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WO2011015662A2 - Procédé pour remodeler une unité d'alkylation de hf ou d'acide sulfurique - Google Patents

Procédé pour remodeler une unité d'alkylation de hf ou d'acide sulfurique Download PDF

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Publication number
WO2011015662A2
WO2011015662A2 PCT/EP2010/061513 EP2010061513W WO2011015662A2 WO 2011015662 A2 WO2011015662 A2 WO 2011015662A2 EP 2010061513 W EP2010061513 W EP 2010061513W WO 2011015662 A2 WO2011015662 A2 WO 2011015662A2
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WO
WIPO (PCT)
Prior art keywords
unit
reactor
catalyst
phase
alkylate
Prior art date
Application number
PCT/EP2010/061513
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English (en)
Other versions
WO2011015662A3 (fr
Inventor
Zhichang Liu
Chunming Xu
Rui Zhang
Xianghai Meng
Ana Cecilia Patroni
Peter Anton August Klusener
Albertus Vincentius Petrus Van Den Bosch
Original Assignee
Shell Internationale Research Maatschappij B.V.
China University Of Petroleum
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Publication date
Application filed by Shell Internationale Research Maatschappij B.V., China University Of Petroleum filed Critical Shell Internationale Research Maatschappij B.V.
Priority to CN201080034599.0A priority Critical patent/CN102510850B/zh
Publication of WO2011015662A2 publication Critical patent/WO2011015662A2/fr
Publication of WO2011015662A3 publication Critical patent/WO2011015662A3/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0066—Stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1812—Tubular reactors
    • B01J19/1837—Loop-type reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • 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
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/56—Addition to acyclic hydrocarbons
    • C07C2/58—Catalytic processes
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00018—Construction aspects
    • B01J2219/00024—Revamping, retrofitting or modernisation of existing plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/00038—Processes in parallel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00042—Features relating to reactants and process fluids
    • B01J2219/00047—Ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/08—Halides
    • C07C2527/10—Chlorides
    • 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
    • C10G2300/4056—Retrofitting operations
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention provides a method for
  • alkylate fuel blending feedstock There is an increasing demand for alkylate fuel blending feedstock.
  • alkylate combines a low vapour pressure, no olefin or aromatic content with high octane properties.
  • an alkylate oil which uses a composite ionic liquid catalyst to react isobutane with a butene.
  • isobutane and butene are supplied to a reactor unit and the alkylate is formed by contacting the reactants with a composite ionic liquid under alkylation conditions.
  • the reactor effluent is separated into a hydrocarbon phase and an ionic liquid phase.
  • the ionic liquid phase is recycled to the reactor unit while the hydrocarbon phase is treated to retrieve the alkylate.
  • the present invention provides a first method for revamping an HF or sulphuric acid alkylation unit to an ionic liquid alkylation unit, wherein the HF or sulphuric acid alkylation unit comprises at least: a reactor unit for contacting catalyst and hydrocarbon reactants;
  • a separator unit for separating a reactor effluent into a catalyst phase and an alkylate-comprising hydrocarbon phase; a fractionator unit for fractionating the alkylate- comprising hydrocarbon phase into at least one stream comprising alkylate;
  • the present invention relates to a first method for revamping an HF or SA alkylation unit to an IL alkylation unit.
  • Reference herein to revamping is to modifying or adapting an existing unit or process line-up designed for operating a specific process, such that it is suitable for operating another process.
  • the obtained IL alkylation unit is used to produce alkylate by reacting an
  • alkylation conditions or process conditions are known in the art, whereby it will be appreciated that actual operational process conditions are among others dependent of the exact composition of the reactants and catalyst.
  • the temperature in the reactor unit is preferably in the range of from -20 to 100 0 C, more preferably in the range of from 0 to 50 0 C, however the temperature must be high enough to ensure that the ionic liquid is in its liquid form.
  • the process is performed under pressure, preferably the pressure in the reactor is in the range of from 0.1 to 1.6 MPa. - A -
  • the alkylation process may be a semi-continues or continuous process.
  • the isoparaffin is an isobutane or an isopentane and the olefin is an olefin comprising in the range of from 2 to 8 carbon atoms, more preferably of from 3 to 6 carbon atoms, even more
  • olefins preferably 4 or 5 carbon atoms.
  • suitable olefins include, propene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 2-methyl-l-butene, 3-methyl-l- butene, 2-methyl-2-butene .
