Innovative Analytical Technique to Evaluate Scale Inhibitors

Vidhi Khatri, Shikha Trivedi, Nalini Ghosh, S. K. Kaul and Harvir Singh
Western Offshore Basin, ONGC, Mumbai

Email bandhu_vidhi@ongc.co.in

Scaling is a matter of concern in the E&P industry as it directly affects the well productivity.
Millions of dollars are lost in revenue every year because scale creates flow restrictions in
our fields. The direct cost of removing scale from a well can be quite high and the cost of
deferred production even higher. As in medical parlance prevention is better than cure
similarly keeping producing wells healthy is ultimately the economically efficient way to
produce hydrocarbons.
In most cases scale prevention through chemical inhibition is the preferred method of
maintaining well productivity. Inhibition techniques can range from basic dilution to the
advanced and cost effective technique of chemical intervention i.e., use of appropriate scale
inhibitors. In industry innumerable scale inhibitors with diverse applications ranging from
heating boilers to oil wells are available. As scale inhibitors are very important products to
tackle scaling problem, their accurate evaluation is the first and most important step towards
effective scale control.
Most scale inhibitors meant for inorganic scales are phosphorous compounds-like
polyphosphate derivatives, organic phosphonates, organic aminophosphates and organic
polymers. The effective concentrations of phosphonate inhibitor cover a range which varies
with temperature, time, degree of supersaturation, type of scale-forming deposit, etc. Hence
their performance can be evaluated on the basis of their active ingredients e.g., phosphonic
acids, phophonates present in them.
The present paper is an attempt to evaluate the active ingredients i.e., phosphonate
derivatives in scale inhibitor samples by two colorimetric techniques. The paper also tries to
correlate the performance evaluation of scale inhibitor based on the standard ONGC/NACE
test procedure with the active ingredient present in it and also compares the two colorimetric
methods used for evaluation. Exhaustive laboratory studies carried out on numerous scale
inhibitors established a direct correlation between the performance evaluation, based on
ONGC/NACE tests procedure (percent inhibition efficiency) and accurate estimation of
active ingredient in a particular scale inhibitor. The results show that the percent inhibition
efficiency of the scale inhibitor increases with increase in the percentage of active ingredient
present in it.
Presently, scale inhibitors are screened on the basis of percentage inhibition efficiency under
standard test conditions by the Chelation test, in which two incompatible solutions are
combined and the precipitated solid (scale) is measured in the presence of an inhibitor of
varying concentrations by means of chemical analysis. However, the reproducibility of the
result by this method is sometimes not very good and data reported by different analysts
contradictory. Analyzing the composition of scale inhibitors would be a better option to
perform quality control checks of commercial scale inhibitor products and to verify that the
product meets specifications for prevailing test conditions.
The two colorimetric techniques A and B used to evaluate the active ingredient employ two
basic processes, i.e., digestion and colour development. Both methods give repeatable and
reproducible results but method B is less time consuming and easy to adopt than method A.
In both the methods the phosphonates are oxidized to phosphate by persulphate, and the
increased phosphate concentration is measured as the classical phosphomolybdate blue
complex by UV spectrophotometer. The increase in colour in the sample is proportional to
the phosphate produced in the digestion.
In method A, 6N HCl along with 0.2 gm potassium peroxidisulphate is used for digestion and
heating is carried out using autoclave at 100-121oC & 15-20 psi for 30 minutes. Color is
developed by using methyl isobutyl ketone (MIBK) and cyclohexane solvent (1:1), molybdate
reagent, alcoholic HCl and stannous chloride solution. In method-B, 6M H2SO4 along with
1.0 gm potassium peroxidisulphate is used for digestion and heating is carried out on hot
plate for 90 minutes. For color development process metol-disulphite-citric acid solution and
molybdate reagent are used. A photometric measurement is made at 720 nm against a
blank that has been treated in the same way as the sample solution using standard
phosphate calibration curve. In both these methods adherence to Beers law is studied by
measuring the absorbance values of solutions varying phosphate concentration. A straight
line graph is obtained by plotting absorbance against concentration of phosphate. Beers law
is obeyed in the concentration range 1.010.0 g/ml of phosphate.
A minimum active ingredient of ~35% gives a performance efficiency of 92%, the passing
criteria for selection of scale inhibitors (ONGC specifications). As the active ingredient in the
scale inhibitor increases above 35%, the percent inhibition efficiency also increases;
Samples which have an active ingredient greater than 55% and inhibition efficiency more
than 92% are in line with the increasing trend. Extensive experimentation done on numerous
scale inhibitor samples show that approximately 1% increase in percent inhibition efficiency
corresponds to 5% increase in active ingredient. The results of laboratory evaluation by this
methodology are reproducible as shown in numerous samples evaluated in present study.
Application of this technique of active ingredient estimation for performance evaluation will
help procure better quality scale inhibitors as results are consistent in terms of repeatability
and reproducibility over the wide range of concentration.
This rapid and meaningful analytical technique will be able to provide an accurate quality
control tool to evaluate scale inhibitor supplies. Also, this technique is suitable for squeeze
treatment jobs where phosphonate based scale inhibitors are used, as the return inhibitor
concentration can be accurately determined by this method. This new estimation technique
and an awareness of quality control in terms of active ingredient, provide a reasonable
selection criterion for the phosphonate based scale inhibitors in the oil field.