the uses of portable ft-ir spectroscopy in the power generation industry the power... · in the...

The Uses of Portable

FT-IR Spectroscopy

in the Power

Generation Industry

Confidentiality Label

1

Jim Fitzpatrick

Mobile FT-IR Product Specialist

Agilent Technologies, Inc.

July 16, 2013

Spectroscopy

“Spectroscopy” is the study of how electromagnetic radiation interacts with the atoms

and molecules that compose matter

“Infrared” spectroscopy is specifically the study of how infrared light (heat) is

absorbed by the bonds between atoms that form molecules


A spectrum is a graph of how much infrared light is absorbed

by molecules at each wavenumber of infrared light


Peaks appear where sample

absorbs light

Infrared

(heat)

Source

Infrared

Detector

2

Hexane


H – C – C – C – C – C – C – H

H

|

H

|

H

|

H

|

H

|

H

|

|

H

|

H

|

H

|

H

|

H

|

H

C – H stretch

H – C – H bend

Ab

so

rban

ce

Wavenumber (cm-1)

Hexanol


4

H – C – C – C – C – C – C – O – H

H

|

H

|

H

|

H

|

H

|

H

|

|

H

|

H

|

H

|

H

|

H

|

H

C – O stretch O – H stretch

Ab

so

rba

nc

e

Wavenumber (cm-1)

What role can FT-IR play in the

Power Generation Industry?


5

FT-IR


6

Infrared has been an

established method for

over fifty years

Relegated to laboratories

due to

• Its large size

• Complexity of use

• Expensive

• Generates data and not

actionable answers.due

to

• Its large size

Mobile FT-IR

•Agilent has pioneered the

introduction of portable

spectrometers

•Comparable results to

laboratory spectrometers

•Field-ruggedized for non-

ideal conditions

•Intuitive, actionable answers

•Methods driven software –

expert user not required


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Analysis of Lubricants

- Lubricants protects parts, inherent part of a machine (without it, the machine does not function

properly) and prevent premature system/ machine failure

- Lubricants have a finite life (determined by certain specifications) beyond which they do not perform their role.

- Without a proper lubrication management program, lubricated machines and engines see their operating costs and maintenance costs skyrocket

- FT-IR spectroscopy can easily determine if an oil is fit for function or not

8


Causes of oil failure

The most common cause of failure of lubricating oil is oxidation.

Oxidation is caused by:

• Heat

• Extreme Pressures

• High sheer conditions

• Water – Accelerates oxidation by forming peroxides

– Can cause wash out of antioxidants and other additives

• Metal wear particles – Acts as a catalysts that accelerate oxidation

• Electrostatic sparking – Introduces nitrates


9

Early detection of oxidation in oil is critical to

the success of any preventative maintenance

program

Oxidation

• Oxidation is a chemical change within the lubricating oil that significantly lowers it

lubricity and shortens remaining useful life.

• It is critical to extend the life of the lubricating oil and to minimize oxidation. This is

done with the use of anti-oxidants

• Aminic and Phenolic Based Additives are sulfur based –

- They function as preservatives to prevent oxidation and to inhibit the

oxidation mechanism

- Will not reverse oxidation damage

- Once they are consumed, consumed oxidation skyrockets


10

Infrared Spectrum of Oil


11

Phenolic

Antioxidant Water/

Amine

Antioxidant

Various Oxidation/

Nitration Products,

and Additives

Demulsifying

Agents, Rust

Inhibitors, Foam

Suppressants,

And Antioxidants

Hydrocarbon Oil Backbone

3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600

2.0

1.8

1.6

1.4

1.2

1.0

0.8

0.6

0.4

0.2

0.0

Wavenumber

Measuring Anti Oxidants in Turbine Oil

R

O H

R

O H

N

H

R R

N

H

R R Phenolic DBPC,

di-tertiary-butyl

paracresol

3680 3675 3670 3665 3660 3655 3650 3645 3640 3635 3630 3625 3620 3615 3610 Wavenumber

Absorb

ance

3680 3675 3670 3665 3660 3655 3650 3645 3640 3635 3630 3625 3620 3615 3610 Wavenumber

Absorb

ance

3460 3455 3450 3445 3440 3435 3430 3425 3420 3415 3410 3405 3400 3395

Absorb

ance

3460 3455 3450 3445 3440 3435 3430 3425 3420 3415 3410 340

5

3400 3395

Wavenumber

Absorb

ance

Aminic aDPA, alkyl di-phenylamine

12


Phenolic/Aminic Antioxidants in Turbine Oil

3700 3690 3680 3670 3660 3650 3640 3630 3620 3610

Wavenumber

Ab

so

rba

nce

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

Concentr

atio

n

13


Typical Oil Monitoring Graph (applicable to all

sorts of Oil)


14

Water – The tribologists nemesis

Water Contamination in power generation turbines causes premature failures • Loss of physical properties of the oil

–Viscosity –Specific Gravity or Density –Surface Tension –Cohesion and Adhesion properties

• Oil loses its ability to coat, lubricate, and protect critical

clearances

• Water accelerates additive depletion and oxidation mechanisms


15

Water in oil – A difficult measurement

Why is it so hard to measure water in oil?

