EP3167027A1 - Procédé de production de btx et de gpl - Google Patents

Procédé de production de btx et de gpl

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Publication number
EP3167027A1
EP3167027A1 EP15732744.6A EP15732744A EP3167027A1 EP 3167027 A1 EP3167027 A1 EP 3167027A1 EP 15732744 A EP15732744 A EP 15732744A EP 3167027 A1 EP3167027 A1 EP 3167027A1
Authority
EP
European Patent Office
Prior art keywords
stream
gas stream
liquid stream
lpg
liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP15732744.6A
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German (de)
English (en)
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EP3167027B1 (fr
Inventor
Thomas Hubertus Maria HOUSMANS
M Steve TURNER
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SABIC Global Technologies BV
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SABIC Global Technologies BV
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Publication of EP3167027A1 publication Critical patent/EP3167027A1/fr
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Classifications

    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • 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
    • C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
    • C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
    • C10G70/06—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes by gas-liquid contact
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/12—Liquefied petroleum gas
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/28—Propane and butane
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics

Definitions

  • the invention is directed to a process for producing BTX and LPG.
  • Aromatics hydrocarbons have a wide variety of applications in the petrochemical and chemical industries. These are important raw materials for many intermediates of commodity petrochemicals and valuable fine chemicals, such as monomers for polyesters, engineering plastics, intermediates for detergents, pharmaceuticals, agricultural products and explosives. Among them, benzene, toluene and xylene (BTX) are the three basic materials for most intermediates of aromatic derivatives.
  • BTX pyrolysis gasoline
  • Reformate is formed in the catalytic reforming of naphtha, a technology primarily directed at the production of high octane gasoline components.
  • Pygas is a liquid byproduct formed in the production of olefins by hydrocracking liquid feeds such as naphtha or gas oil. Extraction from reformate and pygas are the most economical sources of BTX.
  • the composition of BTX depends on the source. Pygas is typically rich in benzene, whereas xylenes and toluene are the main components of reformate.
  • LPG is produced during extraction from reformate or pygas.
  • WO2013/182534 discloses a process for producing BTX from a C5-C12 hydrocarbon mixture using a hydrocracking/hydrodesulphurisation catalyst. According to
  • the process results in a mixture comprising substantially no co- boilers of BTX, thus chemical grade BTX can easily be obtained.
  • the product stream obtained by the process of WO2013/182534 comprises BTX and LPG as well as methane and unreacted hydrogen.
  • the product stream is separated into methane and unreacted hydrogen as a first separate stream, the LPG as a second separate stream and the BTX as a third separate stream.
  • the BTX is separated from the hydrocracking product stream by gas-liquid separation or distillation. A series of distillation steps may be applied.
  • the first distillation step at moderate temperature is for separating most of the aromatic species (liquid product) from the hydrogen, H 2 S, methane and LPG species.
  • the gaseous stream from this distillation is further cooled (to about -30 °C) and distilled again to separate the remaining aromatics species and most of the propane and butane.
  • the gaseous product (mainly hydrogen, H 2 S, methane and ethane) is then further cooled (to about -100 °C) to separate t e ethane and leave the hydrogen, H 2 S and methane in the gaseous stream that will be recycled to the reactor.
  • the gaseous product subjected to this cryogenic cooling must be substantially free from BTX in order to avoid freezing of BTX which would block the system.
  • the separation step requires cryogenic cooling using special equipment, which is energy intensive.
  • step (c) involves
  • step (a) the hydrocracking product stream obtained by step (a) is separated into a first gas stream and a first liquid stream in step (b).
  • the first gas stream comprises hydrogen, methane and LPG.
  • the first liquid stream comprises BTX.
  • step (c) LPG is removed from the first gas stream. This removal of LPG from the first gas stream is performed utilizing the BTX generated by the hydrocracking step (a).
  • a second liquid stream is formed, which comprises the LPG from the first gas stream and the BTX added to the first gas.
  • the hydrogen and methane remaining from the first gas stream forms a second gas stream.
  • the BTX used for the separation step (c) is obtained by the subsequent separation step (d) in which LPG and BTX in the second liquid stream are separated from each other as a third gas stream and a third liquid stream. A part of the BTX obtained is fed back to the separation unit used in step (c).
  • step (c) is performed such that the second liquid stream is substantially free of hydrogen and methane.
