EP2421936A2 - Valorisation de naphtas légers pour une production d'oléfines augmentée - Google Patents

Valorisation de naphtas légers pour une production d'oléfines augmentée

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Publication number
EP2421936A2
EP2421936A2 EP10714027A EP10714027A EP2421936A2 EP 2421936 A2 EP2421936 A2 EP 2421936A2 EP 10714027 A EP10714027 A EP 10714027A EP 10714027 A EP10714027 A EP 10714027A EP 2421936 A2 EP2421936 A2 EP 2421936A2
Authority
EP
European Patent Office
Prior art keywords
stream
light
content
zone
upgraded
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.)
Withdrawn
Application number
EP10714027A
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German (de)
English (en)
Inventor
José Castor GONZALEZ
Jean Mazurelle
Walter Vermeiren
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TotalEnergies Onetech Belgium SA
Original Assignee
Total Petrochemicals Research Feluy SA
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Application filed by Total Petrochemicals Research Feluy SA filed Critical Total Petrochemicals Research Feluy SA
Priority to EP10714027A priority Critical patent/EP2421936A2/fr
Publication of EP2421936A2 publication Critical patent/EP2421936A2/fr
Withdrawn legal-status Critical Current

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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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural parallel stages only
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80—Additives
    • C10G2300/805—Water
    • C10G2300/807—Steam
    • 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
    • C10G2400/20—C2-C4 olefins