  • fresh isoparaffins and olefins are supplied to the process in a molar ratio, which is preferably 1 or higher, and typically in the range of from 1:1 to 40:1, more preferably 1:1 to 20:1.
  • a molar ratio which is preferably 1 or higher, and typically in the range of from 1:1 to 40:1, more preferably 1:1 to 20:1.
  • isoparaffin can be recycled to the reactor unit by recycling one or more isoparaffin-comprising streams.
  • Reference herein below to downstream is to the direction of the fluid flow path from the reactor unit to the fractionator unit.
  • Reference herein upstream is to the opposite direction, i.e. from the fractionator unit to the reactor unit.
  • Existing HF and SA alkylation units comprise at least a reactor unit for contacting the reactants with the catalyst.
  • the reactor unit preferably comprises at least one reactant inlet and at least one reactor effluent outlet.
  • the reactor unit also comprises at least one catalyst inlet.
  • a typical reactor unit provided in sulphuric alkylation unit is a so-called Stratco contactor.
  • the hydrocarbon reactants are introduced into an U-shaped reactor fluid flow path together with the catalyst.
  • typical reactors include e.g. Stratco contactors, gravity circulation reactors and emulsion reactors.
  • cooling tubes are provided in the reactor fluid flow path to remove the heat generated by the exothermic alkylation reaction. Alternatively, cooling is applied to the acid recycle stream.
  • the effluent of the reactor unit is a mixture of catalyst and a hydrocarbon phase, the latter comprising an alkylate and unreacted reactants, predominantly isoparaffin.
  • the effluent of the reactor unit is normally provided to a separator unit to separate the reactor effluent into a catalyst phase and an alkylate-comprising hydrocarbon phase.
  • the separator unit comprises at least one inlet, typically for the reactor effluent or a stream generated there from, and at least one catalyst phase outlet and at least one alkylate-comprising hydrocarbon phase outlet.
  • the separator unit serves to separate the effluent of the reactor unit into an alkylate-comprising hydrocarbon phase and a catalyst phase.
  • the separator unit used in the HF and SA alkylation units to be
  • a settler unit is to any separator unit that separates two liquid phases under the influence of gravity.
  • HF, SA and IL catalysts all have a density, which is higher than that of the hydrocarbon phase, therefore the reactor effluent is typically separated in the settler in an upper hydrocarbon phase and a lower catalyst phase.
  • catalyst phase recycle means are provided to recycle SA catalyst from the settler unit to the reactor unit.
  • part of the SA catalyst is removed from the process as spent catalyst and fresh SA catalyst is added to keep catalyst levels and activity intact.
  • the HF catalyst is
  • an HF alkylation unit comprises catalyst phase recycle means to recycle the HF catalyst, combined a separate regeneration.
  • the alkylate-comprising hydrocarbon phase, which was obtained in the settler is, at least in part, provided to a fractionator unit to obtain the retrieve the alkylate.
  • the fractionator unit preferably comprises at least one alkylate-comprising hydrocarbon phase inlet.
  • distillation sub-units typically, comprises one or more distillation sub-units, including for instance a main fractionator (also referred to in the art as iso-stripper) , an acid stripper and/or a depropaniser .
  • a main fractionator also referred to in the art as iso-stripper
  • acid stripper also referred to in the art as acid stripper
  • depropaniser a depropaniser
  • the obtained alkylate may be used to prepare avgas or as a blending component for gasoline.
  • the hydrocarbon phase may also comprise significant amounts of unreacted isoparaffin.
  • isoparaffin is at least partly recycled back to the reactor unit, via a provided means for recycling
  • isoparaffin from the fractionator unit to the reactor.
  • Other hydrocarbon streams may also be obtained by
  • HF or SA alkylation units means are provided to allow the reactants and catalyst to enter the reactor and to provide the reactor effluent to the separator unit and subsequently the alkylate-comprising hydrocarbon phase to the fractionator unit. It is not necessary to pass the reactor effluent directly from the reactor unit to the separator unit.
  • the reactor effluent may undergo intermediate treatment such as cooling or heating in a heat exchanger.
  • a fluid flow path for the reactants, products and catalyst is created by providing means to introduce reactants and catalyst to the reactor unit.
  • means are provided to provide reactor effluent from the reactor effluent outlet of the reactor unit to the reactor effluent inlet of a separator unit located downstream from the reactor unit in the fluid flow path. Also, means are provided to provide an alkylate-comprising hydrocarbon phase from the alkylate-comprising hydrocarbon phase outlet of the separator unit to the alkylate-comprising hydrocarbon phase inlet of a fractionator unit located downstream from the separator unit in the fluid flow path and catalyst phase recycle means are provided to recycle catalyst from the settler unit to the reactor unit.
