Particularities of sulfamic acid properties increasing the effectiveness of acid treatments

UDK: 622.276.63
DOI: 10.24887/0028-2448-2021-1-44-47
Key words: acidizing, solid acid compositions, sulfamic acid, aminosulfonic acid, ammonium fluoride, ammonium bifluoride, surfactant, oil-acid emulsion, acid corrosion
Authors: M.A. Silin (Gubkin University, RF, Moscow), L.A. Magadova (Gubkin University, RF, Moscow), L.F. Davletshina (Gubkin University, RF, Moscow), Z.R. Davletov (Gubkin University, RF, Moscow), K.A. Poteshkina (Gubkin University, RF, Moscow)

Review of long-term researches on acidizing of production and injection wells using solid acid compositions based on sulfamic acid, that were carried out at the National University of Oil and Gas Gubkin University, is presented in this paper. Sulfamic acid is formed by the interaction of carbamide and oleum at 60–70°C and is produced in the form of non-adsorbing water crystals. The behavior of the acid is associated with the formation of zwitter-ions in water, which contribute to activity increase of synthetic surfactants. Sulfamic acid has advantages over hydrochloric acid; it has a slower reaction rate with carbonate rock and is less aggressive towards metal surfaces of production equipment. Sulfamic acid produces less viscous oil-acid emulsions that do not form sludge deposits. Injection of sulfamic acid solutions into oil-saturated porous medium under thermobaric conditions of the formation leads to higher phase permeability to the displacing fluid than for hydrochloric acid. Based on the obtained regularities of interaction of sulfamic acid with rock, formation fluids and damaging agents of bottomhole formation zone, solid acid compositions for treating wells operating low-temperature depleted formations were developed. The acid treatments results confirmed the effectiveness of multistage technologies based on the application of the solid acid compositions. Previous studies showed that sulfamic acid is prone to hydrolysis at temperatures above 60°C; however, the developed technologies allow the use of the acid compositions at higher temperatures.

Acknowledgment. This work was supported by the Ministry of Science and Higher Education of the Russian Federation under agreement No. 075-15-2020-936 within the framework of the development program for a world-class Research Center.

References

1. Maksin V.I., Standritchuk O.Z., Kinetics and mechanism of hydrolysis of sulfamic acid (In Russ.), Zhurnal fizicheskoy khimii = Russian Journal of Physical Chemistry A, 1995, V. 69, no. 6, pp. 974–979.

2. Amerkhanova Sh.K., Shlyapov R.M., Uali A.S., Features of the dissociation process of sulfamic acid in aqueous-organic solvents (In Russ.), Vestnik Voronezhskogo gosudarstvennogo universiteta. Seriya: Khimiya. Biologiya. Farmatsiya, 2014, no. 3, pp. 5–8.

3. Amiyan V.A., Ugolev V.S., Fiziko-khimicheskie metody uvelicheniya proizvoditel'nosti skvazhin (Physico-chemical methods to increase the productivity of wells), Moscow: Nedra Publ., 1970, 280 p.

4. Magadova L.A., Tsygankov V.A., Pakhomov M.D., Yunusov T.I., Development of thermostable dry acid composition based on sulfamic acid (In Russ.), Trudy Rossiyskogo gosudarstvennogo universiteta nefti i gaza im. I.M. Gubkina, 2019, no. 4 (297), pp. 186–198.

5. Patent RU 2101482 C1, MPK E 21 V 43/27, Acid compound for treating terrigenous reservoirs, Inventors: Magadov R.S., Silin M.A., Gaevoy E.G., Rud' M.I., Magadova L.A., Chekalina G., Maksimova S.V., Poddubnyy Yu.A., Galeev F.Kh., Dyabin A.G., Kan V.A., Sorkin A.Ya.

6. Magadova L.A., Davletshina L.F., Pakhomov M.D., Davletov Z.R., Terrigenous reservoirs rock dissolution investigation in the fluorinated acid compounds (In Russ.), Territoriya Neftegaz, 2015, no. 12, pp. 94–100.

7. Silin M.A., Magadova L.A., Tolstykh L.I. et al., Aspects of interaction of surfactant-acid compositions at phase boundary with hydrocarbons (In Russ.), Zhurnal prikladnoy khimii = Russian Journal of Applied Chemistry, 2019, V. 92, no. 12, pp. 1732–1741.

