Process Solutions from Wet Chemistry to Near-Infrared Spectroscopy – Ensure Product Quality & Prevent Downtime

Tim Deschaines, Ph.D.Product Manager – Applikon GroupBased in Riverview, FLtdeschaines@metrohmusa.com

Introduction

• Introduction to Metrohm-Applikon

• Overview of Process Analysis

• Applikon Process Analyzers

• Example Applications

Overview

• Global HQ in Schiedam, Netherlands• Development, Production, Global Distribution

• North America Operations• Tampa, FL

• Analyzer Assembly Operations• Application Support• Technical Support

• Houston, TX• Demos & Training• Technical Support• Service Operations• Application Support

• Toronto, Ontario• Sales Operations• Service Operations

Metrohm-Applikon

Process Analysis

Inline

• Online Process Monitoring and Control

Process Analysis

• Lab Analytics• <1% RSD• Response time – hours• Advanced technology• Professionally maintained• Clean Environment

• Process Analytics• <5-10% RSD• Response time – mins, secs• Simple technology• Reliability• Low maintenance• Harsh environment• Safety

Process Analysis

Typical Laboratory Typical Production

• A wide array of methods available for on-line, in-line, and at-line analysis

• Most common techniques:• Titration• Ion Selective Electrodes• Dynamic Standard Addition• Photometry/Colorimetry• Voltammetry• Near-Infrared (NIR)

• From % to trace (parts per trillion)

Analysis Methods

Applikon Analyzer Options

ADI 201Y - Online

ADI 2045VA - Online Fully integrated solutions

ADI 2045TI - Online

ADI 2045PL - Atline

ADI Alert - Online

Crude Oil Processing Applications

Applications

• NH3/H2S in SWS• KF in Crude Oil• TAN in Oil• Salt in Crude Oil

• “Sour water” – water that contains sulfur and ammonia• Formed when H2S is liberated in crude oil units during the

refining process. When H2S dissolves in water sour water is the result.

• Reuse or disposal of sour water requires removal of sulfides and ammonia.

Sour Water Stripping

Sour Water with NH3 &

H2S

Stripped Sour Water without NH3

& H2S

Sour Water Stripper

Sour/Acid Gas Removal

Analyzer for sour water monitoring Typical configurationDual Vessel: Left NH3

Right H2S

Analysis Range:NH3: 5-100 ppm

H2S: 0-50 ppm

Methods:Sulfide determined by precipitation titration with silver nitrate

S2- + 2Ag+ Ag2S

Ammonia determined by Dynamic Standard Addition titration

Sour Water Analysis

• Sodium/potassium Analysis indicates process conditions in a chlorine scrubber

• A single upset can lead to:• Loss of up to $100,000 of raw material• Product that is off-spec and can’t be sold• Reprocessing of product – costs $$$

• Example plant – 4 upsets per year

• Compare losses to cost of an analyzer and sample conditioning system

Caustic Scrubber

• DCS Flow Control

Caustic Scrubber

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Date/Time

Cau

stic

%

Actual Caustic Average = 4.81% Actual Caustic Standard Deviation = 1.61

Chlorscrubber DCS Flow Control

• ADI Control – Metrohm-Applikon

Caustic Scrubber

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stic

%

Actual Caustic Average = 2.97% Actual Caustic Standard Deviation = 0.43

Chlorscrubber Titration Control

Process Optimization – Improve quality, speed, safety, less waste, less variance, and save money

DCS Average: 4.8% CausticADI Average: 2.9% Caustic

(Now reduced to 2.0%)

Cost Savings:Approx. $1,000 a day savingsLeads to $200,000 a year savings

(4 on, 2 off schedule)

Caustic Scrubber

Summary:Process Analysis Overview Customizable analyzers: on-line and at-lineRange of Diverse ApplicationsProcess Optimization

Thank you for your attention to the Applikon part of the webinar, up next NIR applications.

Lucy J. Thurston, from Marathon Petroleum Company, will now talk about their Process NIR systems and applications

Conclusion

Fueling Efficient Analysis: An Overview of the Use of

NIR in the Marathon Petroleum System

Lucy J. Thurston

19

Laboratory Installations

Laboratory units installed at all 7 refineries– Measure RON/MON on finished gasoline & component

streams

– Aromatics

– Olefins

– Benzene

– Cetane

– Fatty Acid Methyl Esters

– CORE Aromatics

– Ethanol Percentage

20

Measured Property ASTM Method Length of Analysis

Octane Number (RON/MON Knock Engine)

D2699/D2700 1 hour each

Aromatics(GC/MS)

D5769 11 min per sample~ 1 hour due to QC in lab

Olefin(FIA – Fluorescent Indicator Analysis)

D1319 1 hour

Benzene(GC)

D3606 30 min

Cetane Number(Cetane Engine)

D613 1 hour

FAME, vol %(FTIR)

D7371 N/A

CORE Aromatics 1 hour + data processing

Ethanol, vol %(GC)

D5599 25 min

21

2 MINS VS 4 ½ HOURS

NIR vs Routine Gasoline Certification

22

Knock Engine Room

NIR Set-Up in Knock Engine Room Knock Engine Room

23

Gasoline Certification Lab NIR Set-Up

NIR Workstation System I Unit: Still in Use

24

Spectral Deviations Between 84 & 91 Octane

84 Octane

91 Octane

25

Basis of NIR Equations

Original NIR equations built from over 700 samples nearly 15 years ago

– In process of replacing 2 DOS-based units (only 1 left!!)

