Galvanic Applied Sciences. Galvanic Applied Sciences is a Canada-based company that has facilities in Boston and England and representation all over the.

Galvanic Applied Sciences

Galvanic Applied Sciences is a Canada-based company that has facilities in Boston and England and representation all over the

world. The company develops electronic technology for Gas and Liquids analysis.

Head Office7000 Fisher Road SE, Calgary, Alberta, Canada

Website: www.galvanic.com

Lead Acetate Tape Analysers for Hydrogen

Sulphide and Total Sulphur Determination

SRU Analysers for Tail Gas, Sulphur Pits and Oxygen

Demand

Sulphur Chromatograph

Gas Chromatograph for BTU and Composition measurement in Natural Gas

Electronic VolumeCorrectors

Acoustic and Optic Analysers for Turbidity, Color and Concentration measurements.

Online Viscosity Analysers

Online Automatic Titrators

Field Programmable UV Analyzers

Sulphur Chromatography Analysers

842/843842/843

MEASUREMENT PRINICIPLEMEASUREMENT PRINICIPLE

7

SULFUR CHEMILUMINESCENCESULFUR CHEMILUMINESCENCE• Chemiluminescence: A chemical reaction which produces

light.• Reaction Furnace

◦ R-S + O2 SO2 + other products of combustion◦ SO2 + H2 SO + H2O

• Chemiluminescence Chamber◦ SO + O3 SO2* + O2◦ SO2* SO2 + Light (350 nm)

CHROMATOGRAPHYCHROMATOGRAPHY

• Separation of complex mixtures based on selective adsorption whereby the components of the mixture can be identified and quantified.

GAS CHROMATOGRAPHGAS CHROMATOGRAPH

• The gas chromatograph consists of three major components.◦ The injection system◦ The separation columns◦ The detector

• The injection system and separation columns are located in a temperature controlled oven.

RETENTION TIMERETENTION TIME• The elapsed time between when sample is

injected into the column to when a specific compound is detected.

• Each component in the mixture has a specific retention time.

• The retention time is used to identify the component.

PEAK AREAPEAK AREA• The area under the peak as calculated by a

software algorithm.• The peak area determines the concentration of

the component

TYPICAL CHROMATOGRAMTYPICAL CHROMATOGRAM

Butane

0

10

20

30

40

50

60

70

80

1 16 31 46 61 76 91 106 121 136 151 166 181 196 211 226 241 256 271 286

Seconds

H2S

MeSH

EtSH

DMS

CS2

i-PrSH

40 ppm

9 ppm

35 ppm

35 ppm

70 ppm

30 ppm

Column: 30 m x 0.53 mm id MTX 1 @ 60°C isothermal.

Retention Time

TYPICAL RETENTION TIMES FOR SULFUR TYPICAL RETENTION TIMES FOR SULFUR COMPOUNDS IN NATURAL GAS @ 50°CCOMPOUNDS IN NATURAL GAS @ 50°C• H2S (Hydrogen Sulfide) 80 sec• COS (Carbonyl Sulfide) 86 sec• MeSH(Methyl Mercaptans) 120 sec• EtSH(Ethyl Mercaptans) 180 sec• DMS(Dimethyl Sulfide) 200 sec• CS2(Carbon Disulfide) 220 sec• i-PrSH(iso-Propyl Mercaptan) 250 sec• t-BuSH(tertiary Butyl Mercaptan) 320 sec• n-PrSH (normal-Propyl Mercaptan) 360 sec• THT (Tetrahydrothiophene) 630 sec

842 SULFUR ANALYZER842 SULFUR ANALYZER• Sulfur specific gas chromatograph.• Identify and quantify individual sulfur compounds

in gas streams.

APPLICATIONSAPPLICATIONS

16

MEASURING SULPHURMEASURING SULPHUR

Sulfur is the chemical element that has the atomic number 16. It is denoted with the symbol S. It is an abundant multivalent non-metal. Sulfur, in its native form, is a yellow crystalline solid. In nature, it can be found as the pure element and as sulfide and sulfate minerals. It is an essential element for life and is found in two amino acids, cysteine and methionine.

Its commercial uses are primarily in fertilizers, but it is also widely used in black gunpowder, matches, insecticides and fungicides.

Elemental sulfur crystals are commonly sought after by mineral collectors for their brightly colored polyhedron shapes. In nonscientific context it can also be referred to as brimstone.

SS

TYPICAL SULFUR COMPOUNDSTYPICAL SULFUR COMPOUNDS

TARIFFSTARIFFS• Most pipeline companies enforce tariffs, these are

to:◦ Protect against corrosion◦ Provide safety◦ Aid with odorization◦ Environmental purposes (SO2 emissions)

• Typically the tariff for H2S is 4 ppm and 16 ppm for TS (or ¼ grain and 1 grain respectfully)

ASTM STANDARDSASTM STANDARDS• Many regulatory agencies such as EPA or DOT may

make reference to ASTM standards◦ Lead Acetate Tape adheres to the following ASTM

standards• D3031-81• D4468-85• D4810-88• D4084-82 (most commonly referred to)

ASTM STANDARDSASTM STANDARDS

ACID RAINACID RAIN

The combustion of Sulphur-Based compounds generates Sulphur dioxide (SO2), part of this Sulphur Dioxide goes to the atmosphere and its source is combustion of gases with high content of Total Sulphur.

