43
MEASURE BIOFUEL PARAMETERS When and Where You Need To Coen Duvekot Product Marketing Manager, MicroGC Frank Higgins Applications Development Specialist – Mobile Spectroscopy
MEASURE BIOFUEL PARAMETERS
When and Where You Need To
Coen Duvekot
Product Marketing Manager,
MicroGC
Frank Higgins
Applications Development
Specialist – Mobile
Spectroscopy
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Coen Duvekot
Product Manager Micro GC
March 2013
Fast and Efficient Solutions with
Agilent 490 Micro GC
A closer look the Biogas Analyzers
3
Micro GC
(PL9C)
Mobile FTIR
(PLMA)
Transportable
GC-MS (PLCA)
Mobile HPLC
(PL29)
Mobile Measurement Portfolio
1. 490 Micro GC General Introduction
2. 490 Micro GC Biogas Analyzer
Agenda
5
490 Micro GC Family
Basic cabinets, 19” rack and Field Case
The field case provides “on-the-go”
measurements
490 Micro GC Basic cabinets
2-Channel and 4-channel
The Agilent 490 Micro GC Family
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Mine Safety Monitoring Mine atmosphere,
potential for gas explosion,
early warning of spontaneous combustion
Biogas Analysis of Gases produced
by fermentation of biodegradable materials
Mud Logging Mobile labs on drilling rigs
analyzing hydrocarbons
in mud gases Solvent analysis BTEX, Solvents, Halogenated
Hydrocarbons…
Natural Gas On-/at line analysis of permanent gases,
hydrocarbons and odorants
Refinery Gas On-/at line and lab measurements of
saturated and unsaturated hydrocarbons Reaction Monitoring Research of renewable energy
(biomass gasification) and catalists
Permanent gases Oxygen, Argon, Nitrogen
Fuel Cells Analysis of fuel cell fuels
and reaction product
490 Micro GC: a portfolio of Lab and Mobile Applications
Factory Tested with Check-Out
sample
(delivered with the
Analyzer)
Analytical method
parameters, Data files,
User manual and Reports included *
Application Note,
Data Sheet and
“Solutions” web site
Made-to-stock,
available for shipment
from the LCs worldwide
Single part number, easy to
quote and order
Easy to Order Easy to Install Fast to
deliver
490 Micro GC Analyzers
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.
Reference [1]: http://en.wikipedia.org/wiki/Biogas
Reference [2], [3] and [4]: How to profit from biogas market developments; Global Intelligence Alliance
[3]
[2]
[4]
Biogas, what and why……
CP-Molesieve 5A – Permanent gases
• Biogas; composition CH4, CO2, N2 and some H2, O2 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
C3
Biogas Analyzer
• Biogas mixed with other hydrocarbon streams, like
Liquefied Petroleum Gas (LPG) or Natural gas
• Sample composition primarily CH4, CO2, N2; some H2, O2 and CO
and higher hydrocarbons
• Quad channel cabinet with
3 column channels
• Channel 1 & 2 identical to
biogas analyzer (#110)
• Part number G3582A +
G3582A#111
CP-Sil 5 CB – C4 to C7 hydrocarbons
Biogas Analyzer Extended
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
O2/ N2 separation CO and CO2 analysis Hydrogen sulfide analysis CH4, 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
Biogas Analyzers Overview
Available Sales Collateral
Application Note Data Sheet
+ Ordering guide
EZReporter for calorific value calculations
Product description Compatible with Supported standards
EZReporter for calorific value / BTU calculations
Agilent EZChrom 3.3.2., Agilent OpenLAB CDS EZChrom Edition and Agilent OpenLAB CDS ChemStation Edition
GPA 2172-09 ASTM D 3588-98 (2003)
ISO 6976 (1995)
• 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
“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
QC LAB407 - Forge Rd S.E. Calgary, AB T2H 0S9
INC
.
Customer Quotes
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Agilent Mobile Spectroscopy
5500/4500 FTIR Frank Higgins
Applications Development Scientist
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
Single Transmission Cell
• Fixed path length liquid transmission cell
– Standard 100µm
• Liquids only
• Quantitative analysis
– 50 ppm to 5 %
• Reproducible and easy to use
17
5500t FTIR
5500/4500 Series FTIR Sampling Interfaces
1. Place Sample
on Lower Window
3. Once in place analyze
the sample
2. Rotate into
place 4. Cleaning is easy!
