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TRANSCRIPT
Applied Analytics, Inc.
ApplicationsApplications
Process control
Quality assurance
Environmental complianceIndustries
• Petrochemical• Chemical• Pharmaceutical• Pulp & Paper • Natural Gas
• Metal recovery• Power plants
Applied Analytics, Inc.
•Hydrogen Sulfide
•Sulfur dioxide
•Mercaptans
•Chlorine
•Chlorine dioxide
•Ozone
•Hydrogen Peroxide
•Bromine, Bromide, Methyl Bromide
•Nitrogen oxides
•Metal Ions, CU+2,
Some of the Hundreds of Measurable Chemicals
•Acetone
•Acetaldehyde
•Acetic Acid
•Acetamide
•Ammonia
•Aromatics (BTX)
•Iodide, Methyl Iodide
•Phenols
•Nitromethane
•Color
Applied Analytics, Inc.
• Petrochemical• Chemical• Pharmaceutical• Pulp & Paper• Refining
• Jet Fuel Delivery• Natural Gas• Food and Beverage• Metal recovery• Power plants
Potential Customers
• Process Control• Quality Assurance• Environmental Monitoring
Applicable Industries
Applied Analytics, Inc.
Sulfur Recovery Sulfur Recovery Tail Gas analyzer monitoring - H2S, SO2, COS , CS2 , Sulfur vapor simultaneously and instantaneously. Accurate H2S to SO2 ratio.Feed Forward (FFA, air demand) - H2S, hydrocarbons, oxygen.Sales gas (sweet gas, product gas) -Low levels of H2S and total sulfurStack analysis - SO2 , NOxSulfur pit - H2S SO2 NH3Sulfurine - H2S, SO2, COS and CS2 sulfur vaporAcid gas (high levels) -H2SLean Amine -H2SRich amine - H2SSour gas feed H2S
Stack & Power generation (ammonia slip):Stack & Power generation (ammonia slip):Ammonia slip monitoring (< 5 PPM) in DeNOx units.Measuring ammonia, sulfur dioxide and nitrogen oxides simultaneously in flue gas applications.
Synthetic Fiber QualitySynthetic Fiber Quality On line quality monitoring of fiber grade MEG (Mono Ethylene Glycol) by UV transmittance.
Applied Analytics, Inc.
Petroleum based solvent production (BTX): Petroleum based solvent production (BTX): Measuring concentrations of aromatic compounds in petroleum products - Benzene, Toluene, Xylene total aromaticsToluene and naphta in methanolDifferentiating between xylene and other aromatics by a recognition algorithmMonitoring the interface between aromatic compounds transported sequentially through a pipeline
Monitoring Chlorine and chlorinated compounds in process Monitoring Chlorine and chlorinated compounds in process streamsstreamsUtilize the same instrument to measure the concentration of chlorine at low levels (ppm range) to the high percent levels.Measuring NCl3 (Nitrogen Tri-Chloride) in Chlorine.Low levels of Chlorine in bromine
Applied Analytics, Inc.
Manufacturing Process of the white pigment - TiO2Manufacturing Process of the white pigment - TiO2Monitoring TiCl4 in chlorineLow levels of Vanadium.
Pharmaceutical:Pharmaceutical:Accurate mixing of various products for human consumption. CIP ( Clean In Place) monitoring trace amounts of active materialLow levels of vitamins
Polymerization Polymerization TBC (Tertiary Butyl Catechol), a polymerization inhibitor in Butadiene MEHQ, a polymerization inhibitor in AcrylonitrileExtrusion of Low Density PET: Monitoring additives at the extruder’s mouth (phenolic compounds, pigments etc).
Applied Analytics, Inc.
ColorColorCIE L, a*, b* & xyz tristimulusSaybolt Platinum – CobaltHazen or APHADyed Aviation Gasoline Lactic Acid
TransportationTransportationMonitoring trace amounts of diesel in jet fuel
Pulp and PaperPulp and PaperMonitoring ozone a bleaching agentChlorine chlorine dioxideHydrogen peroxides
Applied Analytics, Inc.
