process solutions from wet chemistry to near-infrared spectroscopy
TRANSCRIPT
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Process Solutions from Wet Chemistry to Near-Infrared Spectroscopy – Ensure Product Quality & Prevent Downtime
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Tim Deschaines, Ph.D.Product Manager – Applikon GroupBased in Riverview, [email protected]
Introduction
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• Introduction to Metrohm-Applikon
• Overview of Process Analysis
• Applikon Process Analyzers
• Example Applications
Overview
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• 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
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Process Analysis
Inline
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• Online Process Monitoring and Control
Process Analysis
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• 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
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• 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
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Applikon Analyzer Options
ADI 201Y - Online
ADI 2045VA - Online Fully integrated solutions
ADI 2045TI - Online
ADI 2045PL - Atline
ADI Alert - Online
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Crude Oil Processing Applications
Applications
• NH3/H2S in SWS• KF in Crude Oil• TAN in Oil• Salt in Crude Oil
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• “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
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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
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• 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
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• DCS Flow Control
Caustic Scrubber
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Cau
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Actual Caustic Average = 4.81% Actual Caustic Standard Deviation = 1.61
Chlorscrubber DCS Flow Control
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• ADI Control – Metrohm-Applikon
Caustic Scrubber
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Cau
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Actual Caustic Average = 2.97% Actual Caustic Standard Deviation = 0.43
Chlorscrubber Titration Control
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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
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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
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Fueling Efficient Analysis: An Overview of the Use of
NIR in the Marathon Petroleum System
Lucy J. Thurston
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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
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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
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2 MINS VS 4 ½ HOURS
NIR vs Routine Gasoline Certification
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Knock Engine Room
NIR Set-Up in Knock Engine Room Knock Engine Room
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Gasoline Certification Lab NIR Set-Up
NIR Workstation System I Unit: Still in Use
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Spectral Deviations Between 84 & 91 Octane
84 Octane
91 Octane
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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
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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
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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
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Overview of Blend Optimization Process
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On-line NIR
New on-line NIR with sampling condition system
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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
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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
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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%
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Ethanol Percentage
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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
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Fatty Acid Methyl Esters (FAME)
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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
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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
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Thank You!
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Online NIR Applications in Polymer Industry
John MartinProduct Specialist Metrohm USA
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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
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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
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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)
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Instrumentation
Dispersive and PDA
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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#
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Polyol Process- Sampling Conditions
• 240C• Nitrogen sparging (bubbles)• Undissolved solids (turbid)• Turbulent mixing
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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
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Overtone Region
1300 1350 1400 1450 1500 1550 1600
Wavelength (nm)
0
0.1
0.2
0.3
-0.1
-0.2
-0.3
Sec
ond
Der
ivat
ive
(log
1/T
)
Acid Value
Moisture
Hydroxyl Number
Polyol Spectra – Overtone Region
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Combination Band Region
1820 1870 1920 1970 2020 2070
Wavelength (nm)
0
0.2
-0.2
Se
cond
Der
ivat
ive
(log
1/T
)
Acid Value
Moisture
Hydroxyl Number
Polyol Spectra –Combination Band
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Calibration Results: Hydroxyl Number
-
.
..
..
.,,,,.,,. ,. . . .
. ..
10 20 30 40 50 60
Laboratory Results (OH #)
10
20
30
40
50
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
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Calibration Results: Acid Value
.
.
.
.
.
.
..........
. . . ..
. ..
0 10 20 30 40 50
Laboratory Results (Acid Value)
0
10
20
30
40
50
Nea
r-In
frar
ed P
redi
cted
Res
ults
(A
.V.)
Validation Results:SEP = 0.26R = 0.99
Calibration Results: 1900 nmSEC = 0.28R = 0.99
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NIR Process Control Chart
*
*
**
*********
******** ** ***** ***** ** ****** ***************
-
-
- -- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
0 2 4 6 8
TIME (HOURS)
0
10
20
30
40
50
60
70
HY
DR
OX
YL
/AC
ID V
AL
UE
S
ACID VALUE
HYDROXYL #
-
*
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NIR Process Control Charts
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-
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-
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---------------------------
-------------------
-----------------------------------
------------------------------------------------------------
-----------------------------------------------------------------------
0 5 10 15 20
Time (hours)
100
150
200
250
300
Hyd
roxy
l N
um
ber
0
0.1
0.2
Water C
on
tent (%
)
Moisture
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)
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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
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Reactor Absorption Spectra
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Reactor Derivative Spectra
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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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0 25 50 75 100 125 150 175 200 225 250 275
Time(minutes)
0
0.1
0.2
0
2
4
6
8
10
Change Range
Batch Control charts
Ave
rage
Cha
nge
(%)
Ran
ge
(%)
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Primary and Routine Methods
• Hydroxyl Number• Acid Value• Isocyanate• Moisture
Primary Method -Titration Routine Method - NIR
Single MeasurementAll Parameters
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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
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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
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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
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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
54.0
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
21.0
24.0
27.0
30.0
33.0
36.0
39.0
42.0
45.0
48.0
51.0
54.0
57.0
60.0
63.0
Validation Set : Calculated vs Lab Data
R2 = 0.9830SEP = 1.94Compared to a Titration with a Visible Endpoint
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Trend Analysis
0
10
20
30
40
50
60
70
80
Ac
id V
alu
e
Time
NIR
LAB
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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.
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Thank You