Single Transmission Cell Operation
Biodiesel Analysis
• Use of biodiesel is increasing.
• 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.
Farnesane : Representative chemical structure for petroleum diesel fuel.
Typical unsaturated biodiesel molecule
Diesel vs. Biodiesel Chemical Structures
• 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
Biodiesel Analysis
• Regulatory methods for blending specify FTIR
• EN 14078 : 2009 Transmission Liquid Cell (0.05-20% biodiesel range)
• ASTM D7371-07 Mulitple Reflection ATR (1-100% biodiesel range)
• EN 14078 : 2009 requires two calibrations
• Range A : 0.05-3% 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 0.0010% (LOQ) .
• The biodiesel FTIR package comes standard with 100um, 500um, and 1000um pathlengths
• The pre-calibrated methods and models are provided.
• ASTM D7371-07 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 = 30-100% biodiesel
• The calibrations are created using partial least squares (PLS) chemometrics.
Biodiesel Analysis
• Agilent’s Biodiesel in Diesel Method is a hybrid of the EN 14078 : 2009 and ASTM
D7371 methods
• Agilent’s method uses the EN 14078 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 (0.001-100% biodiesel)
• The PLS calibrations allow for more accurate biodiesel quantitation for seasonal diesel formulations.
• The EN 14078 : 2009 is calibrated with a single “summer” type diesel fuel.
• Agilent’s Method provides an optional 20-100% 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.
Biodiesel Analysis
EN 14078 : 2009 Biodiesel in Diesel (0.05-20%) &
Agilent’s Biodiesel Method (0.001-100%)
Agilent 5500 DialPath
EN 14078 – 2009 (0.05-20%) 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 (0.001-0.5% Biodiesel)
4500/5500 DialPath Accessory –Closed
26
Biodiesel pct(1746.977 150.661)
biodiesel pct high(1361.730 1.625)
99.80pct biod, high cetane, 100um_2013-02-15t16-13-30(1)
1550 1500 1450 1400 1350 1300 1250 1200 1150 1100 1050
2.8
2.6
2.4
2.2
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
Wavenumber
Absorb
ance
biodiesel pct high(3469.365 2.377)
Biodiesel pct(1746.977 148.265)
99.00pct biod, high cetane, 100um_2013-02-15t16-21-31(1)
4600 4500 4400 4300 4200 4100 4000 3900 3800 3700 3600 3500 3400 3300 3200
0.10
0.08
0.06
0.04
0.02
0.00
-0.02
-0.04
-0.06
-0.08
Wavenumber
Absorb
ance
Biodiesel Analysis- Agilent Method 20-100% using
the 100um DialPath 4500/5500
27
1617
1819
20
21
22
23
24
25
26
27
2829
303132Quant Validation Plot for biodiesel pct highR²=1.000
0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
100
90
80
70
60
50
40
30
20
10
Peak Area
Concentr
ation
Biodiesel Analysis- Agilent Method 20-100%
Calibration Plot 100um DialPath 4500/5500
28
Quant Validation Plot for Biodiesel pct
R²=1.000
1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0 2.1
0.055
0.050
0.045
0.040
0.035
0.030
0.025
0.020
0.015
0.010
0.005
0.000
-0.005
Bio
die
sel C
on
ce
ntr
ation %
(v/v
)
Peak Height Absorbance
Biodiesel Analysis- Range A (1000um)
Biodiesel in Diesel Calibration Plot
1747.0
1950 1900 1850 1800 1750 1700 1650
1.4
1.2
1.0
0.8
0.6
0.4
0.2
Wavenumber
Ab
sorb
an
ce
0.5% biodiesel
0.025% biodiesel
Biodiesel Analysis- Range A Biodiesel in Diesel
Spectral Overlay 1000um
Bio
die
se
l % (
V/V
)(1
74
7.1
)
Biodiesel in Diesel EN 14078:2009 Range B
1820 1810 1800 1790 1780 1770 1760 1750 1740 1730 1720 1710 1700 1690 1680 1670 1660
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
-0.2
Wavenumber
Absorb
ance
Biodiesel Analysis- Range B Biodiesel in Diesel Calibration Plot
ASTM D7371-07 Biodiesel in Diesel (1-100%)
Agilent 5500a Multibounce FTIR
ASTM D7371-07 Biodiesel in Diesel (1-100%)
Multi-reflection Sampling Crystal – 5500a
14
60
17
41
14
36
12
45
1196
72
3
1170
1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700
1.1
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
Wavenumber
Absorb
ance
Biodiesel Analysis- ASTM D7371 Spectral Overlay (0-100% Biodiesel)
Biodiesel Analysis- ASTM D7371 Conditional Reporting
(EN 14078 : 2009 is Similar)
Biodiesel Analysis- ASTM D7371 Final Results Display for a 12%
Biodiesel Qualification Sample
• 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.
