WO2023229484A1 - Procédé de production d'hydrocarbures aromatiques à partir d'une fraction d'hydrocarbures légers - Google Patents

Procédé de production d'hydrocarbures aromatiques à partir d'une fraction d'hydrocarbures légers Download PDF

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Publication number
WO2023229484A1
WO2023229484A1 PCT/RU2022/050381 RU2022050381W WO2023229484A1 WO 2023229484 A1 WO2023229484 A1 WO 2023229484A1 RU 2022050381 W RU2022050381 W RU 2022050381W WO 2023229484 A1 WO2023229484 A1 WO 2023229484A1
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Prior art keywords
reaction
water
supplied
hydrocarbon fraction
reaction volume
Prior art date
Application number
PCT/RU2022/050381
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English (en)
Russian (ru)
Inventor
Кирилл Александрович ОВЧИННИКОВ
Сергей Евгеньевич КУЗНЕЦОВ
Валерий Александрович ГОЛОВАЧЕВ
Андрей Александрович ПЕТИН
Александр Сергеевич НАПАЛКОВ
Михаил Николаевич КИСЕЛЕВ
Original Assignee
Публичное акционерное общество "Газпром нефть"
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Filing date
Publication date
Priority claimed from RU2022113713A external-priority patent/RU2788947C9/ru
Application filed by Публичное акционерное общество "Газпром нефть" filed Critical Публичное акционерное общество "Газпром нефть"
Publication of WO2023229484A1 publication Critical patent/WO2023229484A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G63/00—Treatment of naphtha by at least one reforming process and at least one other conversion process
    • C10G63/02—Treatment of naphtha by at least one reforming process and at least one other conversion process plural serial stages only