  • the second liquid stream substantially consists of LPG and BTX. This allows an easy separation of the second liquid stream in the subsequent step (d) between the third gas stream (LPG) and the third liquid stream (BTX).
  • the separation in step (d) can be performed simply by a gas- liquid separation due to the large difference in the boiling points of C4 hydrocarbons and benzene. LPG as the desired product is directly obtained thereby.
  • the second liquid stream is substantially free of hydrogen and methane' means that the total amount of hydrogen and methane in the second liquid stream is less than 1 wt-%, preferably less than 0.7 wt-%, more preferably less than 0.6 wt-% and most preferably less than 0.5 wt-%.
  • the second gas stream mainly comprises hydrogen and methane, i.e. much of heavier hydrocarbons in the first gas stream go to the second liquid stream.
  • the total amount of hydrogen and methane in the second gas stream is at least 60 wt-%, preferably at least 65 wt-%, more preferably at least 70 wt-%, more preferably at least 80 wt-%, more preferably at least 90 wt-%, more preferably at least 95 wt-%, more preferably at least 98 wt-%.
  • the second gas stream substantially consists of hydrogen and methane, i.e. all heavier hydrocarbons in the first gas stream go to the second liquid stream.
  • the second gas stream substantially consists of hydrogen and methane' means that the total amount of hydrogen and methane in the second gas stream is at least 99 wt-%, preferably at least 99.3 wt-%, more preferably at least 99.4 wt-%, most preferably at least 99.5 wt-%.
  • the third gas stream mainly comprises LPG.
  • the total amount of LPG in the third gas stream is at least 80 wt-%, preferably at least 85 wt-%, more preferably at least 90 wt-%, more preferably at least 95 wt-%, more preferably at least 98 wt-%.
  • the third gas stream substantially consists of LPG. It is herein understood that 'the third gas stream substantially consists of LPG' means that the amount of LPG in the third gas stream is at least 99 wt-%, preferably at least 99.3 wt-%, more preferably at least 99.4 wt-%, most preferably at least 99.5 wt-%.
  • the third liquid stream substantially consists of BTX' means that the amount of BTX in the third liquid stream is at least 99 wt-%, preferably at least 99.3 wt-%, more preferably at least 99.4 wt-%, most preferably at least 99.5 wt-%.
  • step (b) a gas-liquid separation is performed for the hydrocracking product stream.
  • a large portion of BTX ends up in the liquid phase (first liquid stream).
  • the gas phase still contains a substantial amount of BTX (especially benzene) after one separation.
  • the gas phase is preferably further subjected to one or more gas-liquid separations until the gas phase contains a small portion of BTX.
  • the gas-liquid separation of the hydrocracking product stream may be performed such that the first gas stream comprises a small portion of BTX.
  • option I) is preferred for step (c).
  • the hydrocracking product stream is separated into the first gas stream and the first liquid stream, and subsequently the first gas stream is directly mixed with the recycled third liquid stream without a further separation.
  • This recycled third liquid stream which absorbed the LPG in the first gas stream is called the second liquid stream.
  • the gas-liquid separation of the hydrocracking product stream may be performed such that the first gas stream comprises a large portion of BTX.
  • option II) is preferred for step (c).
  • the addition of the third liquid stream is performed after the first gas stream is further separated.
  • the hydrocracking product stream is separated into the first gas stream and the first liquid stream, and subsequently the first gas stream is separated into a further gas stream and a further liquid stream.
  • This further gas stream obtained from the first gas stream is mixed with the recycled third liquid stream.
  • This recycled third liquid stream which absorbed the LPG in the gas stream obtained from the first gas stream is called the second liquid stream.
  • BTX in a liquid form is used for the absorption of the LPG present in the first gas stream. Due to the high affinity between BTX and LPG, LPG present in the first gas stream will be absorbed by BTX. Due to the very low affinity between BTX and H2 or C1 , hydrogen and methane are not absorbed by BTX, and accordingly remains as a gas stream.
  • US4212726 discloses a method for recovering hydrogen gas of increased purity from a hydrotreatment process effluent stream. The method comprises a gas-liquid separation of the effluent stream and producing a stream of relatively pure hydrogen from the gaseous phase by the use of two absorber liquids. In US4212726, the absorber liquids consist of the liquid phase hydrocarbon stream obtained by the first gas-liquid separation and heavier stabilized converted
  • US7563307 discloses a process for separating a hydrocarbon gas stream, such as natural gas, by contacting the stream with a circulating solvent comprising an internal solvent contained in the feed gas.
