slide show ipal for biodiesel oiw ao & wio version 5plus work in progress
TRANSCRIPT
A2 Technologies / Agilent TechnologiesiPAL / PAL
with specific
reference to:1.Biodiesel in Diesel
2.Oil in Water
3.Anti-oxidants
levels of an oil
4.Water in oil
A2 Technologies Portable FTIR Spectrometers• A2 is focused on providing small portable FTIR spectrometers
– ML, MLp, PAL, iPAL
• Designed for use on a table or bench-top
– The ML and the PAL require mains power whereas the MLp and the iPAL are the battery powered analogues of the bench top instruments that can also function from mains power
– PAL and iPAL utilise A2 technologies patented Tumblir transmission cell that enables high throughput without the need for sample cells.
– Other sampling technologies available are:• ATR (a choice of either 1 bounce, 3 bounce or 9 bounce)• Gas cell (a choice of either 15cm or 50 cm)
A2 Technologies Portable FTIR Spectrometers
• All of A2 products measure mid-infrared spectra– Selective
• Spectra measured are unique to the chemistry of the sample
– Sensitive• Small changes in sample chemistry can be measured
– Universal• Most covalent chemical bonds can be measured
– All organic chemicals– Inorganics such as nitrates, phosphates, chlorates,
sulfates, etc.
• 8 lbs
• 8” x 8” x 4.5”
• External Computer
• USB connection
• External Power
• Full spectral analysis
• Designed for mobile/temp. labs
• 15 lbs
• 8” x 11.5” x 7.5”
• Integrated PDA computer
• Optional PC
• Internal battery
• Designed for field use
Common Specifications• Frequency range
– 4000 – 650 cm-1
• Maximum Resolution– 4 cm-1
• Non-hygroscopic optics– ZnSe beam splitter
• Power– 100 – 250 VAC 47 – 63 Hz, Output: 15VDC
• Operating temperature– 0 to 50 C⁰ ⁰
• Humidity– 95% non-condensing
PAL and iPAL• Particularly suited to Oil Analysis
– Predefined methods for many oil types• Turbine• Hydraulic• Motor oil• Gear• Bio-diesel in diesel
• Single sample interface-TumblIR– Oils, greases, pastes, emulsions– Oil in Water filtration technique– Fuels
ML/MLp Sample Interfaces• TumblIR
– Fixed path length liquid transmission cell• Standard 100µm
– Can be special ordered to 50µm or 200µm• Pre-defined Methods have been calibrated using 100µm
– Liquids only– Quantitative analysis
• 50 ppm to 5 %
– Reproducible and easy to use
ML/MLp Sample Interfaces
• TumblIR
1. Place Sample on Lower Window
3. Once TumlIR is in place analyze
the sample
2. Rotate TumblIR into place
4. Cleaning is easy!
• Typical Methods supplied with instrument– Gear Oil - Mineral Oil Based
• Gear Oil condition monitoring “Gear – ASTM E2412 EP Fluid Condition monitoring version 3”
– ASTM 2412 – Engine oil• Crankcase, polyol ester, EP fluid
“Engine – ASTM E2412 Crankcase Condition monitoring Version3”
• Transformer Oil • ASTM D2668
“Transformer oil – ASTM D2668 Version 3”
• Biodiesel in diesel• EN 14078, LOQ of 1%• A2 technologies Method, LOQ of 0.025%
“Fuel – Biodiesel % in Diesel Version4”
Measuring Biodiesel in Diesel Fuel• Biodiesel (FAME) can cause problems in stored
diesel fuel• Water, biological buildup, cold flow…
• % Biodiesel regulated in some areas• B5 – 5%, B10 – 10%, B20 – 20%
• Methods specified for blending B5 to B20• EN 14078• Specifies FTIR with transmission cell• PAL meets specification and has method installed
Note we have a an ASTM method (D73571-07) for B1-B100 (1%-100%) that uses a multi reflection diamond.