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 / 0257047 A1) or application note “Onsite FTIR quantitative analysis of
water in mineral-based oils using a novel water stabilization technique” (5991-
0672EN).
Biodiesel – Quality
38
1
2
345 6
7
8
16Quant Validation Plot for Bound GlycerinR²=0.996
0.09 0.10 0.11 0.12 0.13 0.14 0.15 0.16 0.17 0.18 0.19 0.20 0.21 0.22 0.23
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
Peak Height
Concentr
ation
Biodiesel – Quality Bound Glycerin Calibration Plot (100um
DialPath)
39
Re
fPe
ak3
(13
76
.2 1
.5)
4333.574 0.168
RefPeak1(723.673 1.647)
Bo
un
d G
lyce
rin
(34
67
.45
3 0
.23
1)
acid
nu
mb
er(
17
08
.92
0 0
.37
8)
Soap (1580.040 -0.190)
FA
ME
pct(
13
61
.2 1
.1)
Fre
e G
lyce
rin
(10
61
.16
0 0
.51
8)biod 0604, vial 100um_2013-02-13t14-26-32(1)
4500 4400 4300 4200 4100 4000 3900 3800 3700 3600 3500 3400 3300 3200 3100
0.8
0.6
0.4
0.2
0.0
-0.2
Wavenumber
Absorb
ance
Biodiesel – Quality Bound Glycerin Spectral Overlay
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 20-100%
Fuel - Biodiesel ASTM D7371-07 Version4.a2m Biodiesel 1% - 10%
*requires 5500/4500a w/ Multi-reflection ATR Biodiesel 10% - 30%
Biodiesel 30% - 100%
Fuel - Biodiesel EN 14078 2009 Version5.a2m Biodiesel 0.05% -0.5% (Range A 1000um)
*requires 5500/4500 DialPath Biodiesel 0.05%-3% (Range A 500um)
Biodiesel 3-20% (Range B 100um)
Peak area @ 1745 cm-1
Fuel - Water in Diesel Version4.a2m Water in diesel 100 ppm – 900 ppm
*requires 5500t/4500t or DialPath Water in diesel 900 ppm –3000 ppm
*requires Water in Oil Surfactant Kit Diesel oxidation
Fuel – Biodiesel B100 Quality Analysis Non-Stabilized Bound Glycerin
Acid Number
FAME %
Soap
Fuel – Biodiesel B100 Quality Analysis Stabilized Free Glycerin
Water (ppm)
Biodiesel Methods
Method Name Fuel Type Sample Interface Components Range
Fuel - Gasoline Analysis PAL Gasoline TumblIR MTBE 0.25-16.5 vol% ETBE 0.25-16.5 vol%
Ethanol 0.1-100 vol% Total Aromatics 0.5-45 vol%
Total Olefins 2-12 vol% Benzene 0.2-2.5 vol% Toluene 0.5-25 vol%
RON 85-97 MON 80-86 Water Relative
Fuel - Gasoline Water Analysis Gasoline TumblIR Water 150-6000ppm
Fuel - Water in Diesel Stabilized Diesel TumblIR Water 100-4000ppm
Oxidation Relative Fuel - Water in Gasoline (0-80%) Stabilized Gasoline TumblIR
Water 0 - 80 vol% Fuel - Gasoline in Diesel Version5 Diesel TumblIR
Gasoline 2000-10000ppm Oxidation Relative
Antioxidant 150-10000ppm
Petrochemical - Fuel Methods
•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
Biodiesel Analysis - Conclusions
