Organochlorine compounds in oil: problems and solutions

UDK: 622.276.8
DOI: 10.24887/0028-2448-2021-4-110-113
Key words: organochlorine, crude oil, naphtha, method of analysis, national standard GOST R 51858-2002, technical regulations of Eurasian Economic Union TR EAEU 045/2017
Authors: V.V. Nosov (RN-BashNIPIneft LLC, RF, Ufa), A.Yu. Presnyakov (RN-BashNIPIneft LLC, RF, Ufa), A.G. Badamshin (RN-BashNIPIneft LLC, RF, Ufa), E.Yu. Neviadovskyi (Rosneft Oil Company, RF, Moscow), A.I. Voloshin (RN-BashNIPIneft LLC, RF, Ufa), V.A. Dokichev (RN-BashNIPIneft LLC, RF, Ufa)

Modern problems related to the presence of chlorine-organic compounds (COC) in crude oil, its production and processing, and sources of COC in oil are considered. The tasks set by modern regulatory requirements for the content of COC in oil and naphtha and the possibility of solving them using analytical methods of existing standards are considered in particular. It is shown that the existing methods for determining COC in oil are not optimal. There is an urgent need to expand analytical methods, increase their accuracy and informativeness.

An important aspect related to the sources of the appearance of COC in oil is noted, namely, one of which is natural, determining some components of crude oil, and the other source is chlorine-containing oilfield reagents used at various stages of oil production, transportation and preparation, as well as products of their thermal and chemical transformations. It is assumed that the formation of COC can occur as a result of hydrochloric acid treatments, hydrolysis of chloride salts, and the interaction of oil components with hydrochloric acid. It is noted that understanding the sources of COC in oil will minimize the risks during its processing. Special tests performed using chromatography-mass spectrometry evaluated the effect of the dosage and nature of the chemical reagents used on the mass fraction of COC in oil. In particular, it was shown that wax solvents containing organochlorine components in working dosages lead to an increase in the content of COC in oil. An important aspect related to the sources of COC appearance in oil is considered. Understanding this aspect will help to minimize the risks associated with organic chlorides during processing. In addition, it is indicated that analytical methods should be developed or modified to control COC in the oilfield reagents used, research should be conducted on the possible generation of COC in the implementation of well acid treatment technologies, and the influence of oil composition on their quantity should be taken into account.

References

1. Khutoryanskiy F.M., Organochlorine compounds in oil. History of the issue and problems of the present (In Russ.), Mir nefteproduktov. Vestnik neftyanykh kompaniy, 2002, no. 3, pp. 6–7.

2. Li X., Wu B., Understanding to the composition and structure of organic chlorides in petroleum and its distillates, Petroleum Science and Technology, 2019, DOI: 10.1080/10916466.2018.1514407.

3. Okhlopkov A.S., Svoystva tovarnoy syroy nefti, pozvolyayushchie identifitsirovat' istochnik neftyanogo zagryazneniya okruzhayushchey prirodnoy sredy (Properties of commercial crude oil, allowing to identify the source of oil pollution of the environment): thesis of candidate of chemical science, Nizhniy Novgorod, 2015.

4. Novikov E.A., Analytical methods for quality control of petroleum and petroleum products (In Russ.), Mir nefteproduktov, 2019, no. 7, pp. 39–50.

5. Dutta M., Pathiparampil A., Quon D. et al., Total chloride analysis in petroleum crude samples: Challenges and opportunities, Chemistry Solutions to Challenges in the Petroleum Industry ACS Symposium Series, Washington: American Chemical Society, 2019, V. 1320, Ch. 11, pp. 281–310, DOI: 10.1021/bk-2019-1320.ch011.

6. Podlesnova E.V., Botin A.A., Dmitrieva A.A. et al., Chromatographic method for determining organochlorine compounds in oil (In Russ.), Sorbtsionnye i khromatograficheskie protsessy, 2019, V. 19, no. 5, pp. 581–587, DOI: 10.17308/sorpchrom.2019.19/1173.

7. Atashgahi S., Liebensteiner M.G., Janssen D.B. et al., Microbial synthesis and transformation of inorganic and organic chlorine compounds, Front. Microbiol., 2018, V. 9, pp. 1–22, URL: https://doi.org/10.3389/fmicb.2018.03079.