• Lack of Homogeneity

– Water forms micelles in oil

– Water adheres to container walls

– Separates out quickly (demulsifiers present)

– Forms layers

– Water droplets are attracted to each other

and air bubbles

• Water evaporates into container head space after mixing


16

Problems with Water Measurement

Water in mineral oil forms small, irregular droplets

Droplet can scatter the light

Scattered light shifts baseline and reduces absorbance

Water stabilization method makes droplets uniform and small

I

R Detector

Scatter

Large droplets => IR scattered

I

R

Detector

Small droplets => IR absorbed

17


Water Measurement Comparison

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

nce

ntr

atio

n (

F1

1 C

1 )

Pre

dic

ted

Co

nce

ntr

atio

n (

F1

1 C

1 )

-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

185

186187

188

199200201

202

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 span

500ppm

span

4000 2600 1600

Absorb

ance

Water OH

stretch

Conventional Method

1127.5

0.3

136

4000 3400 2600 1600

Absorb

ance

turbine water surf actant.tdf ,25 (R² = 0.998029969)turbine water surf actant.tdf ,25 (R² = 0.998029969)

Actual Concentration ( C1 )Actual Concentration ( C1 )

Pre

dic

ted

Co

nce

ntra

tion

( F

4 C

1 )

Pre

dic

ted

Co

nce

ntra

tion

( 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

2122

2324

252627

28

2931

32

33343536

37383940

41424344

45

46

4748

49505152

545556

57585960

61

6364

666768

-500

1000

2500

4000

5500

-500 1000 2500 4000 5500

A2 Water Stabilizer method produces a more sensitive, reproducible result.

Stabilization Method

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19

PAL Predictions: Water in Turbine Oil w/

Surfactant Stabilizers

PAL (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

Analysis performed in less than 1 minute

Usefulness of FT-IR for oil analysis


20

Method Types Turbine Oil – • Mineral Oil • Synthetic

Hydraulic Fluid • Mineral Oil • Polyol Ester Synthetic • Phosphate Ester Synthetic

Gear Oil – • Mineral Oil • Mineral Oil / Synthetic

Engine Oil • Mineral Oil • Synthetic

Components Water Anti-Oxidants

Phenolic Quantitative 150 to 5000 ppm

Aminic Quantitative 150 to 5000 ppm

Oxidation Additives

Antiwear Extreme Pressure

Soot Quantitative 0 – 3 %

FT-IR provides an early warning on oil failure based on chemical changes within the oil

FT-IR Spectroscopy - Operation


21

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Single Transmission Cell Operation

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1. Place Sample

on lower Window 3. Analyze the sample

2. Rotate into

place 4. Cleaning is

easy!


Easy-to-understand results

23


Petrochemical - Oil Methods

Gear ASTM 2412 EP Fluid Mineral

DTE PM 220 Mineral

EP 460 Mineral

Spartan EP 220 Mineral

Terrestic 220 Mineral

Duolec LE 1606 Iso 320 Mineral

Duolec LE 1607 ISO 460 Mineral

Mobile 600 XP ISO 460 Mineral/Synthetic

Mobile SHC 220 Mineral/Synthetic

Mobile SHC 636 ISO 680 Mineral/Synthetic

Mobile SHC 636 ISO 68 Mineral/Synthetic

Royal Purple Synfilm 220 Mineral/Synthetic

SL 150 Mineral

SL 220 Mineral

SL 320 Mineral

SL 460 Mineral

Hydraulic ASTM 2412 Polyol Ester Synthetic/ Polyol Ester

Calpar 150 Mineral

Mobile DTE (24, 25, 26) Mineral

EHC (Fyrquel) Phosphate Ester

Exxon Nuto 68 Mineral

Hitachi HN 46 Mineral

Cheveron H46 Mineral

HyGuard Mineral

Quinplex White LE 4010 H1 ISO 46 Mineral

Quinplex White L4030 H1 ISO 100 Mineral

Monolec LE 61110 ISO 46 Mineral

Royal Purple Synfilm GT 100 Synthetic/ Mineral

Quintolub 822-300 Synthetic Polyol Ester

Quintolub 888-68 Synthetic Polyol Ester

24


Turbine

Busch Mineral

Monolec LE 6404 ISO 100 Mineral

Royal Purple Syndraulic ISO 32 Synthetic/ Mineral

Exxon Terrestic GT 32 Mineral

Turbine Oil Mineral

Chevron GST Mineral

Engine ASTM 2412 Crankcase Mineral

Crankcase Oil (A2 Method) Mineral

Military Oil Mineral

Rotella T 15w40 Mineral

Mobile 1 Synthetic

Transformer

ASTM D2668 - Antioxidants

Compressor

Monolec LE6403 ISO 68

Crude

Water in Crude Oil (0 - 1%)

