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RU2013134384A - METHOD FOR CONVERSION OF HYDROCARBON RAW MATERIAL CONTAINING SHALE OIL BY REMOVING CONTAMINATION, HYDROCONVERSION IN A BOILER LAYER AND FRACTION USING ATMOSPHERIC - Google Patents

METHOD FOR CONVERSION OF HYDROCARBON RAW MATERIAL CONTAINING SHALE OIL BY REMOVING CONTAMINATION, HYDROCONVERSION IN A BOILER LAYER AND FRACTION USING ATMOSPHERIC Download PDF

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RU2013134384A
RU2013134384A RU2013134384/04A RU2013134384A RU2013134384A RU 2013134384 A RU2013134384 A RU 2013134384A RU 2013134384/04 A RU2013134384/04 A RU 2013134384/04A RU 2013134384 A RU2013134384 A RU 2013134384A RU 2013134384 A RU2013134384 A RU 2013134384A
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fraction
gas oil
oil
hydrogen
hydroprocessing
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RU2013134384/04A
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RU2592693C2 (en
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Кристоф АЛЕС
Элен ЛЕРУА
Фредерик МЮРЕЛЬ
Сесиль ПЛЕН
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Тоталь Раффинаж Маркетинг
Аксенс
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
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    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
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    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
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    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
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    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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    • C10G2300/20—Characteristics of the feedstock or the products
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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    • C10G2400/02—Gasoline
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  • Chemical & Material Sciences (AREA)
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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

1. Способ конверсии сланцевого масла или смеси сланцевых масел, имеющих содержание азота по меньшей мере 0,1%, часто по меньшей мере 1% и очень часто по меньшей мере 2 мас.%, отличающийся тем, что он содержит следующие стадии:a) сырье подвергается удалению загрязнений с получением остатка и масла, очищенного от загрязнений,b) масло, очищенное от загрязнений, вводится в часть для гироконверсии в присутствии водорода, причем указанная часть содержит по меньшей мере один реактор с кипящим слоем, работающий в режиме газообразного и жидкого восходящего потока и содержащий по меньшей мере один катализатор гидроконверсии на подложке,c) выходящий поток, полученный на стадии b), вводится по меньшей мере частично, и часто полностью, в зону фракционирования, из которой, посредством атмосферной дистилляции, выходят газообразная фракция, фракция лигроина, фракция газойля и фракция, более тяжелая, чем газойль,d) указанная фракция лигроина обрабатывается, по меньшей мере частично и часто полностью, в другой части для гидрообработки в присутствии водорода, причем указанная часть содержит по меньшей мере один реактор с фиксированным слоем, содержащий по меньшей мере один катализатор гидрообработки, иe) указанная фракция газойля обрабатывается по меньшей мере частично, и часто полностью, в части для гидрообработки в присутствии водорода, причем указанная часть содержит по меньшей мере один реактор с фиксированным слоем, содержащий по меньшей мере один катализатор гидрообработки.2. Способ по п.1, отличающийся тем, что он дополнительно содержит стадию f), на которой по меньшей мере часть фракции, более тяжелой, чем газойль, вводится на ста1. A process for the conversion of shale oil or a mixture of shale oils having a nitrogen content of at least 0.1%, often at least 1% and very often at least 2% by weight, characterized in that it comprises the following steps: a) the raw material is subjected to removal of impurities to obtain a residue and oil, free from impurities, b) oil, purified from impurities, is introduced into a part for gyroconversion in the presence of hydrogen, said part comprising at least one fluidized bed reactor operating in a gaseous and liquid mode upstream and containing at least one supported hydroconversion catalyst, c) the effluent obtained in step b) is introduced at least partially, and often completely, into a fractionation zone, from which, by atmospheric distillation, a gaseous fraction, a fraction naphtha, gas oil fraction and a fraction heavier than gas oil, d) said naphtha fraction is processed, at least partially and often completely, in another portion for hydroprocessing in the presence of hydrogen, said portion comprising at least one fixed bed reactor containing at least one hydroprocessing catalyst, and e) said gas oil fraction is treated at least partially, and often completely, in a portion for hydroprocessing in the presence hydrogen, and the specified portion contains at least one fixed bed reactor containing at least one hydrotreating catalyst. The method according to claim 1, characterized in that it further comprises stage f), in which at least part of the fraction heavier than gas oil is introduced into one hundred