  • Ionic liquids are known in the art for their ability to catalyse alkylation reactions.
  • the catalyst used in the present invention is a composite ionic liquid
  • the cations comprise nitrogen atoms, which are saturated with four substituents, among which there is at least one hydrogen atom and one alkyl group. More preferably, the alkyl substituent is at least one
  • Suitable cations include triethyl-ammonium (NEt 3 H + ) and methyl- diethyl-ammonium cations (MeNEt 2 H + ) or
  • the anions of the composite ionic liquid are
  • aluminium based Lewis acids in particular aluminium halides, preferably aluminium (III) chloride. Due the high acidity of the aluminium chloride Lewis acid it is preferred to combine the aluminium chloride, or other aluminium halide, with a second or more metal halide, sulphate or nitrate to form a coordinate anion, in particular a coordinate anion derived from two or more metal halides, wherein at least one metal halide is an aluminium halide.
  • Suitable further metal halides, sulphates or nitrates may be selected from halides, sulphates or nitrates of metals selected from the group consisting of Group IB elements of the Periodic Table, Group HB elements of the Periodic Table and transition elements of the Periodic Table.
  • suitable metals include copper, iron, zinc, nickel, cobalt, molybdenum, or platinum.
  • the metal halides, sulphates or nitrates are metal halides, more preferably chlorides or bromides, such as copper (I) chloride, copper (II) chloride, nickel (II) chloride, iron (II) chloride.
  • the molar ratio of the aluminium compound to the other metal compounds in the range of from 1:100-100:1, more preferably of from 1:1-100:1, or even more preferably of from 2:1-30:1.
  • catalysts are acidic ionic liquid catalysts comprising a coordinate anion derived from aluminium (III) chloride and copper (II) chloride or aluminium (III) chloride and copper (I) chloride.
  • the optimal reaction temperature which is typically lower for IL alkylation for instance than for HF alkylation.
  • the reaction mixture must be cooled to lower temperatures, placing a higher cooling requirement on the Stratco contactor.
  • the reactor unit in the HF or SA alkylation unit to be revamped is adapted by providing a means for recycling at least part of the reactor effluent from the reactor effluent outlet of the reactor unit to the reactant inlet of the reactor unit.
  • Such means allow recycling of at least part of the reactor effluent prior to the separation of the reactor effluent in a catalyst phase and an alkylate-comprising hydrocarbon phase.
  • the HF or SA alkylation unit to be revamped may also be adapted by providing a means for recycling at least part of the alkylate-comprising hydrocarbon phase from the alkylate-comprising hydrocarbon phase outlet of the separator unit to the reactant inlet of the reactor unit.
  • Such means allow recycling of at least part of the alkylate-comprising hydrocarbon phase prior to
  • the HF or SA alkylation unit to be revamped may furthermore be adapted by replacing the original reactor unit by a loop reactor. It will be appreciated that any combination of the above-described methods is also possible.
  • at least a means for recycling at least part of the alkylate-comprising hydrocarbon phase from the alkylate-comprising hydrocarbon phase outlet of the separator unit to the reactant inlet of the reactor unit is provided.
  • the means for recycling at least part of the alkylate-comprising hydrocarbon phase are provided such that the recycled alkylate-comprising hydrocarbon phase may be mixed with the at least part of the reactants prior to entering the reactor unit through the reactant inlet.
  • the means for recycling at least part of the alkylate-comprising hydrocarbon phase are provided such that the recycled alkylate-comprising hydrocarbon phase may be mixed with the at least part of the
  • At least one static mixer device is provided in the reactor unit or loop reactor.
  • the static mixer device is located between the reactant inlet and reactor effluent outlet.
  • the static mixer is placed directly after the reactant inlet or even the inlet may be inside or overlap with the static mixer itself. It is also possible and preferred to adapt the reactor unit or a loop reactor by providing two or more reactant inlets each followed by a separate static mixer device located between two subsequent reactant inlets.
  • the reactor unit or loop reactor is adapted to comprise two or more reactant inlets and at least one static mixer device overlaps with at least two inlets .
  • a alkylation unit may be obtained comprising a reactor unit, which combines a large reactant recycle with an operation under plug flow conditions, i.e. back-mixing is minimised.
  • the adapted reactor or loop reactor is a tube reactor comprising one or more parallel and/or serial aligned tubular passageways.
