, what and why Biogas is produced by anaerobic digestion or fermentation of biodegradable materials such as biomass, manure, sewage, municipal waste, green waste, plant material and energy crops. [1] Composition is related to the origin of the organic material. The main components are methane, carbon dioxide, other permanent gases, hydrogen and hydrogen sulfide. [2] [3] [4] Reference [1]: Reference [2], [3] and [4]: How to profit from biogas market developments; Global Intelligence Alliance

9 Biogas Analyzer Biogas; composition CH 4, CO 2, N 2 and some H 2, O 2 and CO Dual channel cabinet with 2 column channels Heated sample line and injectors Equipped with Backflush functionality UltiMetal treated sample lines: ready for H2S analysis Part number G3582A + G3582A#110 CP-PoraPLOT U C2, CO2, H2S and CP-Molesieve 5A Permanent gases C3

10 Biogas Analyzer Extended Biogas mixed with other hydrocarbon streams, like Liquefied Petroleum Gas (LPG) or Natural gas Sample composition primarily CH 4, CO 2, N 2 ; some H 2, O 2 and CO and higher hydrocarbons Quad channel cabinet with 3 column channels CP-Sil 5 CB C4 to C7 hydrocarbons Channel 1 & 2 identical to biogas analyzer (#110) Part number G3582A + G3582A#111

11 Biogas Analyzers Overview Depending on the composition of the biogas sample two 490 Micro GC based Biogas Analyzer configurations are available: Analyzer characteristics Biogas Analyzer Biogas Analyzer Extended O 2 / N 2 separation CO and CO 2 analysis Hydrogen sulfide analysis CH 4, C2 and C3 hydrocarbon analysis C4, C5, C6 and C7 hydrocarbon analysis Sample type biogas biogas and biogas mixed with other hydrocarbon streams (natural gas or LPG) Analysis time < 120 seconds < 150 seconds

12 Available Sales Collateral Application Note Data Sheet + Ordering guide

13 EZReporter for calorific value calculations Option number G3582A#105 External software compatible with Agilent CDS Key parameters available: In printed format As an export For monitoring incl min/max values For trend analysis Product description EZReporter for calorific value / BTU calculations Compatible with Agilent EZChrom , Agilent OpenLAB CDS EZChrom Edition and Agilent OpenLAB CDS ChemStation Edition Supported standards GPA ASTM D (2003) ISO 6976 (1995)

14 INC. Customer Quotes QC LAB Forge Rd S.E. Calgary, AB T2H 0S9 The 490-PRO Micro GC provides outstanding accuracy and longevity, requiring no maintenance over long periods of time. Two 490-PRO Micro GC s, installed by QC LAB in 1994, are still functioning and providing over 450 analyses per day, without any repair or loss of service. And on another system: Accuracy was recalculated in 2012 using the standard deviation over 10 calibration runs. Exceptionally good accuracy is still observed after 5 years of 24/7 operation. In that period, no maintenance was required and over 1 million (1,160,710) samples were analyzed. This corresponds to over 650 samples per day. Serge Syz, QC LAB Inc, Calgary, Canada 14

15 Click to edit Master title style Agilent Mobile Spectroscopy 5500/4500 FTIR Frank Higgins Applications Development Scientist

16 4500 Series FTIR Out of Lab System Physical Attributes 15 lbs 8 x 11.5 x 7.5 Integrated PDA computer Optional PC Internal battery Dedicated sample interface Designed for field use

17 5500/4500 Series FTIR Sampling Interfaces Single Transmission Cell 5500t FTIR Fixed path length liquid transmission cell Standard 100µm Liquids only Quantitative analysis 50 ppm to 5 % Reproducible and easy to use 17

18 Single Transmission Cell Operation 1. Place Sample on Lower Window 2. Rotate into place 3. Once in place analyze the sample 4. Cleaning is easy!

19 Use of biodiesel is increasing. Biodiesel Analysis Many countries allow or require biodiesel in regular diesel Some states allow up to 3% biodiesel in diesel without disclosure Biodiesel is not appropriate for all fuel uses Inappropriately used biodiesel can clog filters or reduce cold weather performance. Biodiesel can promote biological growth in long term fuel storage, Back up diesel generators for nuclear power plants Remote Locations or Critical applications Storage Depots Biodiesel contamination can reduce the oxidative stability of long term storage diesel. Overtime biodiesel, in temperature cycling conditions, can form oligomers that can plate out of diesel fuel to form harmful varnish deposits. The chemical structure of biodiesel contains an ester carbonyl that makes it a more polar solvent which can solubilize petroleum varnish deposits. These higher molecular weight petroleum varnish products can cause the clogging of engine components.