Sulfur recoverySulfur recovery
Tail gas analyzer Measures H2S, SO2, COS, CS2 &
Sv No Housing required High performance demister
Applied Analytics, Inc.
Refining, Gas Producers and Petroleum Product Users
Monitoring H2S, SO2, and/or Mercaptans – Gasprom- Astrakhan Russia – Pemex –Tampico, Mexico – Distribuidora Galeon S.A. – Mexico City, Mexico– Gas de France – Paris, France – Siemens Pte. Ltd. - Singapore – RasGas Company Ltd. – Doha, Qatar – TREI GmbH - Stuttgart, Germany – Kinetics Technology Corporation – Taipei, Taiwan – Alon – Big Spring, TX
Applied Analytics, Inc.
Refining, Gas Producers and Petroleum Product Users
Monitoring H2S, SO2, and/or Mercaptans – Analytical Systems Engineering Pte Ltd - Singapore – Sappi Saiccor (Pty) Ltd –Umkomaas, South Africa – Sasol –Secunda, South Africa – Caterpillar Inc. –Mossville, IL – Control De Plant As Industriales, S.A. - Vera Cruz, Mexico – Coastal Aruba Ref Co, NV – Aruba
– Ras Laffan CMS Joint Venture – Qatar
Applied Analytics, Inc.
H2S in sour gas feed to the primary amine absorber, feed forwards for the amine circulation rate.
H2S in sweet gas. Product quality assurance.
H2S in rich Amine- control the circulation rate of ammine through the absorber, measuring the H2S in the rich amine leaving the absorber.
H2S in lean amine – reduce regeneration cost by controlling the steam input, measuring the H2S in the amine leaving the generator column.
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Analyzers:Analyzers:OMA-300
Applied Analytics, Inc.
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Analyzers:Analyzers:
Feed forwards analyzer: determines the H2S and total air required to combust all components in the feed gas, also measures aromatics compounds.H2S to SO2 ratio in tail gas, maintain ideal ratio for max sulfur yield by providing feedback control to the Claus plant primary or trim air supply.H2S in sulfur pit for plant safety – measuring the H2S content in the vapor above the liquid sulfur pit. Providing feedback to the purge air flow controller.
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TLG-837
TLG-837
OMA-300
Applied Analytics, Inc.
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Analyzers:Analyzers:
For cleaning process (proprietary) all require process control analyzers. For example Sulfrine measuring H2S and SO2Stack Gas monitor for stack emission to verify regulatory compliance. Measuring H2S SO2 NH3 oxygen (NO NO2 COS CS2).
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TLG-837
OMA-300
Applied Analytics, Inc.
0
0.1
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1
220 240 260 280 300 320 340
Wavelength (nm)
Ab
sorb
an
ce (
AU
)
0.250.50.7511.25
% H2S
0
0.1
0.2
0.3
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220 240 260 280 300 320 340Wavelength (nm)
Ab
sorb
an
ce A
U
0.250.50.7511.25
% SO2
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
220 240 260 280 300 320 340Wavelength (nm)
Abso
rban
ce (
AU
)
COS 0.1% COS 0.2% COS 0.3%CS2 0.1% CS2 0.2%CS2 0.3%
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
220 240 260 280 300 320 340
Wavelength (nm)
Ab
sorb
an
ce (
AU
)
Temp
Sv
Applied Analytics, Inc.
Applied Analytics, Inc.
Applied Analytics, Inc.
DeNox processDeNox process Measuring the ammonia slipMeasuring the ammonia slip
Application:10 PPM ammonia 200 PPM SO2
200 PPM NO 200 PPM NO2.
Example : SCR Process 4NO +4NH3 +O2 4N2 + 6 H2O
ASA-400ASA-400
Applied Analytics, Inc.0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
190 290 390 490 590 690 790
0
0.005
0.01
0.015
0.02
0.025
190 240 290 340 390 440 490 540 590 640
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
190 195 200 205 210 215 220 225 230 235 240
0
0.01
0.02
0.03
0.04
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0.1
190 195 200 205 210 215 220
NO, NO2 & NH3
NH3 NO2
NO
Applied Analytics, Inc.
