MERICHEM-18-2010

ANALYTICAL METHOD FOR DETERMINATION OF DISULFIDE OILS IN CAUSTICS

Introduction
This method is recommended by Merichem to measure the total (dissolved and
suspended) disulfide content of the caustic in REGEN units.
Caution: Please read all relevant MSDSs, follow established safety procedures, and
wear proper PPE.
Equipment and Reagents
A. 1 pint sample container with cap
B. 2 oz. glass bottle with cap
C. 1000 mL separatory funnel
D. Pail containing ice water
E. 10 mL pipette
F. Nitrogen
G. Isooctane (sulfur free)
H. Total Sulfur Analyser (TSA) for hydrocarbons
Procedure
1. Purge 200 mL of isooctane with nitrogen for 30 minutes.
Sampling
2. Fill a pail full of ice and full of water.
3. Purge a glass or metal sample container with nitrogen for five minutes and
immediately cap the container at the completion of the purge.
4. Place the sampling tube from the unit into the neck of the sample container and draw
a caustic sample. Completely fill the bottle as close to the top as possible and
immediately cap the bottle. These sampling procedures are designed to minimize
air introduction and thereby prevent inadvertent mercaptan oxidation.
5. After sampling, immediately store the container in ice to minimize oxidation of
mercaptans in the caustic sample.

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MERICHEM-18-2010

ANALYTICAL METHOD FOR DETERMINATION OF DISULFIDE OILS IN CAUSTICS

Analysis
6. Weigh the 1000 mL separatory funnel to the nearest 0.1g and record the weight as
A.
7. Add 100-200 mL of nitrogen-purged isooctane (from Step 1) to the separatory funnel
and bubble nitrogen into isooctane for two minutes.
8. Cap and weigh the separatory funnel containing isooctane to the nearest 0.1g and
record the weight as B.
9. Analyze the mercaptan content of the caustic sample by MERICHEM-10a-2010.
Record the result as RSH-1.
10. Using a plastic or glass funnel, add 100-200 mL of caustic sample to separatory
funnel while purging with N2. Do not shake. Purge the vapor space above the
isooctane with N2 for one minute. Immediately cap the separatory funnel.
11. Weigh the separatory funnel with isooctane and caustic to the nearest 0.1g and
record the weight as D.
12. Shake vigorously for five minutes. Periodically vent the separatory funnel to
prevent pressure build-up. To retard mercaptan oxidation, minimize opening the
separatory funnel cap. Let the solution settle for thirty minutes with the cap on.
13. As quickly as possible, pipette a 10 mL isooctane sample from the top of the
separatory funnel into a nitrogen blanketed 2 oz. bottle. The top layer is isooctane.
14. Add 5 ml of deionized water to 10 mL isooctane. Nitrogen blanket the bottle and
shake for one minute to remove traces of caustic.
15. Separate the extracted isooctane in the 2 oz. bottle from the aqueous phase.
16. Determine the sulfur content (wppm) in the isooctane extract (from Step 15) using a
Total Sulfur Analyzer (TSA).
17. If sulfur-free isooctane is not used then determine the wppm sulfur in isooctane
used as the starting material (in Step 7) with a Total Sulfur Analyzer (TSA).
Otherwise skip to step 18.
18. Difference between sulfur content (wppm) in the isooctane starting material (Step 7)
and the extracted isooctane (Step 16) is recorded as F.
19. Re-Analyze the mercaptan content of the caustic phase in the separatory funnel by
MERICHEM-10a-2010. Record the value as RSH-2.
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Merichem Confidential and Proprietary Information

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MERICHEM-18-2010

ANALYTICAL METHOD FOR DETERMINATION OF DISULFIDE OILS IN CAUSTICS

20. If RSH-2 < RSH-1 then record the difference as DRSH. This value will be
subtracted from the final calculated total sulfur to correct for any mercaptan
oxidation that may have occurred during the extraction process due to inadequate
nitrogen blanketing. If RSH-2 = RSH-1 then DRSH = 0.
Calculations
Calculation formula for DSO sulfur (wppm) in caustic:

F C
DSO Sulfur in Caustic ( wppm ) =
DRSH
E
Where
C = B (g) A (g)
E = D (g) B (g)
F = wt. ppm sulfur from the Total Sulfur Analyzer (TSA)
DRSH = (RSH-1 RSH-2)
A = weight of separatory funnel (g)
B = A + isooctane (g)
C = B A (g)
D = B + Caustic (g)
E = D B (g)
F = sulfur in isooctane (TSA) (wppm)

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Rev. July 10