8. Magadova L.A., Davletshina L.F., Gubanov V.B. et al., Research of specific aspects in interaction between oil and acid compositions in porous medium (In Russ.), Trudy Rossiyskogo gosudarstvennogo universiteta nefti i gaza im. I.M. Gubkina, 2017, no. 4(289), pp. 132–142.

9. Davletshina L.F., Tolstykh L.I., Davletov Z.R., Vlasova V.D., Study of interfacial tension at the boundary between hydrocarbon phase and acid compositions based on sulfamic acid and surfactants (In Russ.), Territoriya Neftegaz, 2017, no. 9, pp. 20–26.

10. Ganeeva Yu.M., Barskaya E.E., Okhotnikova E.S. et al., Distribution of paraffin hydrocarbons and asphaltenes in acidic water-oil emulsion (In Russ.), Neftekhimiya = Petroleum Chemistry, 2018, V. 58, no. 6, pp. 742–750.

11. Silin M.A., Magadova L.A., Davletshina L.F. et al., Features of interfacial phenomena at the phase boundary between hydrocarbon systems and acids (In Russ.), Khimiya i tekhnologiya topliv i masel, 2020, no. 2, pp. 25–30.

12. Amiyan V.A., Ugolev V.S., Kuznetsov G.N., Physico-chemical methods to increase the productivity of wells (In Russ.), Neftyanoe khozyaystvo = Oil Industry, 1969, no. 10, pp. 62–65.

13. Silin M.A., Magadova L.A., Davletshina L.F. et al., Research of current corrosion inhibitors action in acid systems (In Russ.), Praktika protivokorrozionnoy zashchity, 2016, no. 4 (82), pp. 22–30.

14. Magadova L.A., Davletshina L.F., Efanova O.Yu., Poteshkina K.A., The problem of investigation of coiled tubing corrosion during acid treatment (In Russ.), Tekhnologii nefti i gaza, 2012, no. 2, pp. 12–15.

15. Silin M.A., Magadova L.A., Davletshina L.F., Efanova O.Yu., Stimulation of terrigenous reservoirs through producing wells annulus (In Russ.), Neftepromyslovoe delo, 2012, no. 7, pp. 27–30. 

16. Davletshina L.F., Magadova L.A., Silin M.A.  et al., Acid treatment of injection wells. Old problems - new solutions (In Russ.), Territoriya Neftegaz, 2009, no. 3, pp. 38–41.

17. Davletshina L.F., Gus'kova I.A., Garipova L.I., Akhmetshina A.S., Integrated approach to the development of technology of iInjection well bottomhole treatment and the technology efficiency evaluation (In Russ.), Neftyanoe khozyaystvo = Oil Industry, 2020, no. 7, pp. 40–42.

Review of long-term researches on acidizing of production and injection wells using solid acid compositions based on sulfamic acid, that were carried out at the National University of Oil and Gas Gubkin University, is presented in this paper. Sulfamic acid is formed by the interaction of carbamide and oleum at 60–70°C and is produced in the form of non-adsorbing water crystals. The behavior of the acid is associated with the formation of zwitter-ions in water, which contribute to activity increase of synthetic surfactants. Sulfamic acid has advantages over hydrochloric acid; it has a slower reaction rate with carbonate rock and is less aggressive towards metal surfaces of production equipment. Sulfamic acid produces less viscous oil-acid emulsions that do not form sludge deposits. Injection of sulfamic acid solutions into oil-saturated porous medium under thermobaric conditions of the formation leads to higher phase permeability to the displacing fluid than for hydrochloric acid. Based on the obtained regularities of interaction of sulfamic acid with rock, formation fluids and damaging agents of bottomhole formation zone, solid acid compositions for treating wells operating low-temperature depleted formations were developed. The acid treatments results confirmed the effectiveness of multistage technologies based on the application of the solid acid compositions. Previous studies showed that sulfamic acid is prone to hydrolysis at temperatures above 60°C; however, the developed technologies allow the use of the acid compositions at higher temperatures.

Acknowledgment. This work was supported by the Ministry of Science and Higher Education of the Russian Federation under agreement No. 075-15-2020-936 within the framework of the development program for a world-class Research Center.

References

1. Maksin V.I., Standritchuk O.Z., Kinetics and mechanism of hydrolysis of sulfamic acid (In Russ.), Zhurnal fizicheskoy khimii = Russian Journal of Physical Chemistry A, 1995, V. 69, no. 6, pp. 974–979.