Utilities, Industrial Boiler Operators, Process Heaters in many industries
Continuous Emission Monitoring Measure SO2, NO, NO2, NH3 and O3 in flue gas from burning fossil fuel – non-compliance
Potential customers – utilities, industrial boiler operators, process heaters in many industries
Measure Benzene, Chlorides, and Fluorides in flue gas from incinerators
Potential customers - hazardous waste incinerators, medical incinerators, cement plants
Applied Analytics, Inc.
Ambient Monitoring
Measure Ethylene Oxide, Vinyl Chloride, Acrylonitrile, Methanol, SO2, NO, NO2, O3, Cl2, and Br2 in air
Potential customers - Grain Processing, Oxy Vinyls, Tyco, Kendall, landfill sites
Applied Analytics, Inc.
BTX and Total aromaticsBTX and Total aromaticsThe BTX methodAutomating an ASTM- UV laboratory method (D1017-51) for BTX for an on-line continuous monitoring. The total aromatics method The total aromatics algorithm allows for the variation of aromatics in the stream (which creates a wavelength shift of the Absorbance peak maxima) by applying a Max-peak-find algorithm to the UV absorbance spectrum. The intensity at the peak maxima is correlated via to the total aromatics value.
nm
AU
Applied Analytics, Inc.
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0.14
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nm
Abs
orba
nce
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nm
Abs
orba
nce
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230 240 250 260 270 280 290
nm
Ab
sorb
ance
0
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0.04
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0.12
0.14
230 240 250 260 270 280 290
nm
Ab
sorb
ance
benzenetoluene
xyleneprocess
Applied Analytics, Inc.
Chemical, Plastic and Fiber Manufacturers
Monitor Purity and Color of Products– Honeywell Corporation –Hopewell, VA – Purac - Gorinchem, Netherlands – Aplein Ingenieros S.A. – Madrid, Spain – SNC Lavalin – Calgary, AB, Canada – Petro-Canada – Calgary, AB, Canada – Kimberly Clark –Neenah, WI – Trojan Technologies – London, ON, Canada
Applied Analytics, Inc.
Mono Ethylene Glycol - a quality control application
Measuring the Transmittance on-line of MEG at
220nm, 240nm, 275nm, 350nm.
Continuos on-line
Alert instantaneously on changes in the MEG
process stream composition
The measurement is performed on fresh warm
samples eliminating the possibility of sample
contamination.
Applied Analytics, Inc.
70
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85
90
95
100
nm
%T
220 230 240 250 260 270 280 290 300 310 320 330 340 350
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100
220 230 240 250 260 270 280 290 300 310 320 330 340 350
nm
%T
Transmittance spectra of MEG samples at various purity grade levels.
Transmittance spectrum of potassium dichromate.
Applied Analytics, Inc.
TBC- A POLYMERIZATION INHIBITORTBC- A POLYMERIZATION INHIBITOR
TBC (tert-Butyl Catechol) in butadiene,
styrene and in other reactive monomer streams.
Pure isopropanol can be used for blanking &
calibration.
Correction for toluene and butadiene
interferences.
Applied Analytics, Inc.
0
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0.25
0.3
230 240 250 260 270 280 290 300
165ppm
100ppm
50ppm
nm
AU
Absorbance spectra ofAbsorbance spectra of TBCTBC
Applied Analytics, Inc.
TRACE IMPURITIES IN A REACTION CHAMBER’S CLEANING PROCESS a
Clean In Place application
Validation of cleaning and final purity level. Greater availability of reactor volume Detect possible faulty valves in the flow
system. Full spectrum allows for easy method
development. Allows for calibration of various active
materials.