Definitions

  • the invention relates to the field of oil refining and petrochemical industries. More specifically, the invention relates to a method for processing aliphatic hydrocarbons into an aromatic hydrocarbon concentrate or high-octane gasoline component for the production of gasoline or aromatic concentrates on a zeolite catalyst in a multi-shelf reactor or several independent sequential reactors with a distributed supply of raw materials and a distributed controlled supply of water.
  • the technology for producing a high-octane gasoline product by the method of zeoforming is known from the prior art - a process of catalytic processing of low-octane gasoline fractions (straight-run gasoline fractions of oils and gas condensates, gas gasoline and other fractions that boil in the temperature range 35-200 ° C) into high-octane unleaded gasoline on zeolite-containing catalysts , as well as various options for the development of this technology.
  • SUBSTITUTE SHEET (RULE 26)
  • the technology for converting dimethyl ether is known, for example [RU 2160160 Published: 12/10/2000 Bull. No. 34].
  • This invention relates to a process for producing liquid hydrocarbons enriched with iso- and cycloparaffins, which can be used as an additive in the production of high-octane gasoline with an aromatic hydrocarbon content of no more than 30 wt.%.
  • the catalyst is activated in air at 540-560°C.
  • the process is carried out at a pressure of 0.1-10 MPa, a temperature of 250-400°C, and a volumetric feed rate of raw materials of 250-1100 h-1.
  • a zeolite-containing catalyst also known from the prior art is a zeolite-containing catalyst, a method for its preparation and a method for converting aliphatic hydrocarbons into a concentrate of aromatic hydrocarbons or a high-octane component of gasoline [RU 2221643 Published: 01/20/2004 Bull. No. 2].
  • This technical solution describes the catalyst itself, the method of its preparation and the method of converting aliphatic hydrocarbons into a concentrate of aromatic hydrocarbons or a high-octane component of gasoline (options) by passing a gaseous mixture of low molecular weight saturated hydrocarbons or vapors of straight-run gasoline fraction of oil through a layer of zeolite-containing catalyst.
  • the solution is also known [RU 2172212 Published: 08/20/2001 Bull. No. 23], relating to a catalyst for the conversion of aliphatic hydrocarbons C2-C12 high-octane component of gasoline or a concentrate of aromatic hydrocarbons containing
  • this catalyst composition provides an increase in the yield of liquid C5+ hydrocarbons and an increase in the content of aromatic hydrocarbons in them.
  • a yield of C5+ hydrocarbons of up to 76% wt was achieved. with aromatic content up to 34.7% wt. and OC (by motor method) to 85.8.
  • SUBSTITUTE SHEET effective for separating incoming components into a vapor-phase exhaust stream containing nitrogen, hydrogen and methane, and a liquid-phase I process stream containing ethane, propane and C6+ aromatic hydrocarbons, supplying raw natural gas to the vapor-liquid separation zone; supplying process stream I to a fractionation zone containing at least one distillation column operating under conditions effective for separating hydrocarbons from process stream I into at least process stream II containing propane and product stream I containing C6+ hydrocarbons, and removing this stream from process; supplying process stream II to the dehydrocyclodimerization zone, operating under dehydrocyclodimerization conditions, including at a pressure of less than 0.7 MPa, and producing a stream leaving the reaction zone.
  • the raw material entering the dehydrocyclodimerization reaction zone is separated from methane with an economically acceptable degree of purity, which, however, involves the use of high pressure or deep cold.
  • the fractionation zone consists of several fractionation columns for the separation of ethane and the propane-butane fraction, which is the feedstock for the reaction zone.
  • this raw material can also be light hydrocarbons C2-C4, separated from the first process stream in one fractionation column as the second process stream.
  • non-condensable components and C2-C4 hydrocarbons of raw materials and recycle streams are supplied to the dehydrocyclodimerization reaction zone.
  • Nitrogen, methane and ethane are coolants that ensure the endothermic transformation of propane and butane, which allows the dehydrocyclodimerization reaction of raw materials to be carried out in a single-stage adiabatic reactor without intermediate heating of partially converted raw materials, which complicates the design of the reactor and furnace.
  • SUBSTITUTE SHEET (RULE 26) dehydrocyclization of the C3+ components of the raw material on zeolite-containing catalysts, the stream leaving the reaction zone and containing hydrogen, C1-C4 alkanes and C6+ aromatic hydrocarbons is fed into the separation zone, a vapor-phase stream containing hydrogen and methane, and liquid-phase I stream of the process are removed from the separation zone containing propane, butane and C6+ aromatic hydrocarbons, feed I process stream into the fractionation zone and separate it into at least II process stream containing propane and butane, and I product stream containing C6+ aromatic hydrocarbons, feed II process stream into the dehydrocyclodimerization reaction zone operating under dehydrocyclodimerization conditions, and a stream leaving the reaction zone is obtained, characterized in that the vapor-phase stream from the separation zone also contains ethane, and raw materials containing C1-C4 alkanes and part of the vapor-phase stream from the separation zone are supplied to the reaction zone.
  • the closest analogue is a method for converting aliphatic hydrocarbons into a concentrate of aromatic hydrocarbons or a high-octane component of gasoline, patented as part of a group of inventions [RU 2221643, Published: 19.6.2002].
  • a zeolite catalyst a condensed phase concentrate of aromatic hydrocarbons directly from low molecular weight gaseous hydrocarbons, for example, from associated petroleum gases and a wide fraction of light hydrocarbons (NGL).
  • the technical result regarding the method based on the use of the proposed zeolite-containing catalyst for the conversion of aliphatic hydrocarbons into a concentrate of aromatic hydrocarbons or a high-octane component of gasoline is achieved by passing a gaseous mixture of low molecular weight saturated hydrocarbons (raw materials) (2.2 wt.% ethane, 73.7 wt.% propane, 24.1 wt.% i- and p-butane) through a layer of catalyst heated to a temperature of 500-600 °C.
  • the disadvantages include the unevenness of the reaction due to the use of one reaction volume, including due to the distribution of the temperature field over the catalyst layer and, as a consequence, a decrease in the yield of the target product, as well as a decrease in catalytic activity due to coking of the catalyst, which leads to to the need for its replacement and/or regeneration.
  • This problem is proportional to the technology scaling step. In reactors of larger volume, the situation will be aggravated by these negative factors to a greater extent.
  • SUBSTITUTE SHEET (RULE 26) the product of which is high-octane gasoline.
  • the conversion product is separated with the simultaneous removal of reaction water and waste gases.
  • the reactor is a reactor containing at least two reaction zones, between which there are additionally located means for mixing the reaction product from the previous reaction zone and the supplied alcohol and olefin-containing raw materials.
  • the claimed invention will make it possible to optimize the processes for producing gasoline or concentrated aromatic compounds from available and, as a rule, low-margin, and in some cases
  • the technical result is a method for producing aromatic hydrocarbons from a wide fraction of light hydrocarbons in the gas phase in a multi-shelf reactor or several independent sequential reactors with a distributed supply of raw materials and a distributed controlled supply of water.
  • the technical result is achieved by solving the problem of carrying out the reaction in a reactor that includes at least two independent reaction zones, or in at least two consecutive reactors (hereinafter referred to as independent reaction zones) in which hydrocarbon feedstock is supplied
  • HCF hydrocarbon fraction
  • HCF hydrocarbon fraction
  • Water in a proportion of 76...85% / 15...24%, respectively.
  • HCF hydrocarbon fraction
  • the hydrocarbon fraction (HCF) is supplied to at least the first reaction zone.
  • Water is supplied to the first and subsequent reaction zones.
  • Water is supplied in the form of water vapor.
  • Volumetric water supply is carried out in the following ratio: to the first reaction zone - up to 50% of the total volume of water supplied, to the second - the rest, when implementing the option with two reaction volumes.
  • SUBSTITUTE SHEET (RULE 26) ratio into the first reaction zone -20...30% of the total volume of water supplied, into the second and subsequent ones - the rest, while the volume from 70% to 80% is distributed between subsequent reaction zones in equal shares or in such a way that in each more water was supplied to the subsequent reaction bottom than to the previous one.
  • the volumetric rate of water supply can be adjusted, while the total volume of supplied water is maintained within the range specified in the total volume.
  • the method is carried out as follows:
  • a hydrocarbon stream in particular, representing associated petroleum gas (APG), which can be a by-product at 8
  • SUBSTITUTE SHEET (RULE 26) oil production is sent through the production line to the mixing chamber, or the mixing valve also supplies the water flow there.
  • the proportions of components supplied to the first reaction zone are 76...85 (hydrocarbons) - 15...24 (water).
  • a zeolite catalyst based on ZSM-5 zeolite is loaded into each reaction zone. The reaction is carried out under the following parameters: temperature 550 ... 650 °C, pressure 10 ... 12 atm., reaction time is proportional to the volume of the reaction zones depending on the volumetric feed rate of raw materials.
  • water and, depending on the embodiment, a hydrocarbon stream are supplied to the second and, if any, subsequent reaction zones through connected process pipelines.
  • the volumetric flow rate through water is adjustable.
  • the number of reaction zones is determined by the productivity of the installation based on the fact that a larger volume is more prone to uneven temperature field across the catalyst layer.
  • the parameters of the distributed supply and the reaction carried out in various options are shown in Table 1.
  • the catalyst used was a zeolite based on ZSM-5 with the following composition:
  • Silicon dioxide 72.5;
  • Zinc oxide 3.4;
  • SUBSTITUTE SHEET (RULE 26) described examples of implementation and without deteriorating the quality of the resulting product.
  • the product stream after sequential passage of all reaction volumes is divided into a hydrocarbon fraction of the product and an aqueous fraction of the product.
  • the aqueous fraction of the product is removed.
  • the hydrocarbon fraction of the product is further separated into a liquid hydrocarbon product and a gaseous product, in particular by fractionation and stabilization methods.
  • the gaseous product can be further divided into a gaseous product fraction enriched in C3-C4 hydrocarbons and a gaseous product fraction enriched in C1-C2 hydrocarbons.
  • the main component of the liquid hydrocarbon product is C5+ hydrocarbons (hydrocarbons with five or more carbon atoms).
  • a liquid hydrocarbon product may contain not only C5+ hydrocarbons, but also varying amounts of dissolved C1-C4 gases.
  • the gaseous product may include C1-C4 hydrocarbons, nitrogen, hydrogen and other inorganic gases, as well as heavier hydrocarbons.
  • a model mixture of APG of the following composition was used as a raw material for the experiments: normal paraffins - 79.05%, isoparaffins - 20.95%.
  • the composition of the liquid hydrocarbon product is detailed in Table 2.
  • APG 67% first reaction volume; 33% second reaction volume.
  • APG 100% first reaction volume.
  • APG 100% first reaction volume.
  • SUBSTITUTE SHEET (RULE 26) Water: 30% first reaction volume; 30% second reaction volume; 40% third reaction volume.
  • APG 100% first reaction volume.
  • APG 70% first reaction volume; 30% second reaction volume.
  • APG 70% first reaction volume; 30% second reaction volume.
  • APG 70% first reaction volume; 30% second reaction volume.
  • SUBSTITUTE SHEET (RULE 26) Water: 30% first reaction volume; 30% second reaction volume; 40% third reaction volume.
  • APG 100% first reaction volume.
  • the water supply to the third volume was increased. Due to the additional water supplied to the second volume, the water ratio changed as follows: 30% first reaction volume; 30% second reaction volume; 40% third reaction volume.
  • reaction pressure 12 atm.
  • APG 100% first reaction volume.
  • SUBSTITUTE SHEET (RULE 26) Water: 30% first reaction volume; 30% second reaction volume; 40% third reaction volume.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention se rapporte au domaine de l'industrie pétrochimique et de transformation du pétrole. Plus précisément, l'invention concerne un procédé de transformation d'hydrocarbures aliphatiques en un concentré d'hydrocarbures aromatiques ou en un composant à indice d'octane élevé d'essence pour la production d'essences ou de concentrés de composés aromatiques sur un catalyseur en zéolite dans un réacteur à étages multiples ou dans plusieurs réacteurs indépendants en série avec une alimentation distribuée de la matière première et une alimentation distribuée ajustable de l'eau. Cette invention permet d'optimiser les processus de production d'essences ou de composés aromatiques concentrés à partir de matières premières disponibles et en règle générale à faible marge, voire recyclées dans des cas particuliers.
PCT/RU2022/050381 2022-05-23 2022-12-07 Procédé de production d'hydrocarbures aromatiques à partir d'une fraction d'hydrocarbures légers WO2023229484A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2022113713 2022-05-23
RU2022113713A RU2788947C9 (ru) 2022-05-23 Способ получения ароматических углеводородов из широкой фракции легких углеводородов в газовой фазе