1.Measuring Biodiesel in Diesel Fuel
• A2 developed a more sensitive method to look at biodiesel contamination• 0.025% to 20% • Based on EN 14078 method (1% TO 15%)
• Developed for situations where biodiesel contamination can damage equipment Fuel injectors Filters Seal damage Microbial growth
1.5%
0.8%
0.5%
0.1%
0.05%
0.0%
0.025%
Measuring Biodiesel in Diesel Fuel
Biodiesel (FAME) has a strong infrared absorbance at 1745 cm-1
• Completely free of any diesel interference
Absorbance at 1745 cm-1 of biodiesel in diesel fuel at 0.0, 0.025, 0.05, 0.1, 0.5, 0.8 and 1.5 % (v/v).
Measuring Biodiesel in Diesel Fuel
Validation results for the Biodiesel in diesel method showing an average relative error of only 1%.
Calibration plot for Biodiesel in Diesel method showing excellent correlation
2. Measuring Oil in Water with iPAL/PAL
• Oil content in water is an important measurement• Discharge consent• Proper cooling water operation
• Both oil and water are strong IR absorbers• Traditionally solvent extraction used to separate the two
• Expensive, hazardous, environmental regulations
• A2 developed a filtration technique • Measure directly through filter.• Solventless extraction method• Reduced glassware, solvent use and simpler
Novel Oil in water Method using FTIR
Measuring Oil in Water with A2 OIW KitA2 sells a kit for measuring oil in water• Filters, glass wear and oil stabiliser included
• Only A2 filters should be used, other filters will yield inaccurate readings as our model has a method to compensate for the filter thickness that is specific to the type of filters used for extraction of the oil
• A2 method also warns the user if the filter has not been allowed to dry completely
Measuring Oil in Water
Spectra (A) and calibration curve (B) for oil in water using the A2 filter based method utilising Oil Stabiliser. Mineral oil in water from 0.5 to 45 ppm.
Spectra from filters Calibration chart from filters
SAMPLE RESULT10 mins
• Advantages• Completely Solvent free &
novel oil extraction method.• Only three steps.• Well established FTIR
technique.• <ppm limit of detection.• Sample to spectra then
actual result in ten minutes.• Very little sample
preparation.• On site testing possible.• Much reduced glass ware
usage compared to liquid-liquid extractions.
Microlab PC
3. Measuring Antioxidants in Turbine Oil with iPAL/PAL
3680 3675 3670 3665 3660 3655 3650 3645 3640 3635 3630 3625 3620 3615 3610Wavenumber
Abs
orba
nce
3680 3675 3670 3665 3660 3655 3650 3645 3640 3635 3630 3625 3620 3615 3610Wavenumber
Abs
orba
nce
3460 3455 3450 3445 3440 3435 3430 3425 3420 3415 3410 3405 3400 3395Wavenumber
Abs
orba
nce
3460 3455 3450 3445 3440 3435 3430 3425 3420 3415 3410 3405 3400 3395Wavenumber
Abs
orba
nceR
OH
R
OH
NH
R R
NH
R R
Aminic aDPA, alkyl di-phenylaminePhenolic DBPC, di-tertiary-butyl paracresol
3700 3690 3680 3670 3660 3650 3640 3630 3620 3610
Wavenumber
Abs
orb
anc
e
Example of Phenolic Antioxidant in Turbine Oil
Peak Area
1
4
7
10
13
16
19
22
25
28
Quant Validation Plot for Phenolic (ppm)R²=1.000
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
10000
9000
8000
7000
6000
5000
4000
3000
2000
1000
0
Con
cent
ratio
n
Range50 ppm to 5000 ppm
Accuracy+/- 10% relative
0.00
20.00
40.00
60.00
80.00
100.00
120.00
New
ISO 32
Oil
Day 1 Day 2 Day 5 Day 6 Day 8 Day 9 Day 12 Day 13 Day 16 Day 19 Day 22 Day 23 Day 24 Day 26
Phe
nolic
and
A
min
ic A
ntio
xida
nts
(% o
f C
onc.