Applied Analytics, Inc.
• Recirculated solvent is diverted to a small by-pass flowing through the spectrometer.
• After reaching a steady state a new batch of cleaning solvent is loaded and the process is repeated until the concentration of impurities reaches a pre-set threshold value.
A pplied A nalytics, I nc.
O M A -517
Applied Analytics, Inc.
time
Co
nc
en
tra
tio
n
1st derivative
(dc/dt)
concentration
1st wash
2nd wash
3rd wash
UCL
The concentration of the active ingredient in the methanol increases until it reaches a plateau. The same occurs for each wash. The 1st derivative of the concentration with time (dc/dt) approaches zero when the process reaches steady state. The UCL (Upper Control Limit) is also shown.
Washing cycle - Timing diagramWashing cycle - Timing diagram
4th wash
Applied Analytics, Inc.
Pharmaceutical Industry Users
Hoffman LaRoche - Paris France Merck Sharp & Dohme Ltd. - Tiperrary, Ireland Eli Lilly and Company - Indianapolis, IN Fisons Pharmaceuticals –Kent UK Boehringer Ingelhem - Petersburgh, VA The Wellcome Foundation - Dartford, UK
Applied Analytics, Inc.
Chlorine 10 PPM to 100%Chlorine 10 PPM to 100%
UV absorbance spectra of Cl2
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0.5
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2.5
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3.5
200 250 300 350 400 450
wavelength (nm)
Ab
sorb
ance
(A
U)
Cl2 80%
Cl2 70%
Cl2 60%
Applied Analytics, Inc.
Applied Analytics, Inc.
Figure 1: Calibration of NCl3, Absorbance spectra, 50 psig chlorine above solution of NCl3 in CCl4.,Blank: CCl4 saturated with chlorine
Figure 2 : On-Line measurements of NCl3 and Cl2 in the Headspace
Figure 4: Ultraviolet Spectrum following Ammonia in Brine excursion of in headspace of chlorine bottoms (90% Chlorine, 10% Carbon Tetrachloride)
NCl3 in Cl2
Applied Analytics, Inc.
Pulp & Paper
Monitor ozone in bleaching process– User Ostrand, Timra Sweden
Monitor chlorine & ClO2 in process control (bleaching) and stack emissions
Applied Analytics, Inc.
Paint and Pigment Manufacturing
Monitor TiCl4 and Vanadium in TiO2 manufacturing process
Monitor Cl2 in TiCl4 material Monitor Cu+2 and other metal ions in solution
– DuPont Nylon Ltd. - Middlesbrough, UK – Shepherd Color Company - Cincinnati OH – Orsk - Orsk Russia – Millennium Inorganic Chemicals - Baltimore, MD
Applied Analytics, Inc.
Pigment Users
Dupont -Wilmington, DE Millennium Inorganic Chemicals - Baltimore, MD
– Jay W. Bayors; 410-354-7304; [email protected] – Mike Griffin; [61] 89-7808-627; [email protected]
Kerr McGee - Oklahoma City, OK Tiwest Joint Venture –Kwinana Australia
Applied Analytics, Inc.
TICl4 slipTICl4 slip
Absorbance spectra of TiCl4
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wavelength (nm)
abso
rban
ce (
AU
)
TiCl4 5000 PPM
TiCl4 2500 PPM
TiCl4 1000 PPM
Applied Analytics, Inc.
Applied Analytics, Inc.
Electronic, Semi-conductor, Mining and Metal Processing industries
Monitor Concentrations of Metal Ions Measure Cu+2 in plating solutions
Potential customers - printed circuit board manufacturing, metal recovery and mining industries
Measure CuSO4 and Cl in metal plating solutionsMonitor Co+2, Ni+2, Cu+2 & Fe+2 in process or waste
water streamsPotential customers – Cobalt recovery plants, catalyst manufacturers
Applied Analytics, Inc.