Claims (17)

1. Способ конверсии сланцевого масла или смеси сланцевых масел, имеющих содержание азота по меньшей мере 0,1%, часто по меньшей мере 1% и очень часто по меньшей мере 2 мас.%, отличающийся тем, что он содержит следующие стадии:1. The method of conversion of shale oil or a mixture of shale oils having a nitrogen content of at least 0.1%, often at least 1% and very often at least 2 wt.%, Characterized in that it contains the following stages: a) сырье подвергается удалению загрязнений с получением остатка и масла, очищенного от загрязнений,a) the raw material is subjected to the removal of contaminants to obtain a residue and an oil purified from contamination b) масло, очищенное от загрязнений, вводится в часть для гироконверсии в присутствии водорода, причем указанная часть содержит по меньшей мере один реактор с кипящим слоем, работающий в режиме газообразного и жидкого восходящего потока и содержащий по меньшей мере один катализатор гидроконверсии на подложке,b) an oil purified from contaminants is introduced into the gyroconversion part in the presence of hydrogen, said part comprising at least one fluidized bed reactor operating in a gaseous and liquid ascending mode and containing at least one hydroconversion catalyst on a substrate, c) выходящий поток, полученный на стадии b), вводится по меньшей мере частично, и часто полностью, в зону фракционирования, из которой, посредством атмосферной дистилляции, выходят газообразная фракция, фракция лигроина, фракция газойля и фракция, более тяжелая, чем газойль,c) the effluent obtained in step b) is introduced at least partially, and often completely, into the fractionation zone, from which, through atmospheric distillation, a gaseous fraction, a ligroin fraction, a gas oil fraction and a heavier fraction than gas oil leave d) указанная фракция лигроина обрабатывается, по меньшей мере частично и часто полностью, в другой части для гидрообработки в присутствии водорода, причем указанная часть содержит по меньшей мере один реактор с фиксированным слоем, содержащий по меньшей мере один катализатор гидрообработки, иd) said ligroin fraction is treated, at least partially and often completely, in another part for hydroprocessing in the presence of hydrogen, said part containing at least one fixed-bed reactor containing at least one hydroprocessing catalyst, and e) указанная фракция газойля обрабатывается по меньшей мере частично, и часто полностью, в части для гидрообработки в присутствии водорода, причем указанная часть содержит по меньшей мере один реактор с фиксированным слоем, содержащий по меньшей мере один катализатор гидрообработки.e) said gas oil fraction is processed at least partially, and often completely, in a hydrotreatment portion in the presence of hydrogen, said portion comprising at least one fixed bed reactor comprising at least one hydrotreatment catalyst. 2. Способ по п.1, отличающийся тем, что он дополнительно содержит стадию f), на которой по меньшей мере часть фракции, более тяжелой, чем газойль, вводится на стадию a) для очистки от загрязнений.2. The method according to claim 1, characterized in that it further comprises a step f), in which at least a fraction of a fraction heavier than gas oil is introduced into step a) for purification from contamination. 3. Способ по п.1, в котором выходящий поток, полученный на стадии b), фракционируется с помощью атмосферной дистилляции на газообразную фракцию, имеющую точку кипения менее 50°C, фракцию лигроина, кипящую при температуре от около 50°C до около 150°C, фракцию газойля, кипящую при температуре от около 150°C до около 370°C, и фракцию, которая является более тяжелой, чем фракция газойля, и которая кипит, как правило, при температуре выше 340°C, предпочтительно выше 370°C.3. The method according to claim 1, in which the effluent obtained in stage b) is fractionated by atmospheric distillation into a gaseous fraction having a boiling point of less than 50 ° C, a naphtha fraction boiling at a temperature of from about 50 ° C to about 150 ° C, a gas oil fraction boiling at a temperature of from about 150 ° C to about 370 ° C, and a fraction that is heavier than the gas oil fraction, and which boils, as a rule, at a temperature above 340 ° C, preferably above 370 ° C. 4. Способ по п.1, в котором удаление загрязнений на стадии a) осуществляется с помощью растворителя, выбранного из группы, состоящей из пропана, н-бутана, изобутана, н-пентана, циклопентана, 2-метилбутана, 2,2-диметилпропана и их смесей в любых пропорциях.4. The method according to claim 1, in which the removal of contaminants in stage a) is carried out using a solvent selected from the group consisting of propane, n-butane, isobutane, n-pentane, cyclopentane, 2-methylbutane, 2,2-dimethylpropane and mixtures thereof in any proportions. 