in N
ew O
il)
0.00
5.00
10.00
15.00
20.00
25.00
Oxi
dati
on (
Pea
k A
rea
Abs
orba
nce)
Aminic Antioxidant
Phenolic Antioxidant
Oxidation
PASS MONITOR FREQUENTLY CHANGE IMMEDIATELY
Relationship Between Antioxidant Depletion
and Oxidation
1. Phenolic Diminishes 40% right away- Evaporation, Low molecular weight flash off
2. Aminic stays above 70% until near the end of useful life3. Aminic Stages of depletion
– Stage 1: Mid-way point in oil lifespan, 25% depletion– Stage 2: Decent from 80% to 40% after phenolic reaches 30%
0.00
20.00
40.00
60.00
80.00
100.00
120.00
NewISO 32
Oil
Day 1 Day 2 Day 5 Day 6 Day 8 Day 9 Day 12 Day 13 Day 16 Day 19 Day 22 Day 23 Day 24 Day 26
Ph
eno
lic an
d Am
inic A
nti
ox
ida
nts
(%
of
Co
nc.
in
New
Oil
)
0.00
5.00
10.00
15.00
20.00
25.00
Ox
ida
tio
n (
Pea
k A
rea
Ab
sorb
an
ce)
Aminic Antioxidant
Phenolic Antioxidant
Oxidation
PASS MONITOR FREQUENTLY CHANGE IMMEDIATELY
Critical Saturation of Oxidation Products
11 2
3.Stage 13.Stage 2
4. Water-in-Oil Analysis with iPAL/PAL• Traditionally water by FTIR is difficult • A2 has developed new methods to overcome these
limitationsFor all mineral oil based methods, two types of methods exist
– Water Stabilized– Non-stabilized
• Water stabilized methods use a surfactant to minimize water droplet size
– Improved water predictions– Both application note and video are available
• A2 Technologies sells a kit for water stabilization
A2 water stabilization method makes droplets uniform and small
Oil WITHOUT surfactant•Water in mineral oil forms irregular droplets• Water droplets that are of similar dimensions lead to scattering of the IR Beam• baseline is shifted•Reproducibility affected •Absorbance is reduced
Oil WITH A2 surfactant water stabiliser•Water in mineral oil forms smaller regular droplets• Water droplets that are now smaller than the wavelengths of the IR Beam and therefore scattering is no longer an issue• baseline improves•Reproducibility with surfactant much greater •Absorbance is increased•Accuracy greatly improved and comparable with KF
3410
.8
4600 4400 4200 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
0.022
0.020
0.018
0.016
0.014
0.012
0.010
0.008
0.006
0.004
0.002
0.000
-0.002
Wavenumber
Abs
orba
nce
WITHOUT surfactant
1127
.5 0
.313
6
34
54
.3
4200 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200
2000 1800 1600 1400 1200 1000 800 600
0.045 0.040 0.035 0.030 0.025 0.020 0.015 0.010 0.0050.000
Wavenumber
Abs
orba
nce
3x Abs
Reproducibility greatly improved
Baseline much improved
WITH A2 surfactant
PoorReproducibility
Baseline shift
Reduced Absorbance
Surfactant Quick Guide
1. Collect Kit and PAL2. Load Method3. Decant 20ml of Oil
sample into a suitable container.