Definitions

  • the present invention relates to the upgrading of light naphthas for increased olefins production.
  • Light naphthas are becoming widely available as feedstocks for steam crackers due to the difficulties in its valorization as components of the gasoline pool in refineries.
  • the quality of these naphthas as feeds to steam crackers could be improved by increasing the amount of normal paraffins at the expense of iso-paraffins, which would increase the yield of ethylene while reducing yields of fuel gas, C4s and pygas.
  • the isomerization reaction between normal and iso-paraffins is essentially limited by thermodynamic equilibrium. This has led to consider whether it would be feasible to operate the refinery isomerization units driving the reaction in a reverse mode, namely transforming iso-paraffins into normal paraffins.
  • GB 2 018 815 A1 describes a process for converting unsaturated C4 hydrocarbons into normal butane and more particularly to the conversion of normal butenes and isobutene into normal butane.
  • the normal butane can thereafter be either recovered, or advantageously, recycled to the ethylene process as a premium cracking feedstock to increase the overall yield of ethylene.
  • the feed stream of normal butenes and isobutene is obtained from unsaturated C4 hydrocarbons generated in the recovery zone of a conventional ethylene production facility.
  • the crude unsaturated C4 hydrocarbon by-product stream separated in the recovery zone of a naphtha steam cracker is usually directed to a butadiene recovery facility where h igh purity 1 ,3-butadiene is separated from the remaining C4 hydrocarbons.
  • the remaining C4 hydrocarbons are withdrawn from the butadiene recovery facility primarily as a mixture known in the art as "butene raffinate.” This mixture is generally comprised of normal butenes and isobutene.
  • the process comprises passing a stream of unsaturated C4 hydrocarbons in contact with hydrogen through a hydrogenation zone to react the hydrogen and the unsaturated C4 hydrocarbons to form normal butane and isobutane.
  • the normal butane and isobutane are discharged from the hydrogenation zone and are introduced into a separation zone to separate the normal butane from the isobutane.
  • the normal butane is discharged and recovered from the separation zone.
  • the isobutane from the separation zone is passed into an isomerization zone to convert a portion of the isobutane into normal butane to form a stream of normal butane and isobutane.
  • the normal butane and isobutane stream formed in the isomerization zone is withdrawn from the isomerization zone. This stream can thereafter be directed to the same separation zone which separates the normal butane and isobutane introduced from the hydrogenation zone to recover additional amounts of normal butane.
  • US 5019661 provides a single-stage process for the shape-selective hydroisomehzation of a branched olefin of at least 4 carbon atoms to produce a less branched paraffin product, said process comprising contacting said olefin and a hydrogen-containing gas with a zeolite or zeolite-like catalyst containing at least one metal of Group VIII and in which a major portion of said at least one of these metals is supported within the molecular channels and cavities of the said catalyst, said process being conducted under conditions such that hydroisomerization predominates over both simple hydrogenation and cracking.
  • 2-methylpent-1 -ene or 3,3-dimethylbut-1 - ene may be hydroisomerised to a product containing large amounts of n- hexane.
  • US 2005 101814 relates to a process for the production of light olefins from a naphtha feed stream.
  • the naphtha is sent to an adsorptive separation unit which produces a first process stream comprising primarily n-paraffins, and a second process stream comprising non-normal hydrocarbons.
  • the second process stream is processed through a ring opening reactor that hydrogenates and converts the aromatics and naphthenes to paraffins.
  • the paraffins from the adsorptive separation unit and from the hydrogenation ring opening reactor are then passed through a steam cracking unit to produce light olefins. This process increases the yield of light olefins from a naphtha feedstream.
  • the process may optionally include the passing of a py-gas stream generated in the steam cracking unit to the ring opening reactor to further increase the light olefin production.
  • the paraffins from the hydrogenation ring opening reactor are then passed through an isomerization unit for the conversion of a portion of the iso-paraffins to normal paraffins, and the resulting mixture is recycled to the adsorption unit.
  • the isomerization unit increases light olefin production by increasing the amount of normal paraffins recovered from the naphtha feed stream. This process concerns only the treatment of the conventional naphtha feedstock to be used in a steam cracker.
  • the present invention relates to the use of an existing isomerization zone of an oil refinery to increase the normal paraffins content of a light naphtha which is further cracked in a steam cracking unit to produce olefins.
  • the present invention is a process to upgrade light naphthas comprising branched paraffins and their use as a feedstock in a steam cracking unit, said light naphthas consisting essentially of 90 to 100% (advantageously 95 to 100%) by weight of hydrocarbons having at least 5 and up to 8 carbon atoms, said process comprising, a) providing an isomerization zone recovered from the gasoline unit of an oil refinery, b) providing a separation zone capable to treat an hydrocarbon stream comprising branched paraffins and normal paraffins to produce a first hydrocarbon stream having a reduced branched paraffins content and an enhanced normal paraffins content and a second hydrocarbon stream having an enhanced branched paraffins content and a reduced normal paraffins content, c) optionally providing a depentanizer, d) sending the light naphtha to the isomerization zone and operating said zone at conditions effective to produce a light naphtha having a reduced branched paraffins content and an