Absorbance spectra of Chlorine and Ferric chloride
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Wavelength (nm)
Abs
orba
nce
(AU
)
FeCl3Cl2
Applied Analytics, Inc.0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40
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Wavelength (nm)
Ab
sorb
ance
(A
U)
Copper ionsCopper ions
0
5
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1 3 5 7 9 11
13
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17
19 21 23
sample #C
u+2 p
pm
Cu(PPM) atomicabsorption
Cu(PPM) OMA-517
Applied Analytics, Inc.
CoCo+2+2, Ni, Ni+2+2, Cu, Cu+2+2 & Fe & Fe+2+2 ions ions
0
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200 300 400 500 600 700 800
#1 #2 #3 #4
#8 #5 #9 #6
#7 #10 #11 #12
Applied Analytics, Inc.
Refineries, Gas Producers, Storage Terminals and Pipeline Operators
• Monitor interface between aromatic compounds transmitted sequentially through the same pipeline
• Monitor concentrations of benzene, toluene and xylene (BTX) in petroleum products, solvents and hydrogenation processes (ASTM D1017-51)
• Measure H2S, COS, CS2, SO2 and Mercaptans in Gasoline, Diesel Fuel and Natural and a Variety of Fuel Gases (landfill gases) during production, storage, transportation or custody transfer
Potential Customers – Pipeline operators, gas storage terminals, utilities, refineries, landfill gas combustion, natural gas custody transfer
Applied Analytics, Inc.
Refineries, Gas Producers, Storage Terminals and Pipeline Operators
Applied Analytics, Inc.
Trace amounts of diesel in jet fuelTrace amounts of diesel in jet fuel
0
0.5
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2.5
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250 300 350 400 450 500 550 600
nm
AU
pure diesel
JP pure (no diesel)
JP + low levels of diesel
0
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0 0.5 1 1.5 2 2.5 3 3.5Volume F-76 in JP-5 by gravimetric technique
% V
olum
e of
F-7
6 in
JP
-5 m
easu
red
by t
he
OM
A-5
17
Error bars are +/- 5% of measurement.
Figure 1: absorbance spectra of jet fuel and diesel
Figure 2: % Volume of F-76* in JP-5 *Gravimetric Vs the OMA results
Applied Analytics, Inc.
Incoming Materials Validation ; An On-Incoming Materials Validation ; An On-line Recognition Methodline Recognition Method
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860 870 880 890 900 910 920 930 940
wavelength (nm)
ab
so
rba
nce
(A
U)
11-POWERFORMER FEED
10-RAFFINATE
L.C.N
8-LPF
7_DEB_SCN
12-FAWLEY XYLEEN
6-mixed xylenes
9-ALKYATE
4_SCN-RAW
5_SCN_TREAT
3_FAO_SCN
2_BHC
1_BHC
Applied Analytics, Inc.
Chemical, Plastic and Fiber Manufacturers
Monitor purity of MEG (Mono Ethylene Glycol) Monitor purity of Acetonitrile Monitor MEHQ during production of
Acrylonitrile Monitor solvent concentrations – Methanol,
Toluene and/or Naphta in water Validate incoming chemical materials for
concentration and purity– ESSO Nederlands bv - Rotterdam, Netherlands
Applied Analytics, Inc.
Methanol water toluene and naphthaMethanol water toluene and naphtha
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55.00
60.00
10.00 20.00 30.00 40.00 50.00 60.00
Toluene lab (%)
Tolu
ene (
%)
T(%) lab
T(%) OMA
45.00
50.00
55.00
60.00
65.00
70.00
75.00
80.00
85.00
90.00
45.00 50.00 55.00 60.00 65.00 70.00 75.00 80.00 85.00 90.00
Naphta lab (%)
Naphta
(%
)
N(%) lab
N(%) OMA
Low Toluene rangeAnalyte Name Std.Dev. Toluene (%) 0.03Naphta (%) 0.11Methanol (%) 0.25