Publications (1)

Publication Number Publication Date
WO2023229484A1 true WO2023229484A1 (fr) 2023-11-30

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2225506A1 (fr) * 1995-06-16 1997-01-03 Institut Francais Du Petrole Procede de transformation d'hydrocarbures en composes aromatiques avec un catalyseur contenant au moins un metal dopant choisi dans le groupe constitue du titane, du zirconium, del''hafnium, du cobalt, du nickel, du zinc, et:ou des lanthanides
US20030019792A1 (en) * 1999-11-15 2003-01-30 Cong-Yan Chen Process for converting heavy hydrocarbon feeds to high octane gasoline, BTX and other valuable aromatics
RU2221643C1 (ru) * 2002-06-19 2004-01-20 Закрытое акционерное общество "ЗАО "Экостар-Наутех" Цеолитсодержащий катализатор, способ его получения и способ превращения алифатических углеводородов в концентрат ароматических углеводородов или высокооктановый компонент бензина (варианты)
RU2550354C1 (ru) * 2014-03-28 2015-05-10 Общество С Ограниченной Ответственностью "Новые Газовые Технологии-Синтез" Способ получения концентрата ароматических углеводородов из легких алифатических углеводородов и установка для его осуществления
RU2747867C1 (ru) * 2020-06-29 2021-05-17 Общество с ограниченной ответственностью"Новые газовые технологии-синтез" (ООО "НГТ-Синтез") Способ получения бензинов или концентратов ароматических соединений с различным распределением потоков оксигената и олефинсодержащей фракции и добавлением воды

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2225506A1 (fr) * 1995-06-16 1997-01-03 Institut Francais Du Petrole Procede de transformation d'hydrocarbures en composes aromatiques avec un catalyseur contenant au moins un metal dopant choisi dans le groupe constitue du titane, du zirconium, del''hafnium, du cobalt, du nickel, du zinc, et:ou des lanthanides
US20030019792A1 (en) * 1999-11-15 2003-01-30 Cong-Yan Chen Process for converting heavy hydrocarbon feeds to high octane gasoline, BTX and other valuable aromatics
RU2221643C1 (ru) * 2002-06-19 2004-01-20 Закрытое акционерное общество "ЗАО "Экостар-Наутех" Цеолитсодержащий катализатор, способ его получения и способ превращения алифатических углеводородов в концентрат ароматических углеводородов или высокооктановый компонент бензина (варианты)
RU2550354C1 (ru) * 2014-03-28 2015-05-10 Общество С Ограниченной Ответственностью "Новые Газовые Технологии-Синтез" Способ получения концентрата ароматических углеводородов из легких алифатических углеводородов и установка для его осуществления
RU2747867C1 (ru) * 2020-06-29 2021-05-17 Общество с ограниченной ответственностью"Новые газовые технологии-синтез" (ООО "НГТ-Синтез") Способ получения бензинов или концентратов ароматических соединений с различным распределением потоков оксигената и олефинсодержащей фракции и добавлением воды

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