2. Amerkhanova Sh.K., Shlyapov R.M., Uali A.S., Features of the dissociation process of sulfamic acid in aqueous-organic solvents (In Russ.), Vestnik Voronezhskogo gosudarstvennogo universiteta. Seriya: Khimiya. Biologiya. Farmatsiya, 2014, no. 3, pp. 5–8.

3. Amiyan V.A., Ugolev V.S., Fiziko-khimicheskie metody uvelicheniya proizvoditel'nosti skvazhin (Physico-chemical methods to increase the productivity of wells), Moscow: Nedra Publ., 1970, 280 p.

4. Magadova L.A., Tsygankov V.A., Pakhomov M.D., Yunusov T.I., Development of thermostable dry acid composition based on sulfamic acid (In Russ.), Trudy Rossiyskogo gosudarstvennogo universiteta nefti i gaza im. I.M. Gubkina, 2019, no. 4 (297), pp. 186–198.

5. Patent RU 2101482 C1, MPK E 21 V 43/27, Acid compound for treating terrigenous reservoirs, Inventors: Magadov R.S., Silin M.A., Gaevoy E.G., Rud' M.I., Magadova L.A., Chekalina G., Maksimova S.V., Poddubnyy Yu.A., Galeev F.Kh., Dyabin A.G., Kan V.A., Sorkin A.Ya.

6. Magadova L.A., Davletshina L.F., Pakhomov M.D., Davletov Z.R., Terrigenous reservoirs rock dissolution investigation in the fluorinated acid compounds (In Russ.), Territoriya Neftegaz, 2015, no. 12, pp. 94–100.

7. Silin M.A., Magadova L.A., Tolstykh L.I. et al., Aspects of interaction of surfactant-acid compositions at phase boundary with hydrocarbons (In Russ.), Zhurnal prikladnoy khimii = Russian Journal of Applied Chemistry, 2019, V. 92, no. 12, pp. 1732–1741.

8. Magadova L.A., Davletshina L.F., Gubanov V.B. et al., Research of specific aspects in interaction between oil and acid compositions in porous medium (In Russ.), Trudy Rossiyskogo gosudarstvennogo universiteta nefti i gaza im. I.M. Gubkina, 2017, no. 4(289), pp. 132–142.

9. Davletshina L.F., Tolstykh L.I., Davletov Z.R., Vlasova V.D., Study of interfacial tension at the boundary between hydrocarbon phase and acid compositions based on sulfamic acid and surfactants (In Russ.), Territoriya Neftegaz, 2017, no. 9, pp. 20–26.

10. Ganeeva Yu.M., Barskaya E.E., Okhotnikova E.S. et al., Distribution of paraffin hydrocarbons and asphaltenes in acidic water-oil emulsion (In Russ.), Neftekhimiya = Petroleum Chemistry, 2018, V. 58, no. 6, pp. 742–750.

11. Silin M.A., Magadova L.A., Davletshina L.F. et al., Features of interfacial phenomena at the phase boundary between hydrocarbon systems and acids (In Russ.), Khimiya i tekhnologiya topliv i masel, 2020, no. 2, pp. 25–30.

12. Amiyan V.A., Ugolev V.S., Kuznetsov G.N., Physico-chemical methods to increase the productivity of wells (In Russ.), Neftyanoe khozyaystvo = Oil Industry, 1969, no. 10, pp. 62–65.

13. Silin M.A., Magadova L.A., Davletshina L.F. et al., Research of current corrosion inhibitors action in acid systems (In Russ.), Praktika protivokorrozionnoy zashchity, 2016, no. 4 (82), pp. 22–30.

14. Magadova L.A., Davletshina L.F., Efanova O.Yu., Poteshkina K.A., The problem of investigation of coiled tubing corrosion during acid treatment (In Russ.), Tekhnologii nefti i gaza, 2012, no. 2, pp. 12–15.

15. Silin M.A., Magadova L.A., Davletshina L.F., Efanova O.Yu., Stimulation of terrigenous reservoirs through producing wells annulus (In Russ.), Neftepromyslovoe delo, 2012, no. 7, pp. 27–30. 

16. Davletshina L.F., Magadova L.A., Silin M.A.  et al., Acid treatment of injection wells. Old problems - new solutions (In Russ.), Territoriya Neftegaz, 2009, no. 3, pp. 38–41.

17. Davletshina L.F., Gus'kova I.A., Garipova L.I., Akhmetshina A.S., Integrated approach to the development of technology of iInjection well bottomhole treatment and the technology efficiency evaluation (In Russ.), Neftyanoe khozyaystvo = Oil Industry, 2020, no. 7, pp. 40–42.


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