4. Add 545l of water-in-oil stabiliser
5. Gently Swirl both clockwise and anti (~30s)
6. Run background for method then place a small drop of the stabilised sample into the well and run.
A2 Water Stabilization Method• Addition of surfactant to the oil
– Creates a stable emulsion– Maximum IR water absorbance achieved at 3% surfactant– Two different non-ionic PEO based surfactants used
• Three fold increase in water absorbance– Less IR scattered light, more absorbed– Smaller water particle (micelle) sizes, with a narrower
distribution• Water measurements are very reproducible• Variability in the non-surfactant method has been eliminated • Compares favourably with ‘Gold’ standard Karl Fischer method
turbine water surfactant.tdf,25 (R² = 0.998029969)turbine water surfactant.tdf,25 (R² = 0.998029969)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pred
icted
Con
cent
ratio
n ( F
4 C
1 )
Pred
icted
Con
cent
ratio
n ( F
4 C
1 )
-500
1000
2500
4000
5500
-500 1000 2500 4000 5500
-500
1000
2500
4000
5500
-500 1000 2500 4000 5500
12345678
9101112
13141516
17181920
21222324
252627
28
2931
32
33343536
37383940
41424344
45
46
4748
49505152
545556
57585960
616364
666768
-500
1000
2500
4000
5500
-500 1000 2500 4000 5500
turbine oil water.tdf,105 (R² = 0.859309544)turbine oil water.tdf,105 (R² = 0.859309544)
Actual Concentration ( C1 )Actual Concentration ( C1 )
Pre
dic
ted
Co
nc
en
tra
tion
( F
11
C1
)P
red
icte
d C
on
ce
ntr
ati
on
( F
11
C1
)
-400
200
800
1400
-100 200 500 800 1100 1400 1700
-400
200
800
1400
-100 200 500 800 1100 1400 1700
91
92
93
94
103
104105
106
107
118
119
120
121
122
133
134
135
136
145
146147
148
158
159
160
161
172
173
174
175
185186187
188
199200201202
211212213214
224
225
226
227
238239
240242
253254
255
256
265
266
267
268
277
278
279
280281
294295
296297
306
307
308
-400
200
800
1400
-100 200 500 800 1100 1400 1700
300ppm span500ppm Span
WITHOUTsurfactant
WITH
A2 technologies
Water Stabiliser
Part no# 0020-900
A2 Stabilized Water Method PerformancePAL (ppm) KF (ppm
Difference (ppm) % Error
525 504 21 4.2
1052 965 87 9.0
2027 2002 25 1.2
2914 2838 76 2.7
4835 4753 82 1.7
• Range– 75 – 5000 ppm– 0.075-5.0%
• Accuracy – +/- 10%
Benefits of A2 technologies method compared to KF:
• ppm of water results take the same spectral acquisition time and interpretation time regardless of the level of water.
•Virtually independent from operator removing the requirement of subjective ‘end point’ assignment.
•Does not interfere with any of the major additives or components in a oil therefore can measure water-in-oil concomitant with additives, breakdown products and contaminants
Application1.Biodiesel in DieselCorrelation of the carbonyl of the FattyAcidMethylEster (biodiesel) in Diesel.
2.Oil-in-Water (OIW)filtration with based technique requiring A2 technologies OIW surfactant and lipophilic filters.
3.Anti-oxidants levels of an oil Spectral analysis of peaks corresponding to the additives concurrent with oxidation. Other additives and/or breakdown products and/or contaminants can be quantified simultaneously.
4.Water-in-oil (WIO)A 20ml aliquot of the oil is mixed with a 545ul volume of WIO stabiliser, gently swirled, rested then analysed as normal.
1. iPAL, no additional requirements plus optional GC-MS accredited biodiesel in diesel Stds of 0%, 0.05% and 0.5% are available. (12 packs each with a set of three abovementioned stds).
2. iPAL + OIW kit / refill Kit For those without glassware and pipettes OIW kit is most appropriate alternatively the refill kit for those who either have the requisite glassware or have used up all their surfactant and filters).
3. iPAL, no additional requirements.
4. iPAL + WIO kit / refill KitFor those without pipettes the full WIO kit is most appropriate alternatively the refill kit for those who either have the requisite pipettes (one adjustable micro pipette and 20ml disposable pipettes or have used up all their surfactant and filters). Note sample bottles required for the mixing of the surfactant with the oils are not included and will require to be ordered by the end user.
Requirements
Nb: 3.&4. can be combined into a single method
Biodiesel in Petroleum Diesel