aplications uv vis swnir rev1

Applied Analytics, Inc.

ApplicationsApplications

Process control

Quality assurance

Environmental complianceIndustries

• Petrochemical• Chemical• Pharmaceutical• Pulp & Paper • Natural Gas

• Metal recovery• Power plants


•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


• 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


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.


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


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).


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


Sulfur recoverySulfur recovery

Tail gas analyzer Measures H2S, SO2, COS, CS2 &

Sv No Housing required High performance demister


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


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


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.

1

2

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Analyzers:Analyzers:OMA-300


5

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


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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


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220 240 260 280 300 320 340

Wavelength (nm)

Ab

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ce (

AU

)

0.250.50.7511.25

% H2S

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220 240 260 280 300 320 340Wavelength (nm)

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% SO2

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220 240 260 280 300 320 340Wavelength (nm)

Abso

rban

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AU

)

COS 0.1% COS 0.2% COS 0.3%CS2 0.1% CS2 0.2%CS2 0.3%

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220 240 260 280 300 320 340

Wavelength (nm)

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Temp

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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

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190 290 390 490 590 690 790

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190 240 290 340 390 440 490 540 590 640

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190 195 200 205 210 215 220 225 230 235 240

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190 195 200 205 210 215 220

NO, NO2 & NH3

NH3 NO2

NO


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


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


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


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Ab

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benzenetoluene

xyleneprocess


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


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.


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nm

%T

220 230 240 250 260 270 280 290 300 310 320 330 340 350

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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.


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.


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230 240 250 260 270 280 290 300

165ppm

100ppm

50ppm

nm

AU

Absorbance spectra ofAbsorbance spectra of TBCTBC


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.


• 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


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


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


Chlorine 10 PPM to 100%Chlorine 10 PPM to 100%

UV absorbance spectra of Cl2

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wavelength (nm)

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Cl2 80%

Cl2 70%

Cl2 60%



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


Pulp & Paper

Monitor ozone in bleaching process– User Ostrand, Timra Sweden

Monitor chlorine & ClO2 in process control (bleaching) and stack emissions


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


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


TICl4 slipTICl4 slip

Absorbance spectra of TiCl4

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TiCl4 5000 PPM

TiCl4 2500 PPM

TiCl4 1000 PPM



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


Absorbance spectra of Chlorine and Ferric chloride

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FeCl3Cl2

Applied Analytics, Inc.0.00

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Copper ionsCopper ions

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sample #C

u+2 p

pm

Cu(PPM) atomicabsorption

Cu(PPM) OMA-517


CoCo+2+2, Ni, Ni+2+2, Cu, Cu+2+2 & Fe & Fe+2+2 ions ions

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#1 #2 #3 #4

#8 #5 #9 #6

#7 #10 #11 #12


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


Refineries, Gas Producers, Storage Terminals and Pipeline Operators


Trace amounts of diesel in jet fuelTrace amounts of diesel in jet fuel

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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

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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


Incoming Materials Validation ; An On-Incoming Materials Validation ; An On-line Recognition Methodline Recognition Method

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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


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


Methanol water toluene and naphthaMethanol water toluene and naphtha

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Toluene lab (%)

Tolu

ene (

%)

T(%) lab

T(%) OMA

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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

aplications uv vis swnir rev1

Documents

product gas low levels

sales gas sweet gas

low levels of chlorine

accurate h2s

bromineapplied analytics

flue gas applications

low levels ppm range

high percent levels