  • the present invention is a process to upgrade light naphthas comprising branched paraffins and their use as a feedstock in a steam cracking unit, said light naphthas consisting essentially of 90 to 100% (advantageously 95 to 100%) by weight of hydrocarbons having at least 5 and up to 8 carbon atoms, said process comprising, a) providing an isomerization zone recovered from the gasoline unit of an oil refinery, b) providing a separation zone capable to treat an hydrocarbon stream comprising branched paraffins and normal paraffins to produce a first hydrocarbon stream having a reduced branched paraffins content and an enhanced normal paraffins content and a second hydrocarbon stream having an enhanced branched paraffins content and a reduced normal paraffins content, c) sending the light naphtha to the separation zone to recover a first and a second hydrocarbon streams, d) sending the second hydrocarbon stream recovered from step c) to the isomehzation zone and operating said zone at conditions effective to produce
  • the present invention is a process to upgrade light naphthas comprising branched paraffins and their use as a feedstock in a steam cracking unit, said light naphthas consisting essentially of 90 to 100% (advantageously 95 to 100%) by weight of hydrocarbons having at least 5 and up to 8 carbon atoms, said process comprising, a) providing an isomehzation zone recovered from the gasoline unit of an oil refinery, b) providing a separation zone capable to treat an hydrocarbon stream comprising branched paraffins and normal paraffins to produce a first hydrocarbon stream having a reduced branched paraffins content and an enhanced normal paraffins content and a second hydrocarbon stream having an enhanced branched paraffins content and a reduced normal paraffins content, c) optionally providing a depentanizer, d) sending the light naphtha to the separation zone to recover a first and a second hydrocarbon streams, e) sending the first hydrocarbon stream recovered from step d) to the steam
  • the present invention is a process to upgrade light naphthas comprising branched paraffins and their use as a feedstock in a steam cracking unit, said light naphthas consisting essentially of 90 to 100% (advantageously 95 to 100%) by weight of hydrocarbons having at least 5 and up to 8 carbon atoms, said process comprising, a) providing an isomerization zone recovered from the gasoline unit of an oil refinery, b) providing a deisopentanizer, c) sending the light naphtha to a deisopentanizer to recover a stream comprising essentially isopentane and a stream having a reduced isopentane content, d) sending the stream having a reduced isopentane content recovered from step c) to the steam cracking unit, e) sending the stream comprising essentially isopentane recovered from step c) to the isomerization zone and operating said zone at conditions effective to produce a light naphtha having a reduced branched par
  • the fourth embodiment is of particular interest when the light naphtha to be upgraded is a C5 cut comprising, the total being 100w%, 0 to 10 % of C7+, advantageously 0 to 10% of C6+, more advantageously 0 to 10% of C6, 0 to 10% of C4,
  • said C5 is essentially a mixture of iC5 and nC5.
  • said C5 mixture comprises less than 5w% of NaftC ⁇ (C5 napthenics), preferably less than 3%.
  • the fourth embodiment is of particular interest when the light naphtha to be upgraded is a C5 cut comprising, the total being 100w%,
  • said C5 is essentially a mixture of iC5 and nC5.
  • said C5 mixture comprises less than 5w% of NaftC ⁇ (C5 napthenics), preferably less than 3%.
  • the fourth embodiment is of particular interest when the light naphtha to be upgraded is a C5 cut comprising, the total being 100w%,
  • said C5 is essentially a mixture of iC5 and nC5.
  • said C5 mixture comprises less than 5w% of NaftC ⁇ (C5 napthenics), preferably less than 3%.
  • the isomerization zone operates in the presence of hydrogen.
  • the light naphtha to be upgraded can be a C5 cut comprising, the total being 100w%, 100 to 95% of a mixture of pentane and isopentane and 0 to 5% of cyclopentane.
  • the light naphtha to be upgraded can be a C5/C6 cut comprising, the total being 100w%,
  • the light naphtha to be upgraded can be a C5/C6 cut comprising, the total being 100w%, 0 to 10 % of C7+, advantageously 0 to 10% of C7, 0 to 10% of C4,
  • the light naphtha to be upgraded can be a C5/C6 cut comprising, the total being 100w%,
  • the light naphtha to be upgraded can be a C5/C6 cut comprising, the total being 100w%,
  • the proportion of NaftC5+NaftC6 is less than 7w%, preferably less than 5%.
  • the proportion of Aromatics C6 is less than 5w%, preferably less than 2% more preferably less than 1.5%.
  • Figure 1 shows the equilibrium between the C5 and C6 normal and branched paraffins as function of the reaction temperature. It can be seen that the formation of iso-paraffins is more favorable at higher temperatures although in the considered range it is always found a larger proportion of iso-paraffins. Equilibrium is more favorable for the production of n-C5 than n-C6. The figure also indicates that at higher temperatures other catalytic concepts could be used. It appears clearly from Figure 1 that high reaction temperatures should be preferred for driving the reverse reaction towards n-paraffins and at those conditions a zeolite catalyst could be more advisable. However since existing isomerization units in refineries were designed mainly at low temperature, this case could be also interesting as a minimum investing option.
  • Any catalyst known in the art to be suitable for the isomerization of paraffin-rich hydrocarbon streams may be used as an isomerization catalyst in the isomerization zone.