Still using same equation – Slope & bias adjust with updated sample set every 4-6

months

26

On-line Installations

6 Refineries are currently using on-line NIR for process control

– 3 very successful

– 3 just starting up within last 2 years

With on-line analysis able to achieve blend optimization

– Blend closer to targets

– Minimize give away

– Maximize profit

27

Daily analyses of component tanks

Daily analyses of unit run down streams

Information downloaded into blend program

Gasoline blend recipes generated from program based on tank inventories

Recipes updated based on analysis of finished gasoline

Pumper has ability to “tweak” blends based on real time data from on-line analyzers

28

Overview of Blend Optimization Process

29

On-line NIR

New on-line NIR with sampling condition system

30

Oversight Program

Acceptance of NIR results provides for more immediate recognition of potential issues

Over 4 years worth of NIR & Knock Engine analyses used to show the predictive abilities of NIR with r2

values of 0.983

For any gasoline with NIR (R+M)/2 greater than 0.3 below pump value, knock engine testing is required

To maintain equation, calibration sets are updated every 4-6 months

31

Oversight Program: NIR Technology Savings to Marathon

Totals as of 6/2010

Time per NIR

Time ASTM/IR

Test

NIR Octane 1436 2 min 1 hour

NIR Cetane 900 2 min 1 hour

NIR % Biodiesel

151 2 min 30 mins

~83 hours for NIR vs ~2400 hours for ASTM testing = $684,000 savings for 6 months

32

Ethanol Percentage

Have the predictive capability to determine octane in blends with up to 10% EtOH

Recently added equation for octane determination in blends with 10% EtOH and greater

During trial of XDS could determine EtOH percentages from 0 – 15%

33

Ethanol Percentage

34

Diesel & Biodiesel OversightNIR vs cetane motor to predict cetane number

Biodiesel Equations

Based on 6 refineries of base diesel & 3 sources of B100

0-5% curve to determine if any biodiesel is present – good to ~0.2%

5-25% curve to quantify percentage of biodiesel

35

Fatty Acid Methyl Esters (FAME)

36

Other Work

Useful in predicting oxygenates in reformulated gasoline when MTBE was used in blending

Distillation data – Prefer simulated distillation analyzers since analysis is ~13

mins

Presently working to predict various properties in jet fuel & kerosene

37

Conclusions

NIR has been a very useful tool in octane predictions for a number of years

Big push for smaller refineries in system to adapt to on-line blending techniques

As more & more mandates are pushed through, NIR providing to be reliable in prediction of ecofuels

38

Thank You!

Online NIR Applications in Polymer Industry

John MartinProduct Specialist Metrohm USA

Online NIR - Advantages

• Fast• Process Optimization

• End Point of Reaction monitoring• Reduce Over-Processing of Product• Improve Measurement Precision• Improve Production Consistency

• Multiple Analyses• Safety and Environmental

Real Time Monitoring using NIRSampling : Optical Consistency

Probes: Contact or ContactlessImmersion Probe: 0-15% dissolved solidsReflectance Probe: over 15% Solids

Fiber Optics: Connects Monochromator to Probe

• Fiber Material: Ultra Low Moisture Quartz• Fiber Counts: Illuminators/Collectors

• 1/1, 74/74, 210/210 • Fiber Diameters:

• Single Fibers 600 Microns• Bundles 200 Microns

• Fiber Length: 2 to 250 Meters

Sampling systems: Benefits

• Laminar rather than turbulent flow• No bubbles• Filtering possible (particulate/water)• Temperature control (better accuracy)• Accessibility to probe (for cleaning, running

calibration standards)• Ability to collect the sample at the same point

where the NIR collects the spectra (for calibration / validation /updating of the models)

Instrumentation

Dispersive and PDA

NIR - Polyols & Polyurethane

Matrix AnalytesOxide-based Polyols OH#

Primary OH#Secondary OH#EO/PO RatioResidual OxidesMoisture

Ester-based Polyols Acid ValueOH#

Substituted Polyols Primary AminesSecondary Amines

Polyurethanes Isocyanate LevelsOH#

Polyol Process- Sampling Conditions

• 240C• Nitrogen sparging (bubbles)• Undissolved solids (turbid)• Turbulent mixing

Reactor Spectra

1100 1400 1700 2000 2300

Wavelength (nm )

0

0.5

1

1.5

2

2.5

Abs

orba

nce

(log

1/T

)

Polyol Spectra

Overtone Region

1300 1350 1400 1450 1500 1550 1600

Wavelength (nm)

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ond

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ivat

ive

(log

1/T

)

Acid Value

Moisture

Hydroxyl Number

Polyol Spectra – Overtone Region

Combination Band Region

1820 1870 1920 1970 2020 2070

Wavelength (nm)

0

0.2

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cond

Der

ivat

ive

(log

1/T

)

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Moisture

Hydroxyl Number

Polyol Spectra –Combination Band

Calibration Results: Hydroxyl Number

-

.

