1. Galvanic Applied Sciences

2. Galvanic Applied Sciences Inc.
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 Office
7000 Fisher Road SE, Calgary, Alberta, Canada
Website:

3. Gas Analyzers
Lead Acetate Tape Analysers for Hydrogen Sulphide and Total Sulphur Determination
Electronic
Volume
Correctors
Sulphur Chromatograph
Gas Chromatograph for BTU and Composition measurement in Natural Gas
SRU Analysers for Tail Gas, Sulphur Pits and Oxygen Demand

4. Liquids Analyzers
Acoustic and Optic Analysers for Turbidity, Color and Concentration measurements.
Field Programmable UV Analyzers
Online Automatic Titrators
Online Viscosity Analysers

6. 842/843
Sulphur Chromatography Analysers

7. Measurement Priniciple

8. Sulfur Chemiluminescence
Chemiluminescence: A chemical reaction which produces light.
Reaction Furnace
R-S + O SO2 + other products of combustion
SO2 + H SO + H2O
Chemiluminescence Chamber
SO + O SO2* + O2
SO2* SO2 + Light (350 nm)

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

10. Gas 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.

11. Retention 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.

12. Peak Area
The area under the peak as calculated by a software algorithm.
The peak area determines the concentration of the component

13. Typical Chromatogram Retention Time Butane 10 20 30 40 50 60 70 80 110 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
70 ppm
30 ppm
Column: 30 m x 0.53 mm id MTX 1
@ 60°C isothermal.
Retention Time

14. Typical Retention Times For Sulfur Compounds in Natural Gas @ 50°C
H2S (Hydrogen Sulfide) sec
COS (Carbonyl Sulfide) sec
MeSH(Methyl Mercaptans) 120 sec
EtSH(Ethyl Mercaptans) sec
DMS(Dimethyl Sulfide) sec
CS2(Carbon Disulfide) sec
i-PrSH(iso-Propyl Mercaptan) 250 sec
t-BuSH(tertiary Butyl Mercaptan) sec
n-PrSH (normal-Propyl Mercaptan) sec
THT (Tetrahydrothiophene) 630 sec

15. 842 Sulfur Analyzer Sulfur specific gas chromatograph.
Identify and quantify individual sulfur compounds in gas streams.

16. Applications

17. Measuring 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. S

18. Typical Sulfur Compounds

19. Tariffs 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)

20. ASTM Standards
Many regulatory agencies such as EPA or DOT may make reference to ASTM standards
Lead Acetate Tape adheres to the following ASTM standards D D D
D (most commonly referred to)

21. ASTM Standards

22. Acid 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.

23. Potential Markets
Refining
Petrochemical
Natural Gas
Other

24. Refining 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

25. Petrochemical 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
Other

26. Natural 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
4 ppm H2S , 16 ppm TS, Naturally occurring mercaptans
Plant Inlet
High concentrations of H2S
Flare Lines
Environmental regulations

27. Other 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

28. Features and Benefits

29. What does the 842 offer? Linearity Equimolar Response Repeatability
Sensitivity
Independent of Matrix
Features

30. Equimolar 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

31. Repeatability Generally results are +/- 1% or better
Ideal for applications requiring process control

32. Sensitivity Able to resolve 10 ppb in Gases and 100 ppb in Liquids
lower ranges available
better resolution

33. Linearity 4 orders of magnitude
ppb to percent on the same detection principle
allows calibration to be done with higher concentration standard for ppb applications

34. Independent of Matrix
Hydrocarbon changes do not affect the overall measurement
Multistreaming
Batching applications
Blending
Process upsets

35. Features Autocalibration Combustion On-Board Microprocessor
reduces overall maintenance
Combustion
cross flow design provides complete combustion enhancing measurement
On-Board Microprocessor
No PC required for operation of the analyzer

36. Features Low maintenance Simple Design
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

37. General Description of the Instrument

38. 842 Oven

39. Capillary 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.

40. 842 Injection System
10 port Helium actuated valve for sample injection and column backflush.

41. Sulfur Chemiluminescence
Chemiluminescence: A chemical reaction which produces light.
Reaction Furnace
R-S + O SO2 + other products of combustion
SO2 + H SO + H2O
Chemiluminescence Chamber
SO + O SO2* + O2
SO2* SO2 + Light (350 nm)

42. Step 1: Combustion
Sulfur Compound
Hydrogen
Oxygen
Sulfur compound reacted with air and hydrogen at 750oC under vacuum to form sulfur monoxide (SO). SO

43. Reaction Furnace

44. Step 2: Chemiluminescence
Sulfur monoxide is reacted with ozone in the reaction chamber to form SO2 and LIGHT.

45. Reaction Cell

46. Step 3: Detection by PMT
Light is detected by a photomultiplier tube (PMT).
Photomultiplier tube generates a current proportional to amount of sulfur present. SO
Ozone
Ozone
Light

47. Photomultiplier Tube (PMT)

48. Thermoelectric 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.

49. Detector Assembled

50. PMT Power Supply PMT requires 1100 VDC for operation.
PMT power supply has 24 VDC input and 1100 VDC output.

51. Amplifier Amplifier converts PMT current to millivolts
Dipswitches are used for signal attenuation

52. Ozone 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.

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

54. Chemiluminescence Flow Schematic

55. Services and Utilities

56. Utility 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.

57. Utility Gases Hydrogen.
UHP Hydrogen supplied by dual stage bottle regulator at 60 psig.
Flow is controlled by mass flow controller.

58. Utility Gases Ozone Combustion Air PMT Purge.
Drawn from ambient air through dessicator.
Flow is controlled by rotameter.
Combustion Air
PMT Purge.
Prevents condensation on PMT. Instrument air or nitrogen can be used.

59. Utility Gases Calibration Gas. 5 - 10 ppm H2S in Nitrogen.
Supply at 15 psig with stainless steel dual stage bottle regulator.

60. Maintenance 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.

61. Specifications Specifications Detection limit 0-10 ppb
Number of Streams
4 plus calibration
Sample Injection
Valco Model VIII
Linearity 2%
Repeatability
Cycle time
5 minutes
Electrical Clasification
Class I, Division 1 and 2, Groups B, C and D.
Power Consumption
600 watts at 120 VAC

62. Specifications 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 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

63. Recommended 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