5. Способ по п.1, в котором стадия удаления загрязнений a) осуществляется при соотношении растворитель/сырье от 3/1 до 8/1, предпочтительно от 4/1 до 6/1, при температуре от 60°C до 250°C, предпочтительно от 60°C до 200°C, и при давлении от 4 МПа до 5 МПа.5. The method according to claim 1, wherein the step of removing contaminants a) is carried out at a solvent / feed ratio of 3/1 to 8/1, preferably 4/1 to 6/1, at a temperature of 60 ° C to 250 ° C , preferably from 60 ° C to 200 ° C, and at a pressure of from 4 MPa to 5 MPa. 6. Способ по п.1, в котором часть для гидрообработки с фиксированным слоем на стадии d) и/или e) содержит, выше по ходу потока каталитических слоев гидрообработки, по меньшей мере один специфический защитный слой для соединений мышьяка и соединений кремния.6. The method according to claim 1, in which the part for hydroprocessing with a fixed layer in stage d) and / or e) contains, upstream of the catalytic layers of the hydroprocessing, at least one specific protective layer for arsenic compounds and silicon compounds. 7. Способ по п.1, в котором по меньшей мере часть фракции, более тяжелой, чем газойль, вводится в часть для каталитического крекинга, обозначенную стадией g), в которой она обрабатывается в условиях, обеспечивающих производство второй газообразной фракции, второй бензиновой фракции, второй фракции газойля и второй фракции, более тяжелой, чем газойль.7. The method according to claim 1, in which at least a portion of the fraction heavier than gas oil is introduced into the catalytic cracking portion indicated by step g), in which it is processed under conditions ensuring the production of a second gaseous fraction, a second gasoline fraction , the second fraction of gas oil and the second fraction, heavier than gas oil. 8. Способ по п.7, в котором по меньшей мере часть второй фракции, более тяжелой, чем газойль, полученной в конце стадии g), рециклизуется в начало указанной стадии g).8. The method according to claim 7, in which at least a portion of a second fraction heavier than the gas oil obtained at the end of step g) is recycled to the beginning of said step g). 9. Способ по п.7, в котором по меньшей мере часть второй фракции, более тяжелой, чем газойль, полученной в конце стадии g), рециклизуется на стадию гидрообработки газойля e).9. The method according to claim 7, in which at least a portion of a second fraction heavier than the gas oil obtained at the end of step g) is recycled to the gas oil hydrotreatment step e). 10. Способ по п.7, в котором по меньшей мере часть второй фракции, более тяжелой, чем газойль, полученной в конце стадии g), рециклизуется на стадию удаления загрязнений a).10. The method according to claim 7, in which at least a portion of the second fraction, heavier than the gas oil obtained at the end of stage g), is recycled to the stage of removing contaminants a). 11. Способ по п.1, в котором стадия гидроконверсии b) осуществляется при температуре от 300°C до 550°C, предпочтительно от 400°C до 450°C, при общем давлении от 2 до 35 МПа, предпочтительно от 10 до 20 МПа, при массовом ежечасном расходе ((время сырья/ч)/время катализатора), равном от 0,2 до 1,5 ч-1, и при отношении водород/сырье от 50 до 5000 Нм3/м3, предпочтительно от 100 до 1000 Нм3/м3.11. The method according to claim 1, in which the hydroconversion stage b) is carried out at a temperature of from 300 ° C to 550 ° C, preferably from 400 ° C to 450 ° C, with a total pressure of from 2 to 35 MPa, preferably from 10 to 20 MPa, with a mass hourly flow rate ((feed time / h) / catalyst time) of 0.2 to 1.5 h -1 , and with a hydrogen / feed ratio of 50 to 5000 Nm 3 / m 3 , preferably 100 up to 1000 Nm 3 / m 3 . 12. Способ по п.1, в котором стадия гидрообработки фракции лигроина d) осуществляется при температуре от 280°C до 380°C, предпочтительно от 300°C до 350°C, при общем давлении от 4 до 15 МПа, предпочтительно от 10 до 13 МПа, при массовом ежечасном расходе ((время сырья/ч)/время катализатора), равном от 0,1 до 5 ч-1, предпочтительно от 0,5 до 1 ч-1, и при отношении водород/сырье от 100 до 5000 Нм3/м3, предпочтительно от 100 до 1000 Нм3/м3.12. The method according to claim 1, in which the step of hydrotreating the ligroin fraction d) is carried out at a temperature of from 280 ° C to 380 ° C, preferably from 300 ° C to 350 ° C, at a total pressure of 4 to 15 MPa, preferably from 10 up to 13 MPa, with a mass hourly flow rate ((feed time / h) / catalyst time) of 0.1 to 5 h -1 , preferably 0.5 to 1 h -1 , and with a hydrogen / feed ratio of 100 up to 5000 Nm 3 / m 3 , preferably from 100 to 1000 Nm 3 / m 3 . 