..

..

.,,,,.,,. ,. . . .

. ..

10 20 30 40 50 60

Laboratory Results (OH #)

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60

Nea

r-In

fra

red

Pre

dic

ted

Res

ults

(O

H #

)

Calibration Results: 2030 nmSEC = 0.41R2 = 0.99

Validation Results:SEP = 0.38R2 = 0.99

Calibration Results: Acid Value

.

.

.

.

.

.

..........

. . . ..

. ..

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Laboratory Results (Acid Value)

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Nea

r-In

frar

ed P

redi

cted

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ults

(A

.V.)

Validation Results:SEP = 0.26R = 0.99

Calibration Results: 1900 nmSEC = 0.28R = 0.99

NIR Process Control Chart

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*

**

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******** ** ***** ***** ** ****** ***************

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TIME (HOURS)

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HY

DR

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YL

/AC

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AL

UE

S

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HYDROXYL #

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*

NIR Process Control Charts

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Time (hours)

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roxy

l N

um

ber

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on

tent (%

)

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Hydroxyl #

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-

Real-Time Monitoring of Polyurethane Batch Production

5000 Liter Batch Reactor

Temperature 55 ⁰ C

Immersion Probe: 300⁰C & 5000psi

Pathlength 1cm (5mm gap)

Raw Material Spectra

1100 1300 1500 1700 1900 2100 2300 2500

Wavelength (nm)

0

0.5

1

1.5

2

2.5

log(

1/T

)

Isocyanate

Polyol

Polyurethane

Reactor Absorption Spectra

Reactor Derivative Spectra

Isocyanate Calibration

2 4 6 8 10

Titrimetric Isocyanate (%)

2

4

6

8

10

NIR

Isoc

yana

te (

%)

Calibration: R2 =0.98 at 1648 nm, SEC=0.25%

Validation: R2 =0.97, SEC=0.23%

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Time(minutes)

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Change Range

Batch Control charts

Ave

rage

Cha

nge

(%)

Ran

ge

(%)

Primary and Routine Methods

• Hydroxyl Number• Acid Value• Isocyanate• Moisture

Primary Method -Titration Routine Method - NIR

Single MeasurementAll Parameters

Real-Time Monitoring of a Polyester Batch Reactor

• Acid Value• Trend Analysis• End Point Determination

• Nitrogen Purged• Two Stage Agitation• Ambient Pressure• High Temperature• Multiple Products

Bundle Fiber: With and Without Agitation

1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 2100 2200 2300 2400 25000.7150

1.1132

1.5114

1.9096

2.3077

2.7059

3.1041

3.5023

3.9005

4.2987

Wavelength

Ab

sorb

ance

Samples Spectra

1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 2100 2200 2300 2400 25000.7276

1.2441

1.7605

2.2770

2.7934

3.3099

3.8263

4.3428

4.8592

5.3757

Wavelength

Ab

sorb

ance

1306 1340 1374 1408 1442 1476 1510 1544 1578 1612 1646 1680 1714 1748 1782 1816 1850 1884 1918 1952 1986-0.8976

-0.7273

-0.5570

-0.3867

-0.2164

-0.0461

0.1242

0.2945

0.4648

0.6350

Wavelength

Inte

ns

ity

Calibration & Validation: Acid value

14.0 21.5 29.0 36.5 44.0 51.5 59.0 66.5 74.0

14.0

18.0

22.0

26.0

30.0

34.0

38.0

42.0

46.0

50.0

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58.0

62.0

66.0

70.0

74.0

Calibration Set : Calculated vs Lab Data

• PLS, 2 Factor• 1376-1472nm • and 1878-1936nm• R2 = 0.9945• SEC = 1.18

15.0 19.8 24.6 29.4 34.2 39.0 43.8 48.6 53.4 58.2 63.0

15.0

18.0

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24.0

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30.0

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36.0

39.0

42.0

45.0

48.0

51.0

54.0

57.0

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63.0

Validation Set : Calculated vs Lab Data

R2 = 0.9830SEP = 1.94Compared to a Titration with a Visible Endpoint

Trend Analysis

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id V

alu

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NIR

LAB

Summary• Choose the right analytical technique from wet

chemistry to spectroscopy suitable for your process applications.

• Sampling systems to improve sample presentation and measurement

• Stable NIR instrumentation improves method ruggedness & calibration stability

• Selection of correct probe and fiber count improves the accuracy and precision for process NIR applications.

Thank You