  • One suitable isomerization catalyst comprises a platinum-group metal, hydrogen-form crystalline aluminosilicate zeolite and a refractory inorganic oxide, and the composition preferably has a surface area of at least 580 m2 /g.
  • the preferred noble metal is platinum, which is present in an amount of from about 0.01 to 5 mass % of the composition, and optimally from about 0.15 to 0.5 mass %.
  • Catalytically effective amounts of one or more promoter metals preferably selected from Groups VIB(6), VIII(8-10), IB(1 1 ), IIB(12), IVA(14), rhenium, iron, cobalt, nickel, gallium and indium also may be present.
  • the crystalline aluminosilicate zeolite may be synthetic or naturally occurring, and preferably is selected from the group consisting of FAU, LTL, MAZ and MOR with mordenite having a silica-to-alumina ratio of from 16:1 to 60:1 being especially preferred.
  • the zeolite generally comprises from about 50 to 99.5 mass % of the composition, with the balance being the refractory inorganic oxide.
  • Alumina and preferably one or more of gamma-alumina and eta-alumina, is the preferred inorganic oxide. Further details of the composition are disclosed in U.S. Pat. No. 4,735,929, incorporated herein in its entirety by reference thereto.
  • a preferred isomehzation catalyst composition comprises one or more platinum-group metals, a halogen, and an inorganic-oxide binder. Preferably the catalyst contains a Friedel-Crafts metal halide, with aluminum chloride being especially preferred .
  • the optimal platinum-group metal is platinum which is present in an amount of from about 0.1 to 5 mass %.
  • the inorganic oxide preferably comprises alumina, with one or more of gamma- alumina and eta-alumina providing best results.
  • the carrier material is in the form of a calcined cyl indrical extrudate.
  • the inlet stream of the isomerization zone may also contain an organic polyhalo component, with carbon tetrachloride being preferred, and the total chloride content is from about 2 to 15 mass %.
  • An organic-chloride promoter preferably carbon tetrachloride, is added during operation to maintain a concentration of 30 to 300 mass ppm of promoter in the combined feed.
  • Other details and alternatives of preparation steps and operation of the preferred isomerization catalyst are as disclosed in U.S. Pat. Nos. 2,999,074 and 3,031 ,419 which are incorporated herein by reference.
  • Hydrogen is advantageously mixed with the inlet stream of the isomerization zone to provide a mole ratio of hydrogen to hydrocarbon feed of about 0.01 to 5.
  • the hydrogen may be supplied totally from outside the process or supplemented by hydrogen recycled to the feed after separation from reactor effluent. Light hydrocarbons and small amounts of inserts such as nitrogen and argon may be present in the hydrogen . Water should be removed from hydrogen supplied from outside the process, preferably by an adsorption system as is known in the art.
  • the hydrogen to hydrocarbon mol ratio in the reactor effluent is equal to or less than 0.05, generally obviating the need to recycle hydrogen from the reactor effluent to the feed.
  • Water and sulfur are catalyst poisons especially for the chlorided platinum-alumina catalyst composition described herein below.
  • Water can act to permanently deactivate the catalyst by removing high-activity chloride from the catalyst, and sulfur temporarily deactivates the catalyst by platinum poisoning.
  • a hydrotreating or hydrorefining or hydrodesulfurization step usually reduces water-generating oxygenates to the preferred required 0.1 ppm or less and sulfur to 0.5 ppm or less.
  • Other means such as adsorption systems for the removal of sulfur and water from hydrocarbon streams are well known to those skilled in the art.
  • Isomerization conditions in the isomerization zone include reactor temperatures usually rang ing from about 50 to 350 0 C. H igher reaction temperatures are generally preferred in order to favour equilibrium mixtures having the highest concentration of normal alkanes. Temperatures in the range of about 150 to about 250 0 C are preferred in the present invention.
  • Reactor operating pressures generally range from about 100 kPa to 10 MPa absolute, preferably between about 0.5 and 4 MPa.
  • Liquid hourly space velocities range from about 0.2 to about 15 volumes of isomerizable hydrocarbon feed per hour per volume of catalyst, with a range of about 0.5 to 5 hr-1 being preferred.
  • Contacting within the isomerization zone may be effected using the catalyst in a fixed-bed system, a moving-bed system, a fluidized-bed system, or in a batch-type operation.
  • a fixed-bed system is preferred.
  • the reactants may be contacted with the bed of catalyst particles in either upward, downward, or radial-flow fashion.
  • the reactants may be in the liquid phase, a mixed liquid- vapour phase, or a vapour phase when contacted with the catalyst particles, with excellent results being obtained by application of the present invention to a primarily liquid-phase operation.
  • the isomerization zone may be in a single reactor or in two or more separate reactors with suitable means there between to insure that the desired isomerization temperature is maintained at the entrance to each zone. Two or more reactors in sequence are preferred to enable improved isomerization throug h control of ind ividual reactor temperatures and for partial catalyst replacement without a process shutdown.
  • the isomerization of light naphthas is typically performed in a fixed bed reactor operated at temperatures around about 200 0 C to about 250 0 C in order to favour the formation of normal compounds. Under these conditions it is usually preferred to use a catalyst containing a noble metal supported on a chlorated-alumina.
  • Cooling or heating of the stream at the inlet of the isomerization zone may be appropriate for temperature flexibility or for the start-up of the process.
