A well-established test in the petrochemical industry is the determination of the hydrogen sulfide and mercaptan sulfur content in petroleum distil-lates and other hydrocarbon products. The sulfur content of fuels is a key parameter in their quality control, and its limits are defined by strict quality standards.

Assigning the Correct Equivalence Point in the Titration of Mercaptans

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A high content of sulfur in fuel leads to inefficient combustion and to the formation of corrosive, acidic deposits that damage the metal components of the engine. As well as damage to the engine, atmospheric emissions from sulfur-containing fuels have high levels of sulfur dioxide, which when dissolved in atmospheric moisture, falls as acid rain. This causes dam-age to the environment and building structures (Fig. 1), and has a negative economic impact.

The testing of petroleum distillates for their sulfur content is therefore man-datory. Many different test methods have appeared, but the ones that have proven to be most reliable are those based on titration. The UOP 163-05 laboratory test method outlines a simple titration with alcoholic silver nitrate solution that allows the sulfur compounds to be determined. How-ever, things are seldom that simple... The sulfur compounds most often found in petroleum distillates are

hydrogen sulfide (H2S) and alkyl mercaptans (RSH), although some distillates may also contain elemental sulfur. This reacts with mercaptans to form polysulfide compounds (RSSH).

In practice, most real-world samples contain mixtures of these substances, which will affect the resulting titration curve profile obtained. Any analytical technique used to analyze unknown samples must take account of this variation and yet still allow quick and easy calculation of the correct results.

The UOP163-05 test method (avail-able from ASTM) describes how the different curve types should be evalu-ated in practice. The first stage is to establish the presence or absence of hydrogen sulfide using the qualita-tive lead acetate strip or “Doctor Test” according to UOP 41 where a positive test result indicates the presence of H2S. With this knowledge, there are then five possibilities to consider.

Figure 1: Acid rain can cause great damage to buildings and works of art.

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Interpreting the titration curveThe challenge for automating the pro-cedure is to ensure that irrespective of the type of curve only the correct results are calculated. Two variables need to be taken account of:

• Thenumberofequivalencepoints(EQP) on the curve.

• Theresultofthedoctortest (positive or negative).

The first of these forms part of the raw data (nEQ) and is so easily acces-sible. The result of the doctor test result can be entered with the sample data using the correction factor and a binary format. We set f=1 for samples

that give a positive test result and f=0 for those with a negative test (see Fig. 2.)

If the T90 Excellence titrator is used, we have the possibility of adding condition statements to the calculation functions in the method (see Fig. 3).

The full set of calculations needed in the method to cover all five possibili-ties given is shown in Table 1.

Figure 2: Entry of the correction factor, f, with the sample data.

Figure 3: The condition applied to the calcu-lation function.

Result Formula Condition Valid for n EQPs

ppm H2S R=Q*C/m f=1 1, 2 or 3

ppm RSH R2=Q*C/m nEQ=1ANDf=0 1

ppm RSH R3=Q2*C/m nEQ=2ANDf=1 2

ppm RSH R4=(Q+Q2)*C/m nEQ=2ANDf=0 2

ppm RSH R5=(Q2+Q3)*C/m nEQ=3ANDf=1 3

Table 1: Calculations and conditions for the T90 method.

Ingenious calculations

What can be done if a T90 is not available and we have to use a T50 or T70 for these tests?

The answer is more complex because we cannot use conditional statements to exclude incorrect calculation of results. The best we can hope to do

is to render unhelpful results as either zero or NaN (not a number). The cal-culation formulae themselves need to be altered to allow this. The f or (1-f) terms ensure that H2S is only calcu-lated when it is in fact present. (see Tab. 2).

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The results of these calculations will allow the correct RSH value to be identified as can be seen from the table of outcomes (Tab. 3). The additional (x–nEQ) elements of the second and third calculations

Result Formula

ppm H2S R=Q*C*f/m

ppm RSH R2=Q*C*(1-f)*(2-nEQ)/m

ppm RSH R3=Q2*C*f*(3-nEQ)/m

ppm RSH R4=(Q+Q2)*(1-f)*C/m

ppm RSH R5=(Q2+Q3)*f*C/m

Table 2: Calculations for the T50/T70 method.

nEQ/test R1 R2 R3 R4 R5

1+ xxx 0 NaN NaN NaN

1– 0 xxx NaN NaN NaN

2+ xxx 0 xxx 0 NaN

2– 0 0 0 xxx NaN

3+ xxx 0 0 0 xxx

Table 3: Identification of the correct RSH value (xxx = result, NaN = not a number).

Curve with 1 EQP

a) Positive doctor testThe EQP is caused by titration of the H2S.R = Q*C/m

b) Negative doctor test The EQP is caused by titration of the mercaptan RSH.

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Curve with 2 EQPs

a) Positive doctor test The first EQP is caused by the titration of the H2S (R = Q*C/m).The second EQP is caused by titration of mercaptan RSH. (R = Q2*C/m)

b) Negative doctor test There is elemental sulfur present, so we ignore the first EQP and take the total consumption to the second EQP as caused by the mercaptan. (R = (Q+Q2)*C/m)

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Q mLQ2

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(Tab. 2) prevent the calculation of multiple RSH results in the case of scenarios with two or three equiva-lence points (Figs. 5 and 6). There is only ever one non-zero result for the mercaptan content.

Conclusions

Curve with 3 EQPs

a) Positive doctor test The first EQP is caused by titration of the H2S (R=Q*C/m)The second EQP is from the polysulfide formed when mercap-tan-sulfur reacts with elemental sulfur. This EQP is ignored.

The third EQP is from the titration of the mercaptan, but the calcu-lation must be based on the total titrant consumption from the first to the third EQP. (R = (Q2+Q3)*C/m)

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QmLQ2 Q3

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Figure 7Detail of titrator T90 with OneClick® display

All the models in the Titration Excellence line allow the correct selection of cal-culation according to the UOP 163-05

standard test method, although the most convenient and best solution is available with the T90 model.

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