  • the gas stream is contacted with a solvent in an extractor to produce an overhead stream enriched with unabsorbed component(s) and a rich solvent bottoms stream enriched with absorbed component(s).
  • the rich solvent bottoms stream is then flashed at reduced pressure to regenerate lean solvent and to recover t e absorbed
  • LPG refers to the well-established acronym for the term "liquefied petroleum gas”. LPG generally consists of a blend of C2-C4 hydrocarbons i.e. a mixture of C2, C3, and C4 hydrocarbons.
  • BTX as used herein is well known in the art and relates to a mixture of benzene, toluene and xylenes.
  • aromatic hydrocarbon is very well known in the art. Accordingly, the term “aromatic hydrocarbon” relates to cyclically conjugated hydrocarbon with a stability (due to derealization) that is significantly greater than that of a hypothetical localized structure (e.g. Kekule structure). The most common method for determining aromaticity of a given hydrocarbon is the observation of diatropicity in the 1 H NMR spectrum, for example the presence of chemical shifts in the range of from 7.2 to 7.3 ppm for benzene ring protons.
  • the process according to the invention comprises (a) contacting a feed stream comprising C5-C12 hydrocarbons in the presence of hydrogen with a hydrocracking catalyst in a hydrocracking reactor.
  • Step (a) can be performed in one hydrocracking reactor or in more than one hydrocracking reactors.
  • step (a) is performed in at least two hydrocracking reactors arranged in series.
  • the feed stream used in the process of the present invention is a mixture comprising C5-C12 hydrocarbons.
  • the source feed stream comprises at least 40 wt%, more preferably at least 45 wt%, most preferably at least 50 wt% of the C5-C12 hydrocarbons.
  • the feed stream mainly comprises C6-C8 hydrocarbons.
  • the feed stream has a boiling point in the range of 30-195°C. Suitable feed streams include, but are not limited to pyrolysis gasoline, straight run naphtha, hydrocracked gasoline, light coker naphtha and coke oven light oil, FCC gasoline, reformate or mixtures thereof.
  • the feed stream may have a relatively high sulphur content, such as pyrolysis gasoline (pygas), straight run naphtha, light coker naphtha and coke oven light oil and mixtures thereof.
  • pyrolysis gasoline pygas
  • straight run naphtha straight run naphtha
  • light coker naphtha and coke oven light oil and mixtures thereof.
  • the non- aromatic species comprised in the hydrocarbon feed are saturated (e.g. by prior hydrogenation) in order to reduce the exotherm within the catalyst bed used in the present process.
  • a typical composition of pyrolysis gasoline may comprise 10-15 wt-% C5 olefins, 2-4 wt-% C5 paraffins and cycloparaffins, 3-6 wt-% C6 olefins, 1 -3 wt-% C6 paraffins and naphthenes, 25-30 wt-% benzene, 15-20 wt-% toluene, 2-5 wt-% ethylbenzene, 3-6 wt-% xylenes, 1 -3 wt-% trimethylbenzenes, 4-8 wt-%
  • the feed stream used in the process of the present invention is treated so that it is enriched in mono-aromatic compounds.
  • mono-aromatic compound relates to a hydrocarbon compound having only one aromatic ring. Means and methods suitable to enrich the content of mono-aromatic compounds in a mixed hydrocarbon stream are well known in the art such as the Maxene process; see Bhirud (2002) Proceedings of the DGMK-conference 1 15-122.
  • the feed stream used in the process of the present invention may comprise up to 300 wppm of sulphur (i.e. the weight of sulphur atoms, present in any compound, in relation to the total weight of the feed).
  • the feed stream is depentanized, which means that the feed stream is substantially free from C5 hydrocarbons.
  • the term "feed stream substantially free from C5 hydrocarbons” means that said feed stream comprises less than 1 wt-% C5 hydrocarbons, preferably less than 0.7 wt-% C5 hydrocarbons, more preferably less than 0.6 wt-% C5 hydrocarbons and most preferably less than 0.5 wt-% C5 hydrocarbons.
  • the feed stream can be subjected to hydrodesulphurisation before hydrocracking.
  • the feed stream comprising C5-C12 hydrocarbons is contacted in the presence of hydrogen with a hydrocracking catalyst.