S + O2 → SO2 Sulphur dioxide in presence of the atmospheric humidity (water) becomes Sulphuric

Acid:SO3(g) + H2O(l) → H2SO4(l)

Sulphuric Acid precipitates back to the ground as Acid Rain.

POTENTIAL MARKETSPOTENTIAL MARKETS• Refining• Petrochemical• Natural Gas• Other

REFININGREFINING• Diesel

• Total Sulfur (500 ppm)• New regulation is 15 ppm

• Gasoline• Total Sulfur 30 ppm• Sulfur Chromatography

• Propyl Mercaptan and Thiophenes• Kerosene and Other Fuels• Liquified Petroleum Gases (Propane/Butane)

• H2S, COS, Other Sulfurs• Fuel Gas• Stack Emissions

• Total Reduced Sulfur (TRS)• H2S, COS, MERCAPTANS

PETROCHEMICALPETROCHEMICAL• Ethylene / Propylene

• Trace Levels - Product Quality/ Catalyst Protection• H2S, COS, MeSH, TS

• Liquified Petroleum Gases• Feed Stock - Catalyst Protection

• H2S, COS, TS• Syngas

• H2, CO, CO2, CH4• Product Quality / Catalyst Protection

• Trace (ppb) H2S and TS• Fertilizer

• Catalyst Protection • Feedstock is generally Natural Gas

• Trace (ppb) H2S and TS• Other

NATURAL GASNATURAL GAS• Pipeline

• Product Quality• 4 ppm H2S and 16 ppm TS

• Ordorants• Mercaptan analysis to ensure gas is properly odorized• analysis to ensure no odorant is in the gas as some customers may have sensitive processes

• Corrosion Control• H2S measurement

• Production• Product Quality

• 4 ppm H2S , 16 ppm TS, Naturally occurring mercaptans• Plant Inlet

• High concentrations of H2S• Flare Lines

• High concentrations of H2S• Environmental regulations

OTHEROTHER• Pulp and Paper

• Environmental• TRS - H2S, COS and Mercaptans

• Thermal Power• Thermal Steam

• H2S as a byproduct from the steam

• CO2 (Food Grade)• Product Quality

• Trace (ppb) Total Sulfur

FEATURES AND BENEFITSFEATURES AND BENEFITS

28

WHAT DOES THE 842 OFFER?WHAT DOES THE 842 OFFER?

• Linearity• Equimolar Response• Repeatability• Sensitivity• Independent of Matrix• Features

EQUIMOLAR RESPONSEEQUIMOLAR RESPONSE• Each sulfur compound exhibits the same response

characteristic◦ Provides Quantitive and Qualitative Total Sulfur

measurement◦ Chromatograph can calibrated using single component

standard reducing calibration complexity

REPEATABILITYREPEATABILITY• Generally results are +/- 1% or better

◦ Ideal for applications requiring process control

SENSITIVITYSENSITIVITY• Able to resolve 10 ppb in Gases and 100 ppb in

Liquids◦ lower ranges available ◦ better resolution

LINEARITYLINEARITY• 4 orders of magnitude

◦ ppb to percent on the same detection principle◦ allows calibration to be done with higher

concentration standard for ppb applications

INDEPENDENT OF MATRIXINDEPENDENT OF MATRIX• Hydrocarbon changes do not affect the overall

measurement◦ Multistreaming ◦ Batching applications◦ Blending ◦ Process upsets

FEATURESFEATURES• Autocalibration

◦ reduces overall maintenance• Combustion

◦ cross flow design provides complete combustion enhancing measurement

• On-Board Microprocessor◦ No PC required for operation of the analyzer

FEATURESFEATURES• Low maintenance

◦ General mantenance is required only quarterly for system with vacuum pump

◦ Virtually maintenance free with use of air driven vacuum transducer

• Simple Design◦ Easy to maintain and troubleshoot

GENERAL DESCRIPTION OF THE GENERAL DESCRIPTION OF THE INSTRUMENTINSTRUMENT

842 OVEN842 OVEN

CAPILLARY COLUMNCAPILLARY COLUMN

• Metal coated capillary column for durability.• 30 meter Wall coated open tubular (WCOT) column has thin layer

of liquid on inner diameter of a thin tube.• Useful for complex separations up to C4 mercaptans or sulfides.

842 INJECTION SYSTEM842 INJECTION SYSTEM

• 10 port Helium actuated valve for sample injection and column backflush.