Water in Crude Oil (0 - 80%)

Other

Antifreeze in water

Water in ethanol

Oil in water (0 - 30 ppm)

Petrochemical - Oil Methods (cont.)

25


Detects common contaminations of oil

• Phosphate ester (EHC) hydraulic in turbine, gear, or mineral based hydraulic fluids – “Fingerprint” IR bands for EHC

– Cross contamination from filtration & dehydration units

• ID and/or Quantify a range of impurities

–WD-40 in Hydraulics

–High particulates like Soot, Dirt, and wear metals

Contaminant Detection By FT-IR

26


Environment – Oil in Water

High solids in water requires solvent extraction

•Process waters from offshore oil drilling

•Accidental oil spills

•Harbor water cleanup

•Waste water regulation

Low solids in water can be done with

non-solvent filtration system and FT-IR

•Closed loop turbine cooling water

Good for medium to heavy oils

•Not as good for light

hydrocarbons (i.e. BTEX)

27


Environment –

Oil in Water by Extraction

•Oil in water a key environmental measurement

•FT-IR measurement by Extraction

– Historically extracted by Freon 113 (ASTM D3921)

– Currently extracted by S 316 (ASTM 7066-04)

– Also extracted by cyclohexane in ASTM D7678

•Oil measured directly in extracted fluid using Transmission

•Agilent 4500/5500 DialPath makes measurement easy

– Easy to clean liquid cell

– Reproducible path length

– Easy to use software

28


Environment – Oil in Water by Cyclohexane

Extraction (ASTM D7678)

• Previous Freon FT-IR extraction method is being phased out

- Freon and other halogenated solvents have been banned by the Montreal

protocol due to their ozone depleting activity

• Cyclohexane is a CFC-free non-ozone depleting solvent

• Agilent’s FT-IR version of the ASTM D7678 features a limit of quantification

(LOQ) of .75mg/L (0.75ppm) oil in water

• Standard procedures for liquid-liquid solvent extraction remain unchanged from

previous ASTM methods.

• These ASTM D7678 based FT-IR results will correlate to other methods

- ASTM D3921, D7066, ISO 9377-2, EPA 413.2, and 418.1 methods

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Simple 5 step process –

1. Add Cyclohexane

Add 20mL of cyclohexane to 900mL of process water and vigorously

shake for 2 minutes.

2. Remove Top Layer

Allow layers to separate, and remove the top layer for analysis

3. Add Cleaning Agents

Add 2g drying agent (sodium sulfate) and 2g Florisil™ to the cyclohexane

extract, shake vigorously, and allow to settle for 2minutes.

4. Filter Cyclohexane Extract

Filter the “cleaned” cyclohexane with a 0.45um nylon syringe filter (17mm).

5. Measure FTIR Spectrum

Add the cyclohexane to the Dialpath™ or TumblIR™ cell and initiate the FTIR

scanning. The result will be displayed after 30seconds of scanning.

Environment – Oil in Water by Cyclohexane

Extraction (ASTM D7678) Simplified Procedure

30


The automatically obtained data results from the MicroLab software for the

4500series and 5500series FTIR spectrometers.

This result is from a validation standard of 9.3mg/L mineral oil and 5mg/L

vegetable oil in fresh water, then extracted with 20mL cyclohexane and filtered.

31


The mineral oil in cyclohexane calibration plot of actual (x-axis) vs. predicted

(y-axis) values. The values displayed are the final concentrations of oil in water

based on the ASTM D7678 parameters (900mL water, 20mL cyclohexane).