20 Diesel vs. Biodiesel Chemical Structures Farnesane : Representative chemical structure for petroleum diesel fuel. Typical unsaturated biodiesel molecule

21 Biodiesel Analysis The need exists to measure biodiesel with 3 different goals: Monitoring % biodiesel for fuel blending 5 volume % biodiesel = B5, 10% = B10, 50% = B50 Regulatory and compliance Detecting low levels of biodiesel as a contaminant 0.005% to 20% with a 30 second measurement Contamination needs to be determined onsite, before the fuel is pumped into tanks. Tanker truck deliveries have been rejected at nuclear power plants If not checked and a delivery is accepted, the facility is stuck with a costly problem Proving the source of contamination and cleaning up the large storage tanks is difficult. Residual biodiesel can be present in tanker trucks or fuel distribution pipelines from a previous biodiesel deliveries. Determining the quality of pure biodiesel, B100 21

22 Biodiesel Analysis Regulatory methods for blending specify FTIR EN : 2009 Transmission Liquid Cell ( % biodiesel range) ASTM D Mulitple Reflection ATR (1-100% biodiesel range) EN : 2009 requires two calibrations Range A : % using a high pathlength such as 500um or 1000um Range B : 3-20% using a standard 100um pathlength Agilent s 4500/5500 method includes a third calibration using the 1000um pathlength on the DialPath to provide measurement of biodiesel down to 10ppm or % (LOQ). The biodiesel FTIR package comes standard with 100um, 500um, and 1000um pathlengths The pre-calibrated methods and models are provided. ASTM D specifies 3 calibrations created with low, high and ultra high cetane petroleum diesel Calibration A = 1-10% biodiesel Calibration B = 10-30% biodiesel Calibration C = % biodiesel The calibrations are created using partial least squares (PLS) chemometrics.

23 Biodiesel Analysis Agilent s Biodiesel in Diesel Method is a hybrid of the EN : 2009 and ASTM D7371 methods Agilent s method uses the EN pathlengths, the ASTM D7371 sampling set, and the PLS calibration techniques similar to ASTM D7371 Lower limits of quantitation (LOQ) than the ASTM D7371 method ( % biodiesel) The PLS calibrations allow for more accurate biodiesel quantitation for seasonal diesel formulations. The EN : 2009 is calibrated with a single summer type diesel fuel. Agilent s Method provides an optional % range calibration Its our own development outside of the EN14078 : 2009 specified range Uses the harmonic overtone of the biodiesel s ester carbonyl group at 3470cm -1 and the biodiesel band at 1370cm -1 The biodiesel FTIR package comes standard with 100um, 500um, and 1000um pathlengths The pre-calibrated methods and models are provided.

24 Agilent 5500 DialPath EN : 2009 Biodiesel in Diesel ( %) & Agilent s Biodiesel Method ( %)

25 4500/5500 DialPath Accessory Closed EN ( %) Position 1 = 100um Range B (3-20% Biodiesel) & 3-100% with Agilents Biodiesel Method Position 2 = 500um Range A (0.05-3% Biodiesel) Position 3 = 1000um Range A ( % Biodiesel)

26 Absorbance Absorbance Biodiesel pct( ) Biodiesel Analysis- Agilent Method % using the 100um DialPath 4500/ pct biod, high cetane, 100um_ t (1) biodiesel pct high( ) pct biod, high cetane, 100um_ t (1) biodiesel pct high( ) Wavenumber Wavenumber 26

27 Concentration Biodiesel Analysis- Agilent Method % Calibration Plot 100um DialPath 4500/ Quant Validation Plot for biodiesel pct high R²= Peak Area 27

28 Biodiesel Concentration %(v/v) Biodiesel Analysis- Range A (1000um) Biodiesel in Diesel Calibration Plot Quant Validation Plot for Biodiesel pct R²= Peak Height Absorbance 28

29 Absorbance Biodiesel Analysis- Range A Biodiesel in Diesel Spectral Overlay 1000um % biodiesel % biodiesel Wavenumber

30 Absorbance Biodiesel % (V/V)(1747.1) Biodiesel Analysis- Range B Biodiesel in Diesel Calibration Plot 1.4 Biodiesel in Diesel EN 14078:2009 Range B Wavenumber