  • Separation of normal from iso paraffins can be done using an adsorption process that separates both types of species by using a shape selective zeolite. These separation processes could be also useful to enhance the reverse reaction by recycling iso-paraffins instead of n-paraffins as in the conventional process.
  • the depentanizer is a conventional fractionation to separate the C5 from the C6 and above.
  • the deisopentanizer is known as a super fractionation and separates the iC5 from the C5 cut.
  • the adsorption separation unit may be of any suitable type that is appropriate for the specific situation of the process.
  • the adsorption unit is comprised of a bed of adsorbent comprised of a molecular sieve or other appropriate adsorbent for adsorbing hydrocarbons.
  • suitable adsorption separation units include, but are not limited to, swing bed or simulated moving bed adsorption units.
  • the inlet stream is separated in the adsorption unit by the selective adsorption and retention of normal paraffins in the adsorption bed.
  • the adsorption separation process undergoes an adsorption step, wherein selected components of the inlet stream are adsorbed onto the adsorbent, and followed by a desorption step wherein the selected components are desorbed from the adsorbent.
  • the selected components are the normal paraffins.
  • the normal paraffins remain on the adsorbent until a desorbent is passed through the adsorption unit.
  • the normal paraffins are separated from the inlet stream by adsorption onto the adsorbent.
  • the remaining components of the inlet stream are non-normal (branched) hydrocarbons and pass through the adsorption bed unaffected.
  • the non-normal hydrocarbons pass out of the adsorption unit as a raffinate stream containing a portion of the desorbent (remaining in the adsorbent bed further to the desorption step).
  • Said raffinate is fractionated to separate the desorbent and recover the second hydrocarbon stream having an enhanced branched paraffins content and a reduced normal paraffins content.
  • a desorbent is delivered to the adsorption unit and passes through the adsorbent bed.
  • the desorbent has properties which enable it to displace the heavier normal paraffins from the adsorbent, resulting in the formation of an extract stream.
  • the extract stream comprises normal hydrocarbons and a portion of the desorbent material.
  • the extract stream is fractionated to recycle the desorbent and recover the second hydrocarbon stream having an enhanced branched paraffins content and a reduced normal paraffins content.
  • Fig 2 depicts a process accord ing to the first embodiment of the invention.
  • the light naphtha is sent via line 1 and 2 to the isomerization zone to produce a light naphtha having a reduced branched paraffins content and an enhanced normal paraffins content.
  • the effluent is withdrawn via line 3 and sent to the separation zone to recover a first hydrocarbon stream 4 having a reduced branched paraffins content and an enhanced normal paraffins content and a second hydrocarbon stream 5 having an enhanced branched paraffins content and a reduced normal paraffins content.
  • the first hydrocarbon stream 4 is sent to the steam cracking unit (not shown).
  • a part of the second hydrocarbon stream 5 is recycled via line 7 to the isomerization zone and the other part is purge via line 6.
  • Fig 2-a derives from fig 2, a depentanizer is inserted after the separation zone to recycle the pentane at the isomerization zone via line 7 and purge the C6.
  • Fig 3 depicts a process according to the second embodiment of the invention.
  • the light naphtha is sent via line 1 to the separation zone to recover a first hydrocarbon stream 4 having a reduced branched paraffins content and an enhanced normal paraffins content and a second hydrocarbon stream 3 having an enhanced branched paraffins content and a reduced normal paraffins content.
  • the second hydrocarbon stream 3 is sent to the isomerization zone operating at conditions effective to produce a light naphtha 5 having a reduced branched paraffins content and an enhanced normal paraffins content.
  • the outlet stream 5 is mixed with the first hydrocarbon stream 4 and said mixed stream 7 is sent to the steam cracking unit (not shown).
  • Fig 4 depicts a process according to the third embodiment of the invention.
  • the light naphtha is sent via lines 1 and 2 to the separation zone to recover a first hydrocarbon stream 4 having a reduced branched paraffins content and an enhanced normal paraffins content and a second hydrocarbon stream 3 having an enhanced branched paraffins content and a reduced normal paraffins content.
  • the first hydrocarbon stream 4 is sent to the steam cracking unit (not shown).
  • the second hydrocarbon stream 3 is sent to the isomerization zone via line 6 after a purge 5.
  • the isomerization zone is operated at conditions effective to produce a light naphtha having a reduced branched paraffins content and an enhanced normal paraffins content 7 recycled at the inlet of the separation zone.
  • Fig 4-a derives from fig 4 by insertion of a depentanizer.
  • Hydrocarbon stream 3 is sent to a depentanizer to recover a stream 6 comprising essentially pentane and a stream 5 having a reduced pentane content.
  • the stream 6 comprising essentially isopentane is sent to the isomerization zone.
  • Fig 5 depicts a process according to the fourth embodiment of the invention.
  • the light naphtha is sent via line 1 and 2 to a deisopentanizer to recover a stream 5 comprising essentially isopentane and a stream 4 having a reduced isopentane content.
  • the stream 4 having a reduced isopentane content is sent to the steam cracking unit (not shown).
  • the stream 5 comprising essentially isopentane is sent to the isomerization zone operated at conditions effective to produce a light naphtha 6 having a reduced branched paraffins content and an enhanced normal paraffins content recycled to the inlet of the deisopentanizer.
  • a model charge feed was used: 90 % iC5 + 10 % nC5 + 300 ppm C 2 CI 4 bought from Air Product ®

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  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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Abstract

La présente invention est un procédé pour améliorer des naphtas légers comprenant des paraffines ramifiées et leur utilisation en tant que matière première dans une unité de vapocraquage, lesdits naphtas légers étant constitués essentiellement de 90 à 100 % en poids d'hydrocarbures ayant au moins 5 et jusqu'à 8 atomes de carbone, ledit procédé comprenant, a)facultativement la production d'une zone d'isomérisation récupérée à partir de l'unité de production d'essence d'une raffinerie de pétrole, b)facultativement la production d'une zone de séparation capable de traiter un flux d'hydrocarbures comprenant des paraffines ramifiées et des paraffines normales pour produire un premier flux d'hydrocarbures ayant une teneur réduite en paraffines ramifiées et une teneur augmentée en paraffines normales et un deuxième flux d'hydrocarbures ayant une teneur augmentée en paraffines ramifiées et une teneur réduite en paraffines normales, c)facultativement la production d'un dépentaniseur, de sorte qu'au moins deux de a), b) et c) soient présents, où, le naphta léger est envoyé vers l'un de a), b) et c), les flux circulent entre les différentes zones a), b) ou c), un flux riche en paraffines normales est envoyé vers l'unité de vapocraquage.
EP10714027A 2009-04-23 2010-04-22 Valorisation de naphtas légers pour une production d'oléfines augmentée Withdrawn EP2421936A2 (fr)