8. Kozlov C.A., Frolov D.A., Kuz'mina E.P. et al., Establishment of reasons for the formation of chloric-organic compounds in commodity oil (In Russ.), Neftepromyslovoe delo, 2019, no. 5(605), pp. 65–69.

9. Sinev A.V., Devyashin T.V., Kunakova  A.M. et al., The problem of the formation of volatile organochlorine compounds during the initial distillation of oil as a result of decomposition of chemicals containing salts of quaternary ammonium compounds (In Russ.), PRONEFT''. Professional'no o nefti, 2019, no. 4(14), pp. 63–69.

10. Khutoryanskiy F.M., Chloric-organic compounds. Distribution by fractions and methods of removal from oil at the stage of its preparation for processing (In Russ.), Mir nefteproduktov. Vestnik neftyanykh kompaniy, 2002, no. 4, pp. 9–13.      

11. Wu B., Li Y., Li X. et al., Organochlorine compounds with a low boiling point in desalted crude oil: identification and conversion, Energy Fuels, 2018, V. 32, no. 6, pp. 6475–6481, https://doi.org/10.1021/acs.energyfuels.8b00205.

12. Tat'yanina O.S., Abdrakhmanova L.M., Sudykin S.N., Zhilina E.V., Obrazovanie legkoletuchikh khlororganicheskikh soedineniy pri pervichnoy peregonke nefti v rezul'tate razlozheniya khimicheskikh reagentov, soderzhashchikh soli chetvertichnykh ammonievykh soedineniy (Formation of volatile organochlorine compounds during primary distillation of oil as a result of decomposition of chemical reagents containing salts of quaternary ammonium compounds), Proceedings of TatNIPIneft', 2017, V. 85, pp. 363–369.

13. Huang K.G., Zhu Y.A., Characterization of nonmetal chloride salts and their removal from crude oil, Chemistry Solutions to Challenges in the Petroleum Industry ACS Symposium Series, Washington: American Chemical Society, DC, 2019, V. 1320, Ch. 12, pp. 311–326, DOI: 10.1021/bk-2019-1320.ch012.

14. Gray M.R., Eaton P.E., Le T., Inhibition and promotion of hydrolysis of chloride salts in model crude oil and heavy oil, Petroleum Science and Technology, 2008, V. 26, pp. 1934–1944, DOI: 10.1080/10916460701428607.

Modern problems related to the presence of chlorine-organic compounds (COC) in crude oil, its production and processing, and sources of COC in oil are considered. The tasks set by modern regulatory requirements for the content of COC in oil and naphtha and the possibility of solving them using analytical methods of existing standards are considered in particular. It is shown that the existing methods for determining COC in oil are not optimal. There is an urgent need to expand analytical methods, increase their accuracy and informativeness.

An important aspect related to the sources of the appearance of COC in oil is noted, namely, one of which is natural, determining some components of crude oil, and the other source is chlorine-containing oilfield reagents used at various stages of oil production, transportation and preparation, as well as products of their thermal and chemical transformations. It is assumed that the formation of COC can occur as a result of hydrochloric acid treatments, hydrolysis of chloride salts, and the interaction of oil components with hydrochloric acid. It is noted that understanding the sources of COC in oil will minimize the risks during its processing. Special tests performed using chromatography-mass spectrometry evaluated the effect of the dosage and nature of the chemical reagents used on the mass fraction of COC in oil. In particular, it was shown that wax solvents containing organochlorine components in working dosages lead to an increase in the content of COC in oil. An important aspect related to the sources of COC appearance in oil is considered. Understanding this aspect will help to minimize the risks associated with organic chlorides during processing. In addition, it is indicated that analytical methods should be developed or modified to control COC in the oilfield reagents used, research should be conducted on the possible generation of COC in the implementation of well acid treatment technologies, and the influence of oil composition on their quantity should be taken into account.

References

1. Khutoryanskiy F.M., Organochlorine compounds in oil. History of the issue and problems of the present (In Russ.), Mir nefteproduktov. Vestnik neftyanykh kompaniy, 2002, no. 3, pp. 6–7.