  • the hydrocracking catalyst further has a
  • hydrodesulphurisation activity is advantageous in that it is not necessary to subject the hydrocarbon feed stream to a desulphurisation treatment prior to subjecting said hydrocarbon feed stream to the hydrocracking treatment.
  • hydrocracking/hydrodesulphurisation catalyst are described on pages 13-14 and 174 of Hydrocracking Science and Technology (1996) Ed. Julius Scherzer, A.J. Gruia, Pub. Taylor and Francis. Hydrocracking and hydrodesulphurisation reactions proceed through a bifunctional mechanism which requires a relatively strong acid function, which provides for the cracking and isomerization and which provides breaking of the sulphur-carbon bonds comprised in the organic sulfur compounds comprised in the feed, and a metal function, which provides for the olefin hydrogenation and the formation of hydrogen sulfide. Many catalysts used for the
  • hydrocracking/hydrodesulphurisation process are formed by composting various transition metals with the solid support such as alumina, silica, alumina-silica, magnesia and zeolites.
  • the catalyst is a hydrocracking catalyst comprising 0.01 -1 wt-% hydrogenation metal in relation to the total catalyst weight and a zeolite having a pore size of 5-8 A and a silica (Si0 2 ) to alumina (Al 2 0 3 ) molar ratio of 5-200 and the process conditions comprise a temperature of 425-580 °C, a pressure of 300-5000 kPa gauge and a Weight Hourly Space Velocity of 0.1 -15 lr 1 .
  • the obtained hydrocracking product stream is advantageously substantially free from non-aromatic C6+ hydrocarbons due to the catalyst and the conditions employed.
  • chemical grade BTX can easily be separated from the hydrocracking product stream product stream.
  • the advantageous effects of these embodiments are obtained by strategically selecting the hydrocracking catalyst in combination with the hydrocracking conditions.
  • Hydrocracking is performed under process conditions including a temperature of 425- 580 °C, a pressure of 300-5000 kPa gauge and a Weight Hourly Space Velocity of 0.1 - 15 h 1 .
  • a hydrocracking catalyst having a relatively strong acid function e.g. by selecting a catalyst comprising a zeolite having a pore size of 5-8 A and a silica (Si0 2 ) to alumina (Al 2 0 3 ) molar ratio of 5-200
  • a relatively strong hydrogenation activity e.g. by selecting a catalyst comprising 0.01 -1 wt-% hydrogenation metal
  • chemical grade BTX and LPG can be produced from the hydrocracking product stream.
  • the hydrocracking of the feed stream is performed at a pressure of 300- 5000 kPa gauge, more preferably at a pressure of 600-3000 kPa gauge, particularly preferably at a pressure of 1000-2000 kPa gauge and most preferably at a pressure of 1200-1600 kPa gauge.
  • a pressure of 300- 5000 kPa gauge more preferably at a pressure of 600-3000 kPa gauge, particularly preferably at a pressure of 1000-2000 kPa gauge and most preferably at a pressure of 1200-1600 kPa gauge.
  • preferred hydrocracking conditions thus include a temperature of 425-580 °C, a pressure of 300-5000 kPa gauge and a Weight Hourly Space Velocity of 0.1 -15 h ⁇ 1 . More preferred hydrocracking conditions include a temperature of 450-550 °C, a pressure of 600-3000 kPa gauge and a Weight Hourly Space Velocity of 1 -10 h ⁇ 1 .
  • Particularly preferred hydrocracking conditions include a temperature of 450-550 °C, a pressure of 1000-2000 kPa gauge and a Weight Hourly Space Velocity of 2-9 h ⁇ 1 .
  • Hydrocracking catalysts that are particularly suitable for the process of the present invention comprise a molecular sieve, preferably a zeolite, having a pore size of 5-8 A.
  • Zeolites are well-known molecular sieves having a well-defined pore size.
  • zeolite or "aluminosilicate zeolite” relates to an aluminosilicate molecular sieve.
  • the hydrocracking catalyst comprises a medium pore size aluminosilicate zeolite or a large pore size aluminosilicate zeolite.
  • Suitable zeolites include, but are not limited to, ZSM-5, MCM-22, ZSM-1 1 , beta zeolite, EU-1 zeolite, zeolite Y, faujastite, ferrierite and mordenite.
  • the term "medium pore zeolite" is commonly used in the field of zeolite catalysts. Accordingly, a medium pore size zeolite is a zeolite having a pore size of about 5-6 A.