  • Reference herein to a loop reactor is to a reactor wherein the recycle of the reactor effluent incorporated into the reactor by
  • isoparaffin and olefin to the catalyst phase and rapid dissipation of heat of reaction thereby preventing the creation of localised high temperatures areas or volume elements .
  • the high isoparaffin to olefin ratio and improved mixing efficiency of the loop reactor according to the invention results in high selectivity towards the
  • the means for recycle of the reactor effluent/alkylate-comprising phase or the loop reactor comprises a means to apply a high shear to a circulating liquid mixture, such as for instance a circulating pump.
  • a high shear to a liquid alkylation mixture a large inter-phase surface area may be may be obtained.
  • the reactor preferably comprises at least one
  • reactant inlet for introducing olefin and/or isoparaffin. It is preferred that the reactants inlet is provided with individual dispersion devices, e.g. atomizing nozzles, intended to produce a fine disperse phase into a
  • liquid alkylation mixture which may comprise unreacted hydrocarbons, alkylate and catalyst.
  • the reactor preferably also comprises at least one outlet for reactor effluent, which may be used to provide reactor effluent to the settler.
  • a static mixer In between an inlet and an outlet a static mixer is located, i.e. the static mixer is located in the fluid flow path downstream from the inlet and upstream from the outlet.
  • Reference herein, to a static mixer is to a device compressing one or more mixer elements and which mixes without an external power source.
  • the static mixer is located close to the inlet to ensure that the reactants, which are introduced via the inlet, are rapidly mixed with the circulating alkylation mixture.
  • each reactant inlet is followed by a separate static mixer, wherein the static mixers are provided in between two subsequent reactant inlets and before the reactor effluent outlet, i.e. each static mixer is located in the fluid flow path downstream of a first inlet and upstream of the subsequent inlet or the outlet.
  • one or more static mixers are provided which extend from a reactants inlet to and beyond one or more subsequent reactant inlets located downstream of the first reactant inlet.
  • the number of inlets is dependent on the size of the reactor and the desired molar ratio of isoparaffins to olefins in the reactor.
  • the distance between the reactants inlets in terms of residence time is larger than the residence time required for nearly complete conversion, i.e. 90 mol% or more based on the olefin feed to the reactor unit.
  • reactor unit or loop reactor with two or more reactor effluent outlets, e.g. to reduce the volume which has to be withdrawn via a single outlet.
  • the present invention also provides a second method for revamping an HF or sulphuric acid alkylation unit to an ionic liquid alkylation unit, wherein the HF or sulphuric acid alkylation unit comprise at least:
  • a separator unit for separating a reactor effluent into a catalyst phase and an alkylate-comprising hydrocarbon phase, ;
  • a fractionator unit for fractionating the alkylate- comprising hydrocarbon phase into at least one stream comprising alkylate, ;
  • a catalyst phase recycle means to recycle at least part of the catalyst phase from the separator unit to the reactor unit;
  • which method includes: adapting the catalyst phase recycle means by providing a means for acid injection into the catalyst recycle means .
  • a suitable acid to the, at least partly, deactivated catalyst.
  • such acid is a halo acid, more preferably hydrochloric acid.
  • the catalyst may be contacted with hydrogen chloride to rejuvenate the catalyst. This can be done by introducing hydrogen chloride or another suitable acid into the reactor unit or into at least part of the reactor effluent, which comprises at least part of the acidic ionic liquid catalyst.
  • hydrogen chloride or another suitable acid is contacted with at least part of the reactor effluent, which comprises at least part of the acidic ionic liquid catalyst. More preferably, the hydrogen chloride or another suitable acid is contacted with the IL catalyst after separation from the hydrocarbons in the settler unit.
  • a catalyst phase recycle means for providing HF or SA catalyst from the separator unit to the reactor unit is adapted, by additionally providing a means for acid injection into the catalyst phase recycle means, i.e. between the separator unit and the reactor unit.
  • Suitable means for acid injection comprise gas and liquid injectors or gas bubblers, preferably combined with a suitable storage vessel for the acid.
  • the means for injecting an acid may comprise a gas injector or bubbler fluidly connected to a vessel for storing gaseous hydrogen chloride.
  • circulation means comprising a venturi absorber may be provided to circulate at least part of the catalyst phase recycle and mix it with the gas cap using the venturi absorber.
  • the hydrogen chloride reacts with the acidic ionic liquid catalyst. Hydrogen chloride is added until no hydrogen chloride is consumed any longer, i.e. until saturation. