Peculiar aspects of removal of chlororganic compounds from crude oil

UDK: 622.276.8 + 546.13
DOI: 10.24887/0028-2448-2020-8-103-105
Key words: crude oil, naphtha, removal, chlororganic compounds, sodium hydroxide
Authors: О.S. Tatyanina (TatNIPIneft, RF, Bugulma), F.R. Gubaidulin (TatNIPIneft, RF, Bugulma), S.N. Sudykin (TatNIPIneft, RF, Bugulma), L.М. Abdrakhmanova (TatNIPIneft, RF, Bugulma)
Treatment of naphtha contaminated with highly volatile chlororganic compounds using aqueous solutions of sodium hydroxide at high temperatures enables considerable reduction of organic chlorine content. Chromatography-mass spectrometry studies have demonstrated that alkyl halides degrade firstly. Efficiency of the removal of organic chlorine depends directly on naphtha treatment temperature: efficiency of reaction between chlororganic compounds and alkali improves with temperature increase. Degree of reduction in highly volatile chlororganic compounds depends on initial concentration and the composition of such compounds. The fullest extent of removal of highly volatile chlororganic compounds is achieved when chlorine is present in alkanes and alkenes: chloroform, dichloroethane, trichloroethylene, tetrachlorethylene. Based on the results of the studies, a technology for extraction of highly volatile chlororganic compounds from crude oil was proposed to enable efficient removal of chlorinated alkenes and alkanes. Considering future practical implementation of the technology, the optimal treatment temperature should be at least 180°С. To prevent boiling of reaction mixture the process should be conducted at excess pressure of at least 2 MPa. Treatment time at constant stirring – at least 6 hours. Loading and concentration of alkaline aqueous solution should be at least 25% and 10%, respectively. After the treatment, the main volume of aqueous phase is removed and crude oil can be directed to further processing.
Reaction of sodium hydroxide with chlorine-containing aromatic compounds requires harder conditions: temperatures in the range of 300 to 350°С and high pressures. Therefore, looking for new methods for removal of chlorinated aromatic compounds from crude oil is of current concern. Solution to this challenge is of great practical importance for all oil production companies because despite current prohibition to use chemicals containing chlororganic compounds, highly volatile chlororganic compounds can form as a result of reactions between chlorides-containing chemicals and interactions with petroleum hydrocarbons.
References
1. Nadirov N.K., Kotova A.V., Kam'yanov V.F. et al., Novye nefti Kazakhstana i ikh ispol'zovanie. Metally v neftyakh (New Kazakh oil and their use. Metals in oils), Alma-Ata: Nauka Publ., 1984, 448 p.
2. Germash V.M., Lyalin V.A., Shreyder A.V. et al., Sources of formation of hydrogen chloride in oil refining (In Russ.), Neftepererabotka i neftekhimiya, 1974, no. 8, pp. 8–10.
3. Patent RU2605601C1, Method of reducing content of organic chlorides in oil, Inventors: Tat'yanina O.S., Sudykin S.N., Gubaydulin F.R., Sakhabutdinov R.Z., Sannikova A.L., Mukhametgaleev R.R., Nosov S.K.
4. Hiraoka et al., Japan Kokai 74,822,570, Chemical Abstracts, 8988831 K, 1975, V. 82.
5. Patent US4639309A, Process for the dehalogenation of polyhalogenated hydrocarbon containing fluids, Inventors: Lalancette J.-M., Belanger G.
6. Patent US4337368A, Reagent and method for decomposing halogenated organic compounds, Inven-tors: Pytlewski L.L., Krevitz K., Smith A.B.
7. Patent US4353793A, Method for removing polyhalogenated hydrocarbons from nonpolar organic sol-vent solution, Inventor: Brunelle D.J.
8. Patent RU2191768C2, Method for utilizing chlorine-containing poisonous products, Inventors: Gormay V.V., Alimov N.I., Medvetskiy I.V., Frolov V.N., Savostin V.S.
9. Patent US4532028A, Method for reducing content of halogenated aromatics in hydrocarbon solutions, Inventor: Peterson R.L.
10. Patent US4284516A, Process for the removal of low level (ppm) halogenated contaminants, Inventors: Parker D.K., Steichen R.J.
11. Patent US4761221A, Process for the decomposition of halogenated organic compounds, Inventors: Rossi C.A., Nelis Ph.
12. Patent RU2221837C1, Method of processing of gasoline fractions containing organochlorine com-pounds on reforming installations, Inventors: Tomin V.P., Mikishev V.A., Elshin A.I., Kuzora I.E., Kolotov V.Yu.
13. Patent US4618686A, Process for of aryl and alpha-araliphatic halides, Inventors: Boyer St.K., Hills F.
14. Patent US5490919A, Process for the dehalogenation of organic compounds, Inventors: Pri-Bar I., Azoulay D., Buchman O.
15. Patent US3539653A, Method of removing alkyl halides from a hydrocarbon stream with an alkanol amine, Inventors: Frevel L.K., Kressley L.J.
16. Patent RU2672263C1, Method of reducing content of organic chlorides in oil, Inventors: Abdrakh-manova L.M., Tat'yanina O.S., Sudykin S.N.
Treatment of naphtha contaminated with highly volatile chlororganic compounds using aqueous solutions of sodium hydroxide at high temperatures enables considerable reduction of organic chlorine content. Chromatography-mass spectrometry studies have demonstrated that alkyl halides degrade firstly. Efficiency of the removal of organic chlorine depends directly on naphtha treatment temperature: efficiency of reaction between chlororganic compounds and alkali improves with temperature increase. Degree of reduction in highly volatile chlororganic compounds depends on initial concentration and the composition of such compounds. The fullest extent of removal of highly volatile chlororganic compounds is achieved when chlorine is present in alkanes and alkenes: chloroform, dichloroethane, trichloroethylene, tetrachlorethylene. Based on the results of the studies, a technology for extraction of highly volatile chlororganic compounds from crude oil was proposed to enable efficient removal of chlorinated alkenes and alkanes. Considering future practical implementation of the technology, the optimal treatment temperature should be at least 180°С. To prevent boiling of reaction mixture the process should be conducted at excess pressure of at least 2 MPa. Treatment time at constant stirring – at least 6 hours. Loading and concentration of alkaline aqueous solution should be at least 25% and 10%, respectively. After the treatment, the main volume of aqueous phase is removed and crude oil can be directed to further processing.
Reaction of sodium hydroxide with chlorine-containing aromatic compounds requires harder conditions: temperatures in the range of 300 to 350°С and high pressures. Therefore, looking for new methods for removal of chlorinated aromatic compounds from crude oil is of current concern. Solution to this challenge is of great practical importance for all oil production companies because despite current prohibition to use chemicals containing chlororganic compounds, highly volatile chlororganic compounds can form as a result of reactions between chlorides-containing chemicals and interactions with petroleum hydrocarbons.
References
1. Nadirov N.K., Kotova A.V., Kam'yanov V.F. et al., Novye nefti Kazakhstana i ikh ispol'zovanie. Metally v neftyakh (New Kazakh oil and their use. Metals in oils), Alma-Ata: Nauka Publ., 1984, 448 p.
2. Germash V.M., Lyalin V.A., Shreyder A.V. et al., Sources of formation of hydrogen chloride in oil refining (In Russ.), Neftepererabotka i neftekhimiya, 1974, no. 8, pp. 8–10.
3. Patent RU2605601C1, Method of reducing content of organic chlorides in oil, Inventors: Tat'yanina O.S., Sudykin S.N., Gubaydulin F.R., Sakhabutdinov R.Z., Sannikova A.L., Mukhametgaleev R.R., Nosov S.K.
4. Hiraoka et al., Japan Kokai 74,822,570, Chemical Abstracts, 8988831 K, 1975, V. 82.
5. Patent US4639309A, Process for the dehalogenation of polyhalogenated hydrocarbon containing fluids, Inventors: Lalancette J.-M., Belanger G.
6. Patent US4337368A, Reagent and method for decomposing halogenated organic compounds, Inven-tors: Pytlewski L.L., Krevitz K., Smith A.B.
7. Patent US4353793A, Method for removing polyhalogenated hydrocarbons from nonpolar organic sol-vent solution, Inventor: Brunelle D.J.
8. Patent RU2191768C2, Method for utilizing chlorine-containing poisonous products, Inventors: Gormay V.V., Alimov N.I., Medvetskiy I.V., Frolov V.N., Savostin V.S.
9. Patent US4532028A, Method for reducing content of halogenated aromatics in hydrocarbon solutions, Inventor: Peterson R.L.
10. Patent US4284516A, Process for the removal of low level (ppm) halogenated contaminants, Inventors: Parker D.K., Steichen R.J.
11. Patent US4761221A, Process for the decomposition of halogenated organic compounds, Inventors: Rossi C.A., Nelis Ph.
12. Patent RU2221837C1, Method of processing of gasoline fractions containing organochlorine com-pounds on reforming installations, Inventors: Tomin V.P., Mikishev V.A., Elshin A.I., Kuzora I.E., Kolotov V.Yu.
13. Patent US4618686A, Process for of aryl and alpha-araliphatic halides, Inventors: Boyer St.K., Hills F.
14. Patent US5490919A, Process for the dehalogenation of organic compounds, Inventors: Pri-Bar I., Azoulay D., Buchman O.
15. Patent US3539653A, Method of removing alkyl halides from a hydrocarbon stream with an alkanol amine, Inventors: Frevel L.K., Kressley L.J.
16. Patent RU2672263C1, Method of reducing content of organic chlorides in oil, Inventors: Abdrakh-manova L.M., Tat'yanina O.S., Sudykin S.N.


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