  • Suitable medium pore size zeolites are 10-ring zeolites, i.e. the pore is formed by a ring consisting of 10 SiC tetrahedra.
  • Suitable large pore size zeolites have a pore size of about 6-8 A and are of the 12-ring structure type. Zeolites of the 8-ring structure type are called small pore size zeolites. In the above cited Atlas of Zeolite Framework Types various zeolites are listed based on ring structure. Most preferably the zeolite is ZSM-5 zeolite, which is a well-known zeolite having MFI structure. Preferably, the silica to alimuna ratio of the ZSM-5 zeolite is in the range of 20-200, more preferably in the range of 30-100.
  • the zeolite is in the hydrogen form: i.e. having at least a portion of the original cations associated therewith replaced by hydrogen.
  • Methods to convert an aluminosilicate zeolite to the hydrogen form are well known in the art.
  • a first method involves direct ion exchange employing an acid and/or salt
  • a second method involves base-exchange using ammonium salts followed by calcination.
  • the catalyst composition comprises a sufficient amount of hydrogenation metal to ensure that the catalyst has a relatively strong hydrogenation activity.
  • Hydrogenation metals are well known in the art of petrochemical catalysts.
  • the catalyst composition preferably comprises 0.01 -1 wt-% hydrogenation metal, more preferably 0.01 -0.7 wt-%, most preferably 0.01 -0.5 wt-% hydrogenation metal, more preferably 0.01 -0.3 wt-%.
  • the catalyst composition may more preferably comprise 0.01 -0.1 wt-% or 0.02-0.09 wt-% hydrogenation metal.
  • wt% when relating to the metal content as comprised in a catalyst composition relates to the wt% (or "wt-%") of said metal in relation to the weight of the total catalyst, including catalyst binders, fillers, diluents and the like.
  • the hydrogenation metal is at least one element selected from Group 10 of the Periodic Table of Elements.
  • the preferred Group 10 element is platinum (Pt).
  • the hydrocracking catalyst used in the process of the present invention comprises a zeolite having a pore size of 5-8 A, a silica (Si0 2 ) to alumina (Al 2 0 3 ) molar ratio of 5-200 and 0.01 -1 wt-% platinum (in relation to the total catalyst).
  • the hydrocracking catalyst composition may further comprise a binder.
  • Alumina Al 2 0 3
  • the catalyst composition of the present invention preferably comprises at least 10 wt-%, most preferably at least 20 wt-% binder and preferably comprises up to 40 wt-% binder.
  • the hydrogenation metal is deposited on the binder, which preferably is Al 2 0 3 .
  • the hydrocracking catalyst is a mixture of the hydrogenation metal on a support of an amorphous alumina and the zeolite.
  • the hydrocracking catalyst comprises the hydrogenation metal on a support of the zeolite.
  • the hydrogenation metal and the zeolite giving cracking functions are in closer proximity to one another which translates into a shorter diffusion length between the two sites. This allows high space velocity, which translates into smaller reactor volumes and thus lower CAPEX.
  • the hydrocracking catalyst is the hydrogenation metal on a support of the zeolite and step (b) is performed at a Weight Hourly Space Velocity of 10-15 Ir 1 .
  • the hydrocracking step is performed in the presence of an excess amount of hydrogen in the reaction mixture. This means that a more than stoichiometric amount of hydrogen is present in the reaction mixture that is subjected to hydrocracking.
  • the molar ratio of hydrogen to hydrocarbon species (H 2 /HC molar ratio) in the reactor feed is between 1 :1 and 4:1 , preferably between 1 :1 and 3:1 and most preferably betweenl :1 and 2:1 .
  • a higher benzene purity in the product stream can be obtained by selecting a relatively low H 2 /HC molar ratio.
  • hydrocarbon species means all hydrocarbon molecules present in the reactor feed such as benzene, toluene, hexane, cyclohexane etc. It is necessary to know the composition of the feed to then calculate the average molecular weight of this stream to be able to calculate the correct hydrogen feed rate.
  • the catalyst is a hydrocracking catalyst comprising 0.01 -1 wt-% hydrogenation metal in relation to the total catalyst weight and a zeolite having a pore size of 5-8 A and a silica (Si0 2 ) to alumina (Al 2 0 3 ) molar ratio of 5-200 and the first process conditions comprise a temperature of 425-580 °C, a pressure of 300-5000 kPa gauge and a Weight Hourly Space Velocity of 0.1 -15 h ⁇
  • the product produced by the hydrocracking step of the process of the present invention mainly comprises hydrogen, methane, LPG and BTX.
