THE CHEMICAL DETERMINATION OF H 2S, RSH AND

COS IN HYDROCARBON GAS

REF: OP 084 REV: 04 DATE: 24 March 1998 PAGE 1 of 7

SCOPE

Typically this procedure can be used to determine H 2S values from as low as 0.3 ppm to as high as
several thousand ppm. For high levels (approx 1,600 ppm and above) the procedure requires
additional gas scrubbers, see later in this procedure.

OUTLINE

This method is typical of UOP Method 212-77. Refer to this method for further details, reagent,
make up, etc. H 2S and/or RSH are absorbed together from a gas, into a solution of potassium
hydroxide. COS is absorbed into a solution of monoethanolamine. Each solution is titrated with
alcoholic silver nitrate to a single endpoint for COS, a double endpoint for combined H 2S and RSH
or a single for either on their own.

NOTE: H 2S is the chemical structure of hydrogen sulphide, COS and RSH are the general
abbreviations for carbonyl sulphide and mercaptans respectively.

SAFETY PRECAUTIONS

1. Appropriate safety gear must be worn when working with pressurised gas containing H2S.
Safety boots, hard hat, coveralls and safety glasses are minimum. Wear breathing apparatus
according to rig guidelines.

2. Wear protective gloves when handling chemicals.

3. Vent lines must be run to safe area and tied down.

PROCEDURE FOR H2S LEVELS LESS THAN 1,600 PPM BUT GREATER THAN 0.3 PPM

1. Prepare 2 or more dreschels depending on the expected level of H 2S. To do this put 100 mls of
40 wt% potassium hydroxide, plus 2 mls of "Unitest 212" in each dreschel.

NOTE: A blank should be performed on all reagents. The procedure is followed exactly, including
the nitrogen purge but no sample gas is flowed through the scrubbers. The value obtained is
subtracted from subsequent endpoint values.

2. Prepare a "blacked-out" dreschel containing 100 ml of a 5% monoethanolamine solution in

ethanol.

3. Attach the dreschel heads (which have a sintered head porosity = 2) to the bottles. Connect
up the bottles using tubing, with the order of scrubbing being through the two potassium
hydroxide scrubbers first, then the blacked out monoethanolamine/ethanol scrubber last.

4. Place some silicon grease around the 3 scrubbers ground glass joints.

5. Attach 2 tie wraps if not already present, to each dreschel. Place elastic bands around each to
hold the dreschel head firmly in place.

Warning: The controlled source document of this procedure is stored on Oilphase homepage
(http://www.aberdeen.oilphase.slb.com). Any paper version of this procedure is uncontrolled and
should be compared with the source document at time of use to ensure it is up-to-date.

PREPARED BY: CF VERIFIED BY: DH APPROVED BY: GD

 THE CHEMICAL DETERMINATION OF H 2S, RSH AND
COS IN HYDROCARBON GAS
REF: OP 084 REV: 04 DATE: 24 March 1998 PAGE 2 of 7

6. Connect, via tubing, the outlet of the last dreschel to the inlet of the wet test gas meter.

7. Connect the outlet of the wet test meter, via tubing, to a safe area such that the vented gas
presents no hazard.
8. Connect a control manifold to the gas line of the separator.

9. Note the points and connect between the control manifold on the separator and the inlet of the
first dreschel with tubing. Check that all the dreschel heads are connected the right way
round. If not the solution will be pushed though to the meter upon flowing gas and the test
shall be required to be restarted. (See Figure 1.)

Figure 1
NOTES

i) At this point, if liquid carry over is expected, from the separator gas line or has been
experienced, put an extra dreschel BEFORE the two 40% potassium hydroxide (KOH)
dreschels. The head of this bottle should not be sintered. It is purely to stop carryover of
liquids into the KOH solutions.

ii) Be aware that it is preferable to keep all connecting lines as short as possible and not to
include the "extra" dreschel for carry over. This is to avoid any of the sulphur compounds
being adsorbed.

iii) It is advisable to put in tubing connectors at some point in the train, at least between the last
dreschel and the wet test meter and separator manifold and first dreschel. This allows quick
connection/disconnection. Join the two ends (of the system), to prevent air entering. (See
Figure 2.

Figure 2
 THE CHEMICAL DETERMINATION OF H 2S, RSH AND
COS IN HYDROCARBON GAS
REF: OP 084 REV: 04 DATE: 24 March 1998 PAGE 3 of 7

iv) One can also be added between the last KOH and the blacked out dreschel to isolate the last
dreschel as it is titrated separately to the KOH ones.

10. Connect a cylinder of oxygen free nitrogen to the system and purge for 15 minutes.

NOTE

i) The oxygen free nitrogen regulator must be equipped with a regulating valve at its outlet
unless it has been checked that the regulator control goes low enough not to create leaks or
pushes the solutions into the gas meter.

ii) Ideally a double valve is used so that no tubing needs to be removed when disconnecting the
nitrogen and connecting to the separator gas line. Tubing clamps shall be used to prevent air
entering the system if a double valve is not available.
11. Switch off the nitrogen and leave the system for 2 minutes until the pressure has bled off.

12. If a double valve has not been incorporated in the system for the nitrogen purge (see 10 Note
ii), then clamp the tubing as close to the nitrogen control valves as possible. Disconnect
tubing to separator gas line control valve and remove tubing clamp.

13. Note the wet test meter reading on H 2S, RSH and COS Determination Form (Form 152).

14. Note the barometric air pressure on Form 152.

15. Note the wet test meter temperature on Form 152.

16. Slowly and carefully open the control valve from the separator gas line, allowing the sample
gas to flow through the scrubbing solutions.

Table 1

H2S/RSH No of 100 ml Flow Volume Dilute Volume Aliquote End Point

(ppm) 30% KOH (litres) (~ml)

Upto 40 2 30 n/a all 10

at 80 2 30 n/a all 20
upto 160 2 15 n/a all 20
At 250 2 15 500 100 6
500 2 30 500 40 10
1,000 2 30 500 20 10
1,600 2 30 500 20 16

Above 1,600 ppm need to modify the set up. See Section at the end of this procedure.

2,000 2 20 500 20 10
3,000 2 15 500 20 15

NOTE

i) When opening the valve watch the first dreschel for signs of gas flow - not the wet test water.

ii) There is a back pressure in the system. When increasing flow rates, adjust valve and wait 30
seconds for pressures in the system to stabilise before re-adjusting.

iii) The maximum flow rate shall be 500 mls per minute (0.5 dm-3 min-1).

iv) The volume of gas and dilution, if required, can be got from Table 1 if the H 2S level is known.
 THE CHEMICAL DETERMINATION OF H 2S, RSH AND
COS IN HYDROCARBON GAS
REF: OP 084 REV: 04 DATE: 24 March 1998 PAGE 4 of 7

17. After the required volume of gas has been sampled, shut off the control valve from the
separator. Leave for 2 minutes to let the pressure equalise.

18. Note the wet test meter final reading on Form 152.

19. Note the barometric air pressure final reading on Form 152.

20. Note the wet test meter temperature final reading on Form 152.

21. Disconnect each dreschel. Avoid air getting into the system by connecting the tubing between
the inlet and outlet of the dreschels.

22. During the titration, the chemical reaction is

2AgNO3 + 2KOH + H 2S ⇒ Ag2S + 2KNO3 + 2H2O

23. The titrant used for the subsequent titration is 0.01M silver nitrate. The potassium hydroxide
solution can be titrated with an aqueous - or alcoholic solution. The carbonyl sulphide
dreschel can only be titrated with alcoholic silver nitrate. Accurately dilute the 0.1M stock
silver nitrate (25 mls ⇒ 250 mls), in an amber volumetric flask, with appropriate solvent ie
deionised water or propan-2-ol (iso-propyl alcohol).

NOTE

i) 0.1M silver nitrate, once opened, will keep⇒for about 1 week.

ii) 0.01M silver nitrate will keep for about 24 hours.

iii) Silver nitrate solutions must be kept in the dark and stoppered when not in use.

24. Prepare the reference electrode for titration. Fill the reference electrode inner junction with
"inner" filling solution first (green-silver chloride). Slide cover back over filling hole and
gently wipe with a tissue. Reassemble the electrode. Fill the outer junction with "outer"
filling solution (clear-potassium nitrate).

NOTE: Be careful not to over tighten the electrode when reassembling. The glass cone should
protrude approx 1 mm from the plastic sheath.

25. Prepare the sulphide electrode. Wet the glass paper and gently clean the electrode using
circular motions until it is polished. Rinse with deionised water.

26. Connect the electrodes to the millivolt meter.

27. Fill and zero the 10 mls burette with 0.01M silver nitrate.

28. For the first 2 potassium hydroxide scrubbers, prepare a solution for titration as per Table 1.
In most cases, where low levels of hydrogen sulphide is expected, the whole solution would
be taken and rinsed into a 400 ml beaker. If an aliquote is required, pipette this into a 400 ml
beaker.

29. If at Step 28 an aliquote was taken, dilute it to approx 200 cc in the 400 cc beaker with de-
ionised water.

30. Add 5 mls of 1M ammonium hydroxide for EACH 100 mls of potassium hydroxide.

31. Add a magnetic follower to the beaker.

 THE CHEMICAL DETERMINATION OF H 2S, RSH AND
COS IN HYDROCARBON GAS
REF: OP 084 REV: 04 DATE: 24 March 1998 PAGE 5 of 7

32. Place the beaker on the magnetic stirrer. Insert the electrodes and adjust the stirring such that
no air is drawn into the solution.

33. Switch on the millivolt meter.

34. Add a small portion of silver nitrate (approx 0.02 mls) and check how the millivolt read-out
responds. If it does not change add another small portion. Do this upto around 0.2 mls. You
do not need to record the read-out if it does not change much but do record at least one point
every 0.2 mls.

NOTE

i) The reason for this is the slow response of the ion selective electrode. A small addition of
silver nitrate can (and will, at the endpoint) give a large change in potential. This potential is
slow to be seen and slow to stabilise. It is therefore very easy to go past the endpoint without
realising it. If the level of hydrogen sulphide is known, longer increments can be added up to
the endpoint providing time is given for stabilising. It is quoted that a reading be considered
stable if it changes by less than 6 mV in one minute.

ii) At the equivalence point, the maximum titrant added should be 0.02 mls. At this point it can
take up to 15 minutes for the reading to become stable. You want the test to proceed as
quickly as possible, as atmospheric oxygen can interfere, but care must be taken to ensure a
stable value is obtained prior to moving onto the next point.

35. Record the millivolts and cumulative volume of silver nitrate added on the Titration Sheet
(Form 151).

36. Continue the titration until the potential change is less than 2 millivolts per 0.1 ml of silver
nitrate added. The range of the titration should be about 500 - 800 mV depending on whether
hydrogen sulphide and/or mercaptans are present.

i) If hydrogen sulphide and mercaptans are present, there will be two endpoints (inflexions).

37. Transfer the blacked out carbonyl sulphide dreschels contents into a 400 mls beaker.

38. Wash the dreschel with two 50 ml portions of acid titration solvent, adding the washings to
the beaker.

39. It is exactly the same set up as previous for the electrode system, etc but the titrant must be
alcoholic ie 0.01M silver nitrate in propan-2-ol.

40. Manually plot emf vs volume of silver nitrate added for both of the titrations.
 THE CHEMICAL DETERMINATION OF H 2S, RSH AND
COS IN HYDROCARBON GAS
REF: OP 084 REV: 04 DATE: 24 March 1998 PAGE 6 of 7

41. The end point is taken as the most positive value of the steepest portion of the curve. (See
Figure 3 for typical curves for H 2S/RSH systems and Figure 4 for COS systems).

Figure 3

NOTE In the above where H 2S and RSH are present, the H 2S endpoint is from zero to where
marked. The RSH endpoint is from the H 2S to the RSH endpoint NOT from zero to the RSH.
Software entry is the total amount to reach second endpont. It will subtract the H 2S titration
volume.

Figure 4

NOTE Both these Figures are typical titration curves. The actual values and starting points
vary with different electrode systems and depending on what compounds the sample
contains.
 THE CHEMICAL DETERMINATION OF H 2S, RSH AND
COS IN HYDROCARBON GAS
REF: OP 084 REV: 04 DATE: 24 March 1998 PAGE 7 of 7

42. Enter all information into the excel spreadsheet HYDROGEN SULPHIDE3.XLS. The results
for the respective components will be calculated.

PROCEDURE FOR H 2S GREATER THAN 1,600 PPM

For gases where the level of H 2S is high, relative to the mercaptans (say > 1,600 ppm H 2S < 160 ppm
RSH, the accuracy of the mercaptan sulphur determination may be affected. To overcome this,
follow the previous procedure to determine the H 2S and COS level then repeat the analysis but
knock out the H 2S prior to scrubbing the mercaptan sulphur. Then titrate, as before, but only
mercaptans will be present. The procedure for this is listed below.

1. Prepare 100 mls of a 5 wt% sodium carbonate solution.

2. Prepare a cadmium chloride solution:- 20g of cadmium chloride in 100 mls de-ionised water.
Add 2 mls of concentrated hydrochloric acid then make up to a final volume of 200 mls.

3. A simplified schematic of the set up is in Figure 5.

Figure 5

4. This set up will knock out the H 2S allowing a more accurate determination of mercaptans.
The rest of the procedure is exactly the same as before.