SULFUR CHEMILUMINESCENCESULFUR CHEMILUMINESCENCE• Chemiluminescence: A chemical reaction which produces

light.• Reaction Furnace

◦ R-S + O2 SO2 + other products of combustion◦ SO2 + H2 SO + H2O

• Chemiluminescence Chamber◦ SO + O3 SO2* + O2◦ SO2* SO2 + Light (350 nm)

STEP 1: COMBUSTIONSTEP 1: COMBUSTION

• Sulfur compound reacted with air and hydrogen at 750oC under vacuum to form sulfur monoxide (SO).

Sulfur Compound

Hydrogen

Oxygen

SO

REACTION FURNACEREACTION FURNACE

STEP 2: STEP 2: CHEMILUMINESCENCECHEMILUMINESCENCE

• Sulfur monoxide is reacted with ozone in the reaction chamber to form SO2 and LIGHT.

REACTION CELLREACTION CELL

STEP 3: DETECTION BY PMTSTEP 3: DETECTION BY PMT

• Light is detected by a photomultiplier tube (PMT).• Photomultiplier tube generates a current

proportional to amount of sulfur present.

SO

OzoneOzone

Light

PHOTOMULTIPLIER TUBE (PMT)PHOTOMULTIPLIER TUBE (PMT)

THERMOELECTRIC COOLERSTHERMOELECTRIC COOLERS

• PMT operates best at 0 – 5o C.

• Two Peltier Elements wired in series are used to keep PMT cool

• Dry air purge is used to prevent water condensation on PMT.

DETECTOR ASSEMBLEDDETECTOR ASSEMBLED

PMT POWER SUPPLYPMT POWER SUPPLY

• PMT requires 1100 VDC for operation.

• PMT power supply has 24 VDC input and 1100 VDC output.

AMPLIFIERAMPLIFIER

• Amplifier converts PMT current to millivolts

• Dipswitches are used for signal attenuation

OZONE GENERATOROZONE GENERATOR

• Ozone is supplied from an onboard ozone generator.• Air is passed through a steel tube at 7500 VAC.• Atmospheric oxygen is converted to ozone.

VACUUMVACUUM

• The sample combustion and chemiluminescence are done at near vacuum conditions to preserve the SO intermediate.

CHEMILUMINESCENCE FLOW CHEMILUMINESCENCE FLOW SCHEMATICSCHEMATIC

SERVICES AND UTILITIESSERVICES AND UTILITIES

55

UTILITY GASESUTILITY GASES• Carrier Gas.

◦ UHP Helium supplied by dual stage bottle regulator at 80 psig.

◦ Controlled at analyzer by carrier gas regulator and mass flow controller.

◦ Helium also controlled to 60 psi by another regulator for valve actuation.

UTILITY GASESUTILITY GASES• Hydrogen.

◦ UHP Hydrogen supplied by dual stage bottle regulator at 60 psig.

◦ Flow is controlled by mass flow controller.

UTILITY GASESUTILITY GASES

• Ozone◦ Drawn from ambient air through dessicator.◦ Flow is controlled by rotameter.

• Combustion Air◦ Drawn from ambient air through dessicator.◦ Flow is controlled by rotameter.

• PMT Purge.◦ Prevents condensation on PMT. Instrument air

or nitrogen can be used. ◦ Flow is controlled by rotameter.

UTILITY GASESUTILITY GASES• Calibration Gas.

◦ 5 - 10 ppm H2S in Nitrogen.◦ Supply at 15 psig with stainless steel dual stage bottle

regulator.

MAINTENANCE CYCLEMAINTENANCE CYCLE• Perform regular preventative maintenance every

3 months.◦ Change pump oil every cycle.◦ Change inlet trap every cycle.

• Use 50/50 mix of charcoal and desiccant.

◦ Replace valve diaphragm as needed.• 1,000,000 cycles.

◦ Replace air desiccant as needed.◦ Ceramic tubes should not need to be replaced.

SPECIFICATIONSSPECIFICATIONS

61

Specifications

Detection limit 0-10 ppb

Number of Streams 4 plus calibration

Sample Injection Valco Model VIII

Linearity 2%

Repeatability 2%

Cycle time 5 minutes

Electrical Clasification Class I, Division 1 and 2, Groups B, C and D.

Power Consumption 600 watts at 120 VAC

SPECIFICATIONSSPECIFICATIONS

62

Specifications

Electronic Platform Dallas 87C530. Microprocessor c/w 20 Bit A/D, 12 Bit D/A, 4-20 ma Output, and Intrinsically Safe Keypad

Outputs 2, 4-20 ma Scaled, 4-20 ma Raw Sensor, 6–5 amp SPDT Relays, Modbus, Optional 32 4-20 ma Outputs (User Assignable)

Contact Inputs Remote Calibration Start, 4 Status (Dry Contacts)

Dimensions 36”H x 34”W x 12”D

Weight 250 lbs

RECOMMENDED SPARE PARTSRECOMMENDED SPARE PARTS• PMT BA0755• Valve Rebuild Kit BA1274• Ceramic Tubes MC0745/MC0746• Pump Oil CO01672• Charcoal CO1746• Moisture Trap Refill CO0888• 1/8” Teflon Ferrules• 1/16” Teflon Ferrules