2. Li X., Wu B., Understanding to the composition and structure of organic chlorides in petroleum and its distillates, Petroleum Science and Technology, 2019, DOI: 10.1080/10916466.2018.1514407.

3. Okhlopkov A.S., Svoystva tovarnoy syroy nefti, pozvolyayushchie identifitsirovat' istochnik neftyanogo zagryazneniya okruzhayushchey prirodnoy sredy (Properties of commercial crude oil, allowing to identify the source of oil pollution of the environment): thesis of candidate of chemical science, Nizhniy Novgorod, 2015.

4. Novikov E.A., Analytical methods for quality control of petroleum and petroleum products (In Russ.), Mir nefteproduktov, 2019, no. 7, pp. 39–50.

5. Dutta M., Pathiparampil A., Quon D. et al., Total chloride analysis in petroleum crude samples: Challenges and opportunities, Chemistry Solutions to Challenges in the Petroleum Industry ACS Symposium Series, Washington: American Chemical Society, 2019, V. 1320, Ch. 11, pp. 281–310, DOI: 10.1021/bk-2019-1320.ch011.

6. Podlesnova E.V., Botin A.A., Dmitrieva A.A. et al., Chromatographic method for determining organochlorine compounds in oil (In Russ.), Sorbtsionnye i khromatograficheskie protsessy, 2019, V. 19, no. 5, pp. 581–587, DOI: 10.17308/sorpchrom.2019.19/1173.

7. Atashgahi S., Liebensteiner M.G., Janssen D.B. et al., Microbial synthesis and transformation of inorganic and organic chlorine compounds, Front. Microbiol., 2018, V. 9, pp. 1–22, URL: https://doi.org/10.3389/fmicb.2018.03079.

8. Kozlov C.A., Frolov D.A., Kuz'mina E.P. et al., Establishment of reasons for the formation of chloric-organic compounds in commodity oil (In Russ.), Neftepromyslovoe delo, 2019, no. 5(605), pp. 65–69.

9. Sinev A.V., Devyashin T.V., Kunakova  A.M. et al., The problem of the formation of volatile organochlorine compounds during the initial distillation of oil as a result of decomposition of chemicals containing salts of quaternary ammonium compounds (In Russ.), PRONEFT''. Professional'no o nefti, 2019, no. 4(14), pp. 63–69.

10. Khutoryanskiy F.M., Chloric-organic compounds. Distribution by fractions and methods of removal from oil at the stage of its preparation for processing (In Russ.), Mir nefteproduktov. Vestnik neftyanykh kompaniy, 2002, no. 4, pp. 9–13.      

11. Wu B., Li Y., Li X. et al., Organochlorine compounds with a low boiling point in desalted crude oil: identification and conversion, Energy Fuels, 2018, V. 32, no. 6, pp. 6475–6481, https://doi.org/10.1021/acs.energyfuels.8b00205.

12. Tat'yanina O.S., Abdrakhmanova L.M., Sudykin S.N., Zhilina E.V., Obrazovanie legkoletuchikh khlororganicheskikh soedineniy pri pervichnoy peregonke nefti v rezul'tate razlozheniya khimicheskikh reagentov, soderzhashchikh soli chetvertichnykh ammonievykh soedineniy (Formation of volatile organochlorine compounds during primary distillation of oil as a result of decomposition of chemical reagents containing salts of quaternary ammonium compounds), Proceedings of TatNIPIneft', 2017, V. 85, pp. 363–369.

13. Huang K.G., Zhu Y.A., Characterization of nonmetal chloride salts and their removal from crude oil, Chemistry Solutions to Challenges in the Petroleum Industry ACS Symposium Series, Washington: American Chemical Society, DC, 2019, V. 1320, Ch. 12, pp. 311–326, DOI: 10.1021/bk-2019-1320.ch012.

14. Gray M.R., Eaton P.E., Le T., Inhibition and promotion of hydrolysis of chloride salts in model crude oil and heavy oil, Petroleum Science and Technology, 2008, V. 26, pp. 1934–1944, DOI: 10.1080/10916460701428607.


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