13. Способ по п.1, в котором стадия гидрообработки фракции газойля e) осуществляется при температуре от 320°C до 450°C, предпочтительно от 340°C до 400°C, при общем давлении от 7 до 20 МПа, предпочтительно от 10 до 15 МПа, при массовом ежечасном расходе ((время сырья/ч)/время катализатора), равном от 0,1 до 1 ч-1, предпочтительно от 0,3 до 0,8 ч-1, и при отношении водород/сырье от 100 до 5000 Нм3/м3, предпочтительно от 200 до 1000 Нм3/м3.13. The method according to claim 1, in which the step of hydrotreating the gas oil fraction e) is carried out at a temperature of from 320 ° C to 450 ° C, preferably from 340 ° C to 400 ° C, with a total pressure of from 7 to 20 MPa, preferably from 10 up to 15 MPa, with a mass hourly flow rate ((feed time / h) / catalyst time) equal to from 0.1 to 1 h -1 , preferably from 0.3 to 0.8 h -1 , and with a hydrogen / feed ratio from 100 to 5000 Nm 3 / m 3 , preferably from 200 to 1000 Nm 3 / m 3 . 14. Способ по п.1, в котором катализаторы на стадии гидроконверсии b) и стадиях гидрообработки d) и e) независимо выбираются из группы катализаторов, содержащих металл группы VIII, выбранный из группы, состоящей из Ni и/или Co, при необходимости металл группы VIB, выбранный из группы, состоящей из Mo и/или W, на аморфной подложке, выбранной из группы, состоящей из оксида алюминия, оксида кремния, алюмосиликатов, оксида магния, глин и их смесей.14. The method according to claim 1, in which the catalysts in the hydroconversion stage b) and the hydroprocessing stages d) and e) are independently selected from the group of catalysts containing a metal of group VIII selected from the group consisting of Ni and / or Co, optionally a metal group VIB selected from the group consisting of Mo and / or W, on an amorphous substrate selected from the group consisting of alumina, silica, aluminosilicates, magnesium oxide, clays, and mixtures thereof. 15. Способ по любому из предшествующих пунктов, в котором сланцевое масло или смесь сланцевых масел обеспечивается из углеводородного сырья, выбранного из группы, состоящей из масел, полученных из угля, масел, полученных из тяжелых смол и битуминозного песка, вакуумных дистиллятов и остатков прямой дистилляции, вакуумных дистиллятов и непревращенных остатков, полученных из процесса переработки мазута, масел, деасфальтированных с помощью растворителей, легких циклических масел, тяжелых циклических масел, фракций газойля, происходящих из каталитического крекинга и имеющих, как правило, температурный интервал кипения фракции от около 150°C до около 650°C, ароматических экстрактов, полученных при производстве смазочных масел, пиролитических масел древесных остатков, таких как древесные отходы, сырой нефти, полученной из биомассы (″биосырье″), растительных масел и животных жиров, или смесей такого сырья.15. The method according to any one of the preceding paragraphs, in which shale oil or a mixture of shale oils is provided from hydrocarbon raw materials selected from the group consisting of oils derived from coal, oils derived from heavy resins and tar sand, vacuum distillates and direct distillation residues , vacuum distillates and unconverted residues obtained from the processing of fuel oil, oils deasphalted with solvents, light cyclic oils, heavy cyclic oils, gas oil fractions originating from atalytic cracking and typically having a boiling range of a fraction from about 150 ° C to about 650 ° C, aromatic extracts obtained in the manufacture of lubricating oils, pyrolytic oils of wood residues such as wood residues, crude oil derived from biomass (″ bio-raw materials ″), vegetable oils and animal fats, or mixtures of such raw materials. 16. Синтетическое нефтяное сырье, полученное способом по любому из предшествующих пунктов.16. Synthetic petroleum feedstock obtained by the method according to any of the preceding paragraphs. 17. Установка для обработки сланцевого масла, содержащая:17. Installation for processing shale oil, containing: - часть для удаления загрязнений сланцевого масла, подлежащего обработке,- a part for removing contaminants of the shale oil to be treated, - часть для гидроконверсии в присутствии водорода, содержащую реактор с кипящим слоем, работающий в режиме газообразного и жидкого восходящего потока и содержащий по меньшей мере один катализатор гидроконверсии на подложке,- part for hydroconversion in the presence of hydrogen, containing a fluidized bed reactor operating in a gaseous and liquid ascending mode and containing at least one hydroconversion catalyst on a substrate, - зону для фракционирования с помощью атмосферной дистилляции,- zone for fractionation using atmospheric distillation, - часть для гидрообработки в присутствии водорода, содержащую реактор с фиксированным слоем, содержащий по меньшей мере один катализатор гидрообработки,- part for hydroprocessing in the presence of hydrogen, containing a fixed-bed reactor containing at least one hydroprocessing catalyst, - другую часть для гидрообработки в присутствии водорода, содержащую по меньшей мере один реактор с фиксированным слоем, содержащий по меньшей мере один катализатор гидрообработки,- another part for hydroprocessing in the presence of hydrogen, containing at least one fixed-bed reactor containing at least one hydroprocessing catalyst, где эти элементы расположены для осуществления способа по любому из пп.1-15. where these elements are located to implement the method according to any one of claims 1 to 15.
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