  • chemical grade BTX can easily be separated from the hydrocracking product stream.
  • chemical grade BTX relates to a hydrocarbon mixture comprising less than 5 wt-% hydrocarbons other than benzene, toluene and xylenes, preferably less than 4 wt-% hydrocarbons other than benzene, toluene and xylenes, more preferably less than 3 wt-% hydrocarbons other than benzene, toluene and xylenes, and most preferably less than 2.5 wt-% hydrocarbons other than benzene, toluene and xylenes.
  • the "chemical grade BTX" produced by the process of the present invention comprises less than 1 wt-% non-aromatic C6+ hydrocarbons, preferably less than 0.7 wt-% non-aromatic C6+ hydrocarbons, more preferably less than 0.6 wt-% non-aromatic C6+ hydrocarbons and most preferably less than 0.5 wt-% non-aromatic C6+ hydrocarbons.
  • the most critical contaminants are the non-aromatic species which have boiling points close to benzene including, but not limited to, cyclohexane, methylcyclopentane, n-hexane, 2-methylpentane and 3-methylpentane.
  • hydrocracking product stream is substantially free from non-aromatic C6+ hydrocarbons as these
  • hydrocarbons usually have boiling points close to the boiling point of C6+ aromatic hydrocarbons. Hence, it can be difficult to separate the non-aromatic C6+
  • hydrocarbons from the aromatic C6+ hydrocarbons comprised in the hydrocracking product stream by distillation are hydrocarbons from the aromatic C6+ hydrocarbons comprised in the hydrocracking product stream by distillation.
  • the term "product stream substantially free from non-aromatic C6+ hydrocarbons” means that said product stream comprises less than 1 wt-% non- aromatic C6+ hydrocarbons, preferably less than 0.7 wt-% non-aromatic C6+ hydrocarbons, more preferably less than 0.6 wt-% non-aromatic C6+ hydrocarbons and most preferably less than 0.5 wt-% non-aromatic C6+ hydrocarbons.
  • the hydrocracking product stream is also substantially free from C5 hydrocarbons.
  • the term "hydrocracking product stream substantially free from C5 hydrocarbons” means that said hydrocracking product stream comprises less than 1 wt-% C5 hydrocarbons, preferably less than 0.7 wt-% C5 hydrocarbons, more preferably less than 0.6 wt-% C5 hydrocarbons and most preferably less than 0.5 wt-% C5 hydrocarbons.
  • the hydrocarbons of the hydrocracking product stream substantially consist of methane, LPG and BTX.
  • the term "the hydrocarbons of the hydrocracking product stream substantially consist of methane, LPG and BTX" means that the total amount of methane, LPG and BTX in the hydrocarbons of the
  • hydrocracking product stream is at least 99 wt-%, preferably at least 99.3 wt-%, more preferably at least 99.4 wt-%, most preferably at least 99.5 wt-% .
  • step (b) the hydrocracking product stream is separated into a first gas stream mainly comprising hydrogen, methane and LPG and a first liquid stream mainly comprising BTX.
  • the hydrocracking product stream is subjected to separation by standard means and methods suitable for separating the gases from the liquids comprised in the hydrocracking product stream.
  • the separation may be performed e.g. by flashing, conventional distillation or absorption.
  • the separation of step (b) is preferably performed in a flash vessel.
  • the temperature is for example between 100 and 300 2 C
  • the pressure is the same as or lower than the pressure in the hydrocracking reactor.
  • the first liquid stream is preferably combined with the second liquid stream obtained by step (c) and the mixture is subjected to step (d). step (c)
  • step (c) the first gas stream is separated to obtain a second gas stream mainly comprising hydrogen and methane and a second liquid stream mainly comprising LPG and BTX.
  • the first gas stream is subjected to separation by standard means and methods suitable for separating the gases from the liquids comprised in the first gas stream.
  • the separation may be performed e.g. by flashing, conventional distillation or absorption.
  • the separation of step (c) is preferably performed by distillation.
  • Step (c) involves using a part of a third liquid stream mainly comprising BTX to absorb the LPG in the gas stream. In this way the second gas stream is obtained having little amount of components other than hydrogen and methane.
  • the part of the third liquid stream to be added to the first gas stream is cooled before it is added to the first gas stream.
  • the conditions of the cooling such as the temperature and the pressure, are chosen such that the BTX of the third liquid stream remains liquid.
  • the temperature of the third liquid stream is not very low, unlike the temperature required for the separation of ethane and methane (e.g. -100 2 C). The process of the invention can therefore be carried out in a simpler and less energy- intensive manner even when the part of the third liquid stream to be added to the first gas stream is cooled.
  • the cooling of the part of the third liquid stream to be added to the first gas stream has an advantage that the amount of the LPG absorbed in the BTX is increased.
  • the third liquid stream to be added to the first gas stream is cooled to a temperature of below 0 2 C.
  • the third liquid stream to be added to the first gas stream is cooled to a temperature of -40 2 C to 0 2 C, more preferably -40 2 C to -10 2 C, more preferably -40 2 C to -20 2 C, more preferably -40 2 C to -30 2 C, e.g. -35 2 C.
  • the pressure of the cooled stream may e.g. be 25-50 bar, for example 30 bar.
  • the part of the third liquid stream to be added to the first gas stream is cooled to a temperature just above the temperature at which the third liquid stream freezes, before being added to the first gas stream.
  • the part of the third liquid stream to be added to t e first gas stream is cooled to a temperature 0.5-5 Q C higher than the temperature at which the third liquid stream freezes, before being added to the first gas stream.
  • the temperature at which the third liquid stream freezes can easily be determined by the skilled person depending on the pressure.
  • step (c) involves adding a part of the third liquid stream directly to the first gas stream. This is also described as option (I) elsewhere in the description. Step (c) may involve compressing the first gas stream and adding the part of the third liquid stream to the compressed first gas stream. Compressing the first gas stream will further improve the separation of components between the second gas stream and the second liquid stream by increasing the absorption of LPG in BTX. In other embodiments of the invention, step (c) is performed in two or more steps. In these embodiments step (c) involves
  • step (d ) The liquid stream obtained by step (d ) is preferably combined with the second liquid stream obtained by step (c2) and the mixture is subjected to step (d).
  • Step (c2) may involve compressing the gas stream of step (c1 ) and adding the part of the third liquid stream to the compressed gas stream. Compressing the gas stream of (c1 ) will further improve the separation of components between the second gas stream and the second liquid stream by increasing the absorption of LPG in BTX.
  • At least part of the second gas stream is fed back to be mixed with the feed stream.
  • the hydrogen that is not consumed during hydrocracking is recycled within the process. This is an economical and environmental advantage.
  • a proportion of recycle gas stream is removed from the system as a purge.
  • the quantity of material that is purged depends on the levels of methane in the recycle stream which in-turn depend on the feed composition.
  • the purge stream will have the same composition as the recycle stream.
  • the purge will contain mainly hydrogen and methane it is suitable for use as a fuel gas or may be further treated (e.g. via a pressure swing adsorption unit) to separately recover a high purity hydrogen stream and a methane stream which can be used as a fuel gas. step (d)
  • step (d) the second liquid stream is separated into a third gas stream comprising LPG and a third liquid stream comprising BTX.
  • the second liquid stream may be subjected to separation by standard means and methods suitable for separating a third gas stream comprising LPG and a third liquid stream comprising BTX from each other.
  • the separation is performed by gas-liquid separation or distillation.
  • the process according to the invention further comprises step (e) of separating benzene from the third liquid stream.
  • the third liquid stream is separated into benzene and a liquid stream comprising toluene and xylene and (part of) the liquid stream comprising toluene and xylene is used for absorbing the LPG and BTX in step (c). Since the liquid stream comprising toluene and xylene comprises heavier hydrocarbons than the third liquid stream before separation, a more effective absorption will occur in step (c) resulting in a better separation during step (c).
  • Figure 1 illustrates a scheme of an example of a process not according to the invention
  • Figure 2 illustrates a scheme of an example of a process according to the invention.
  • FIG. 1 illustrates a scheme of an example of a process not according to the invention.
  • a feed stream comprising C5-C12 hydrocarbons is hydrocracked in the reaction section illustrated in the left part of the figure and the obtained hydrocracking product stream comprising hydrogen, methane, LPG and BTX is fed to the separation section illustrated in the right part of the figure via a heat exchanger H-003.
  • the hydrocracking product stream is fed to a heat exchanger H-003 where it is cooled to e.g. 140 Q C, after which it is fed to a flash vessel V0001 .
  • the hydrocracking product stream is separated in the flash vessel V001 into a gas stream and a liquid stream.
  • the gas stream from the flash vessel V0001 is compressed in a compressor K0002 and separated again in a flash vessel V002 at e.g. -100 Q C into a gas stream and a liquid stream.
  • the flash vessel V002 separates most of C4+ hydrocarbons as a liquid stream from a gas stream.
  • a gas stream mostly comprising hydrogen and C1 -C3 hydrocarbons is led to a heat exchanger H005 which compresses the gas to e.g. 30 bar and -100 Q C and then to a flash vessel V003 wherein a cryogenic separation between hydrogen and methane and C2-C3 hydrocarbons is performed.
  • the gas stream containing hydrogen and methane is recycled to the reaction section, wherein it is partly recycled and partly purged.
  • the liquid stream leaving the flash vessel V003 comprising C2-C3 is combined with the LPG stream obtained from the liquid stream from V001 .
  • the liquid steam leaving V001 is, together with the liquid stream coming from V002, fed to a distillation column C001 via a heat exchanger H006.
  • the liquid steam is separated into an LPG stream and a BTX stream.
  • the BTX stream is fed to a distillation column C002 for separation of the BTX stream in a stream 17 of lighter products, a benzene stream 18 and a toluene/xylene stream 19.
  • Figure 2 illustrates a scheme of an example of a process according to the invention.
  • the reaction section of Figure 2 is the same as that of Figure 1 .
  • the hydrocracking product stream is fed to a flash vessel V001 , where it is separated into a gas stream and a liquid stream.
  • the gas stream from the flash vessel V001 is heated in a heat exchanger H003 and separated again in a flash vessel V002.
  • the gas stream from the flash vessel V002 is compressed in a compressor K002 and fed to a distillation column C003.
  • the liquid streams from V001 , V002 and C003 go through a heat exchanger H004 and enter a distillation column C001 , which separates the liquid streams into an LPG stream and a BTX stream.
  • Part of the BTX stream is led to a distillation column C002 for separation of the BTX stream into a stream of lighter products, a benzene stream and a toluene/xylene stream.
  • a part of the BTX stream is fed via a pump 003 to the top of the distillation column C003.
  • this BTX stream is used to obtain a better separation between hydrogen and methane and the heavier components in the gas mixture fed to C003.
  • the liquid stream leaving C003 is combined with the liquid streams from V001 and V002 and fed to the distillation column C001 .

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention se rapporte à un procédé de production de BTX et de GPL, comprenant : (a) la mise en contact d'un flux d'alimentation contenant des hydrocarbures C5-C12 en présence d'hydrogène avec un catalyseur d'hydrocraquage dans un réacteur d'hydrocraquage pour produire un flux de produit d'hydrocraquage comprenant de l'hydrogène, du méthane, du GPL et du BTX, (b) la séparation du flux de produit d'hydrocraquage en un premier flux gazeux et un premier flux liquide, (c) la séparation du premier flux gazeux pour obtenir un deuxième flux gazeux comprenant de l'hydrogène et du méthane et un deuxième flux liquide comprenant du GPL et du BTX, la séparation étant effectuée de façon que le deuxième flux liquide soit sensiblement exempt d'hydrogène et de méthane, (d) la séparation du deuxième flux liquide en un troisième flux gazeux comprenant du GPL et un troisième flux liquide comprenant du BTX, l'étape (c) impliquant l'ajout d'une partie du troisième flux liquide au premier flux gazeux pour absorber le GPL dans le premier flux gazeux et obtenir le deuxième flux liquide ou l'ajout d'une partie du troisième flux liquide à un flux gazeux séparé du premier flux gazeux pour absorber le GPL dans ledit flux gazeux séparé du premier flux gazeux et obtenir le deuxième flux liquide.
EP15732744.6A 2014-07-08 2015-07-06 Procédé de production de gaz de pétrole liquéfié (gpl) et btx Active EP3167027B1 (fr)

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KR20170028971A (ko) 2017-03-14
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JP2017524772A (ja) 2017-08-31
EP3167027B1 (fr) 2019-03-13
SG11201610697YA (en) 2017-01-27
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EA201790149A1 (ru) 2017-05-31
CN111808633A (zh) 2020-10-23

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