Oil Calibration Set

Standard Name Oil (mg/L)

OIW Soln A 0.00

OIW Soln B 0.05

OIW Soln C 0.15

OIW Soln D 0.26

OIW Soln E 0.84

OIW Soln F 1.70

OIW Soln G 2.54

OIW Soln H 4.20

OIW Soln I 8.30

OIW Soln J 16.54

OIW Soln K 24.90

OIW Soln L 32.55

32


Fuel Analysis By FT-IR


33

Petrochemical - Fuel Methods

In addition to oil analysis, FT-IR can be used to determine fuel quality parameters. • Water Contamination

– Gasoline – Diesel

• Gasoline contamination in diesel

• Gasoline performance characteristics

– Oxygenates, RON, MON, Aromatics

34


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 0.1-16.5 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 Version3 Diesel TumblIR

Gasoline 1000-20000ppm Oxidation Relative

Antioxidant 150-10000ppm

Petrochemical - Fuel Methods

35


Gasoline in Diesel Fuel

Gasoline fuel contamination in diesel fuel causes engine failures

-- Causes coke formation on fuel injectors, and excessive wear on fuel contact

parts

-- Problem is worse in Ultra low sulfur diesel (ULSD) engines

Much less lubricity than off-road, agricultural or older diesel formulations

Sulfonated hydrocarbons are removed in ULSD

Gasoline can wash varnish deposits into the engine

Lowers the diesel cetane value or energy content

Manufacturers want proof of no gasoline in diesel for warranty engine repairs


36

Gasoline, 87 Oct

Diesel


Wavenumber

3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0.0

Absorb

ance

Ethanol Light

Aromatics

37


1150 1100 1050 1000 950 900 850 800 750 700

0.60

0.55

0.50

0.45

0.40

0.35

0.30

0.25

0.20

0.15

0.10

0.05

0.00

-0.05

Wavenumber

Ab

so

rba

nce

Ethanol, Gasoline

Diesel Aromatics

Toluene,

Gasoline

Benzene, Gasoline

0.0% Gasoline

0.5% Gasoline

1.5% Gasoline

3.0% Gasoline

5.0% Gasoline


38


Biodiesel Analysis

Increased use of Biodiesel. 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

Can clog filters, reduce cold weather performance, or cause problems with storage Need exists to measure biodiesel for 2 different goals

Monitor % biodiesel for blending B5, B10, B50 Regulatory and compliance

Monitor low levels of biodiesel as a contaminant 0.025% to 20%

Regulatory methods specify FTIR

EN 14078 : 2009 Transmission Liquid Cell ASTM D7371-07 Mulitple Reflection ATR

39


Petrochemical - Biodiesel Methods

Method Name Components

Fuel - Biodiesel % in Diesel Version4.a2m Biodiesel 0.025% – 1%

*requires 5500t/4500t Biodiesel 1% - 10%

Biodiesel 10% - 20%

Interference – water vapor

Interference – diesel oxidation

Fuel - Biodiesel ASTM D7371-07 Version3.a2m Biodiesel 1% - 10%

*requires 5500/4500 w/9 reflection ATR Biodiesel 10% - 30%

Biodiesel 30% - 100%

Fuel - Biodiesel EN 14078 Version3.a2m Biodiesel 0.5% -20%

*requires 5500t/4500t Peak area @ 1745 cm-1

Fuel - Water in Diesel Version4.a2m Water in diesel 100 ppm – 900 ppm

*requires 5500t/4500t Water in diesel 900 ppm –3000 ppm

*requires Water in Oil Surfactant Kit Diesel oxidation

40


Agilent 5500a Multibounce FT-IR

ASTM D7371-07 Biodiesel in Diesel (1-100%)


41

Material Verification /Degradation


39

Hand Held FTIR Material Identification Germanium ATR

43

•Selectivity of FT-IR is ideal for material

identification.

•Well suited to polymers and elastomers

•Ge ATR ideal for carbon filled materials

•Industrial need for positive ID

•O-rings and seal materials

•Safety requirement to prevent leaks

•Compatible with the use of XRF for pipes


Exoscan can identify all 10 groups of seals Fluorosilicone, Silicone, Viton, EPR/EPDM, Neoprene, Butyl, Kalrez, NBR,

Polyurethane, Natural Rubber

Easy Identification by spectral search Similarity = correlation

Highest correlation = correct ID

Demonstration 15 samples provided by Material Research Society

Exoscan correctly identified all samples

Only one sample had a close second match

Hand Held FT-IR Material Identification O-ring and Seal Identification

44



45


46

Cable Degradation Analysis

Cables in a nuclear power plant are submitted to a variety of environment stressors

Heat,

Humidity,

Steam,

Dust,

Oil,

UV exposure,

Radiation.

The protective jacket made from XLPE, EPR, Hypalon, EPDM etc are losing their

original properties

Insulating power,

Mechanical properties.

Hand-held FT-IR provides a means for non-destructive cable analysis in the field.


47

Degradation at elevated temperatures over time


48

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49

the uses of portable ft-ir spectroscopy in the power generation industry the power... · in the...

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