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EP10714027A EP2421936A2 (fr) 2009-04-23 2010-04-22 Valorisation de naphtas légers pour une production d'oléfines augmentée

Applications Claiming Priority (3)

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EP09158607A EP2243814A1 (fr) 2009-04-23 2009-04-23 Amélioration de naphte léger pour améliorer la production d'oléfines
EP10714027A EP2421936A2 (fr) 2009-04-23 2010-04-22 Valorisation de naphtas légers pour une production d'oléfines augmentée
PCT/EP2010/055370 WO2010122115A2 (fr) 2009-04-23 2010-04-22 Valorisation de naphtas légers pour une production d'oléfines augmentée

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CN105308159B (zh) 2013-07-02 2018-06-22 沙特基础工业公司 用于将原油转化成具有改进的乙烯产率的石化品的方法和设施
JP6427180B2 (ja) 2013-07-02 2018-11-21 サウディ ベーシック インダストリーズ コーポレイション 精製重質残油を石油化学製品にアップグレードする方法
US20150045602A1 (en) * 2013-08-07 2015-02-12 Uop Llc Process for promoting disproportionation reactions and ring opening reactions within an isomerization zone
US9302956B2 (en) 2014-05-01 2016-04-05 Uop Llc Process for increasing the yield of an isomerization zone fractionation
US9302959B2 (en) 2014-05-01 2016-04-05 Uop Llc Process for increasing the yield of an isomerization zone
US9302957B2 (en) 2014-05-01 2016-04-05 Uop Llc Process for controlling the yield of an isomerization zone
US9302960B2 (en) 2014-05-01 2016-04-05 Uop Llc Process for producing a feed stream for a steam cracker
US9302958B2 (en) 2014-05-01 2016-04-05 Uop Llc Process for increasing the yield of an isomerization zone
CN105441120B (zh) * 2015-12-16 2017-06-09 中国寰球工程公司 一种轻石脑油异构化全循环系统
WO2017196501A1 (fr) * 2016-05-11 2017-11-16 Uop Llc Isomérisation de configuration de flux dans l'unité de reformage
EP3788026A1 (fr) 2018-04-30 2021-03-10 SABIC Global Technologies B.V. Procédé de production d'oléfines légères à partir de naphta de passe directe isomérisé
US11021422B1 (en) * 2019-12-04 2021-06-01 Saudi Arabian Oil Company Integrated processes to produce gasoline blending components from light naphtha
US20230078452A1 (en) * 2021-09-13 2023-03-16 Uop Llc Process for isomerizing light paraffins
WO2024040049A1 (fr) * 2022-08-15 2024-02-22 Chevron U.S.A. Inc. Adsorption, séparation et isomérisation sélectives d'isomères d'alcane
EP4608792A1 (fr) * 2022-10-28 2025-09-03 SABIC Global Technologies B.V. Procédés et systèmes pour améliorer le rendement en éthylène à partir d'une charge d'iso-pentane par isomérisation inverse et séparation
US11920093B1 (en) * 2022-11-18 2024-03-05 Saudi Arabian Oil Company Systems and processes for producing ethylene from naphtha and butanes

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WO2010122115A3 (fr) 2011-02-17
EP2243814A1 (fr) 2010-10-27
US20120074039A1 (en) 2012-03-29

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