Concept model of the APG catalytic desulfurization

UDK: 66.074.5.097.094.2
DOI: 10.24887/0028-2448-2020-12-143-146
Key words: hydrogen sulfide, mercaptans, desulfurization, catalysis
Authors: A.A. Ahmadeev (Zarubezhneft JSC, RF, Moscow), I.A. Kabanov (Zarubezhneft JSC, RF, Moscow), A.V. Svetkin (Zarubezhneft JSC, RF, Moscow), A.P. Sergeev (Zarubezhneft JSC, RF, Moscow), A.A. Tyurin (Start-Catalyst LLC, RF, Moscow)2, E.A. Babakov (Start-Catalyst LLC, RF, Moscow), N.A. Bumagin (Start-Catalyst LLC, RF, Moscow; Lomonosov Moscow State University, RF, Moscow), M.Ya. Melnikov (Lomonosov Moscow State University, RF, Moscow), L.A. Tyurina (Start-Catalyst LLC, RF, Moscow; Lomonosov Moscow State University, RF, Moscow

The catalytic desulfurization is one stage selective catalytic oxidation of hydrogen sulfide and mercaptanes into sulfur and disulfides respectively. The reaction takes place in the presence of catalyst and air oxygen. Oxygen content is about 50 % of total SH concentration. Air concentration needed is far from the range of ignition. The yield of sulfur and disulfides is about 99,9999%, including of heavy mercaptanes. Reaction selectivity is 100%. Temperature is more than 25 °C. Pressure is above 0.1 MPa. The process of APG desulfurization/demercaptanization based on one-stage reaction has been realized at 25–35 °C, 0.5 MPa in the presence of catalyst in non aqueous solvent accordingly to the reaction equation. The prototype of mobile catalytic desulfurization unit has been created and tested in the field. Initial total hydrogen sulfide and mercaptans content was about 2% vol. The gas consumption was 4–25 nm3/h, catalyst content was 1–30 %. Residual hydrogen sulfide and mercaptans content was 1–3 ppm. It is shown hydrogen sulfide and mercaptane conversion is 99.995-100 and 99.875-100 % respectively. Thus, according to the APG treatment data at the field, it was found that the catalytic desulfurization technology can provide a solution to the entire set of desulfurization problems in one technological stage, including: gas desulfurization with residual hydrogen sulfide content up to 1 ppm; gas demercaptanization with residual mercaptans content up to 1 ppm; hydrogen sulfide utilization with conversion more than 99,9 %; mercaptans utilization with conversion more than 99,9 %. The prototype of mobile catalytic desulfurization unit can be used for optimization of technological conditions depending on demands of desulfurization object to enhance the technical and economic characteristics of gas treatment in various fields.

References

1. Amosa M.,Mohammed I.,Yaro S., Sulphide scavengers in oil and gas industry. A review, Nafta, 2010, no. 61, pp. 85–92.

2. Mazgarov A.M., Kornetova O.M., Tekhnologii ochistki poputnogo neftyanogo gaza ot serovodoroda (Technologies for associated petroleum gas desulphurization) Kazan': Publ. of KFU, 2015, 70 p.

3. Busygina N.V., Busygin I.G., Tekhnologii pererabotki prirodnogo gaza i gazovogo kondensata (Natural gas and gas condensate processing technologies), Orenburg: Gazprompechat' Publ., 2002, 432 p.

4. El-Gendy N.S., Speight J.G., Handbook of refinery desulfurization, Taylor & Francis: Boca Raton, 2019, 492 p.

5. Grunval'd V.R., Tekhnologiya gazovoy sery (Gas sulfur technology), Moscow: Khimiya Publ., 1992, 272 p.

6. Patent RU 2649442 C2, Apparatus, method and catalyst for the purification of a gaseous raw hydrocarbon from hydrogen sulfide and mercaptans, Inventors: Tyurin A.I., Tarkhanova I.G., Tyurina L.A.

7. Patent US 10144001B2, Device, process, and catalyst intended for desulfurization / demercaptanization / dehydration of gaseous hydrocarbons, Inventors: Tyurina L.A., Tyurin A.I., Tarkhanova I.G., Tyurin A.A.

8. Kohl A.L., Nielsen R.B., Gas purification, Chapter 2. Alkanolamines for hydrogen sulfide and carbon dioxide removal, 5th ed.: Houston, TX, USA, 1997, pp. 40–186.

9. Mathias P.M., Jasperson L.V., von Niederhausern D. et al., Assessing anhydrous tertiary alkanolamines for high-pressure gas purifications, Ind. Eng.Chem. Res., 2013, no. 52, pp. 17562–17572.

10. Khayrulin S.R., Ismagilov Z.R., Kerzhentsev M.A., Direct heterogeneous catalytic oxidation of hydrogen sulfide to elemental sulfur (In Russ.), Khimicheskaya promyshlennost', 1996, no. 4, pp. 265–268.

11. Ismagilov Z.R., Khayrulin S.R., Kerzhentsev M.A. et al., A fluidized bed reactor for the direct oxidation of hydrogen sulfide to elemental sulfur. Creation of a pilot plant at the Bavlinskaya hydrogen sulfide oxidation unit (In Russ.), Kataliz v promyshlennosti, Special Issue, 2004, pp. 50–55.

The catalytic desulfurization is one stage selective catalytic oxidation of hydrogen sulfide and mercaptanes into sulfur and disulfides respectively. The reaction takes place in the presence of catalyst and air oxygen. Oxygen content is about 50 % of total SH concentration. Air concentration needed is far from the range of ignition. The yield of sulfur and disulfides is about 99,9999%, including of heavy mercaptanes. Reaction selectivity is 100%. Temperature is more than 25 °C. Pressure is above 0.1 MPa. The process of APG desulfurization/demercaptanization based on one-stage reaction has been realized at 25–35 °C, 0.5 MPa in the presence of catalyst in non aqueous solvent accordingly to the reaction equation. The prototype of mobile catalytic desulfurization unit has been created and tested in the field. Initial total hydrogen sulfide and mercaptans content was about 2% vol. The gas consumption was 4–25 nm3/h, catalyst content was 1–30 %. Residual hydrogen sulfide and mercaptans content was 1–3 ppm. It is shown hydrogen sulfide and mercaptane conversion is 99.995-100 and 99.875-100 % respectively. Thus, according to the APG treatment data at the field, it was found that the catalytic desulfurization technology can provide a solution to the entire set of desulfurization problems in one technological stage, including: gas desulfurization with residual hydrogen sulfide content up to 1 ppm; gas demercaptanization with residual mercaptans content up to 1 ppm; hydrogen sulfide utilization with conversion more than 99,9 %; mercaptans utilization with conversion more than 99,9 %. The prototype of mobile catalytic desulfurization unit can be used for optimization of technological conditions depending on demands of desulfurization object to enhance the technical and economic characteristics of gas treatment in various fields.

References

1. Amosa M.,Mohammed I.,Yaro S., Sulphide scavengers in oil and gas industry. A review, Nafta, 2010, no. 61, pp. 85–92.

2. Mazgarov A.M., Kornetova O.M., Tekhnologii ochistki poputnogo neftyanogo gaza ot serovodoroda (Technologies for associated petroleum gas desulphurization) Kazan': Publ. of KFU, 2015, 70 p.

3. Busygina N.V., Busygin I.G., Tekhnologii pererabotki prirodnogo gaza i gazovogo kondensata (Natural gas and gas condensate processing technologies), Orenburg: Gazprompechat' Publ., 2002, 432 p.

4. El-Gendy N.S., Speight J.G., Handbook of refinery desulfurization, Taylor & Francis: Boca Raton, 2019, 492 p.

5. Grunval'd V.R., Tekhnologiya gazovoy sery (Gas sulfur technology), Moscow: Khimiya Publ., 1992, 272 p.

6. Patent RU 2649442 C2, Apparatus, method and catalyst for the purification of a gaseous raw hydrocarbon from hydrogen sulfide and mercaptans, Inventors: Tyurin A.I., Tarkhanova I.G., Tyurina L.A.

7. Patent US 10144001B2, Device, process, and catalyst intended for desulfurization / demercaptanization / dehydration of gaseous hydrocarbons, Inventors: Tyurina L.A., Tyurin A.I., Tarkhanova I.G., Tyurin A.A.

8. Kohl A.L., Nielsen R.B., Gas purification, Chapter 2. Alkanolamines for hydrogen sulfide and carbon dioxide removal, 5th ed.: Houston, TX, USA, 1997, pp. 40–186.

9. Mathias P.M., Jasperson L.V., von Niederhausern D. et al., Assessing anhydrous tertiary alkanolamines for high-pressure gas purifications, Ind. Eng.Chem. Res., 2013, no. 52, pp. 17562–17572.

10. Khayrulin S.R., Ismagilov Z.R., Kerzhentsev M.A., Direct heterogeneous catalytic oxidation of hydrogen sulfide to elemental sulfur (In Russ.), Khimicheskaya promyshlennost', 1996, no. 4, pp. 265–268.

11. Ismagilov Z.R., Khayrulin S.R., Kerzhentsev M.A. et al., A fluidized bed reactor for the direct oxidation of hydrogen sulfide to elemental sulfur. Creation of a pilot plant at the Bavlinskaya hydrogen sulfide oxidation unit (In Russ.), Kataliz v promyshlennosti, Special Issue, 2004, pp. 50–55.


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