31 Agilent 5500a Multibounce FTIR ASTM D Biodiesel in Diesel (1-100%)

32 Multi-reflection Sampling Crystal 5500a ASTM D Biodiesel in Diesel (1-100%)

33 Absorbance Biodiesel Analysis- ASTM D7371 Spectral Overlay (0-100% Biodiesel) Wavenumber

34 Biodiesel Analysis- ASTM D7371 Conditional Reporting (EN : 2009 is Similar)

35 Biodiesel Analysis- ASTM D7371 Final Results Display for a 12% Biodiesel Qualification Sample

36 Biodiesel Quality In addition to Biodiesel contamination, the 5500/4500 can be used to determine fuel quality parameters. Agilent s B100 quality method measures the following components using the 100um Dialpath 4500/5500 Bound Glycerin Free Glycerin (requires stabilizer method) Total Glycerin = Bound Glycerin + Free Glycerin values Water (requires stabilizer method) Acid Number Fame Percent Soap Agilent s Stabilized B100 quality method requires the same surfactant stabilizer kit and procedure used in the oil analysis methods for water in oil / fuels.

37 Biodiesel Quality Our research indicates the glycerol or Free Glycerin is not soluble in biodiesel and therefore scatters IR light when mixed. Scattered IR light is not absorbed and therefore does not result in a measurable infrared absorbance band. The only possible way to see all of the free glycerin or water in a biodiesel sample by infrared spectroscopy is to extract it or dissolve it fully. Glycerol behaves very similar to water in oil. Described in Aglent s Water in Oil Measurement Using Stabilizer patent (US2009 / A1) or application note Onsite FTIR quantitative analysis of water in mineral-based oils using a novel water stabilization technique ( EN).

38 Concentration Biodiesel Quality Bound Glycerin Calibration Plot (100um DialPath) 0.7 Quant Validation Plot for Bound Glycerin R²= Peak Height 38

39 Absorbance Bound Glycerin( ) Biodiesel Quality Bound Glycerin Spectral Overlay biod 0604, vial 100um_ t (1) Wavenumber 39

40 Biodiesel Methods Method Name Components Fuel - Biodiesel % in Diesel Version5.a2m Biodiesel 0.001% 1% *requires 5500t/4500t or DialPath Biodiesel 1% - 10% Biodiesel 10% - 20% Biodiesel % Fuel - Biodiesel ASTM D Version4.a2m Biodiesel 1% - 10% *requires 5500/4500a w/ Multi-reflection ATR Biodiesel 10% - 30% Biodiesel 30% - 100% Fuel - Biodiesel EN Version5.a2m *requires 5500/4500 DialPath Fuel - Water in Diesel Version4.a2m *requires 5500t/4500t or DialPath *requires Water in Oil Surfactant Kit Fuel Biodiesel B100 Quality Analysis Non-Stabilized Fuel Biodiesel B100 Quality Analysis Stabilized Biodiesel 0.05% -0.5% (Range A 1000um) Biodiesel 0.05%-3% (Range A 500um) Biodiesel 3-20% (Range B 100um) Peak 1745 cm -1 Water in diesel 100 ppm 900 ppm Water in diesel 900 ppm 3000 ppm Diesel oxidation Bound Glycerin Acid Number FAME % Soap Free Glycerin Water (ppm)

41 Petrochemical - Fuel Methods Method Name Fuel Type Sample Interface Components Range Fuel - Gasoline Analysis PAL Gasoline TumblIR Fuel - Gasoline Water Analysis Gasoline TumblIR Fuel - Water in Diesel Stabilized Diesel TumblIR Fuel - Water in Gasoline (0-80%) Stabilized Gasoline TumblIR Fuel - Gasoline in Diesel Version5 Diesel TumblIR MTBE vol% ETBE vol% Ethanol vol% Total Aromatics vol% Total Olefins 2-12 vol% Benzene vol% Toluene vol% RON MON Water Relative Water Water Oxidation Water Gasoline Oxidation Antioxidant ppm ppm Relative 0-80 vol% ppm Relative ppm

42 Biodiesel Analysis - Conclusions The 4500t/5500 DialPath or Multireflection ATR can be used for multiple biodiesel analysis applications Biodiesel Blending, B5, B10, B50 etc Biodiesel Contamination in diesel fuel Mainly long term or remote diesel storage applications 3 Methods are available Calibrations are pre-defined in the Microlab software and use conditional reporting features Pure Biodiesel (B100) quality analysis Measures some critical quality parameters, such as Bound Glycerin, Free Glycerin, Acid Number, and water Water in oil surfactant technology applies to biodiesel as well as other fuels, such as diesel, gasoline, and crude oil Makes FTIR water and glycerol measurements consistent Calibrated to Coulometric Karl Fischer water

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