A Systematic Investigation of Factors Affecting the Formation of Zinc Sulfide (ZnS)
- Alexander J. Graham (Heriot-Watt University) | Michael A. Singleton (Heriot-Watt University) | Ken S. Sorbie (Heriot-Watt University) | Ian R. Collins (Upstream Technology Chemical Sciences Centre of Expertise)
- Document ID
- Society of Petroleum Engineers
- SPE Production & Operations
- Publication Date
- August 2017
- Document Type
- Journal Paper
- 314 - 324
- 2017.Society of Petroleum Engineers
- Sulfides, Scale formation
- 0 in the last 30 days
- 142 since 2007
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Work was undertaken to systematically investigate the factors that affect the formation of zinc sulfide (ZnS) in an aqueous system. Experiments were performed at a series of temperatures from room temperature up to 90°C, at a range of initial pH values and in two brine systems. The effect of pH was examined further by changing the salt from Na2S·9H2O to NaSH·xH2O, therefore changing the initial sulfide source from S2– to HS–, as part of an ongoing method-development strategy.
The formation of ZnS was achieved by the equivolume mixing of two preheated bottles, which contained aqueous “H2S” and zinc ions, respectively. Having pH adjusted the zinc brine to values calculated by an in-house thermodynamic model, the brines were preheated to the required temperature and mixed. Aliquots were removed at 2, 4, and 24 hours to perform elemental analysis by inductively coupled plasma optical emission spectrometry (ICP-OES), and pH measurements were performed on all samples after they had returned to room temperature. In addition, particlesize analysis and environmental scanning electron microscopy (ESEM) examination of the resulting precipitate were also performed for a subset of the samples prepared.
The reaction between zinc ions and aqueous “H2S” was quantitative at all temperatures up to 90°C and in both brines. The final pH values of the supernatant were independent of the zinc brine pH, and instead were dependent on the molar ratio of zinc and sulfide ions. With a high pH, sulfide-dominated, and a low pH, zinc-dominated, plateau regions were seen with a sharp inflection between the two. As a consequence, reaching field-representative pH values was seen to be extremely difficult while retaining the ability to alter the relative concentrations of the reacting ions. Altering the sulfide source yielded the same trend, although with different absolute values. These observations have been rationalized with reference to the thermodynamic constants governing the reaction through scale-prediction modeling. The work presented here provides a greater understanding of the factors governing the formation of ZnS scale and the considerations required for more industrially relevant formation and inhibition experiments in the future.
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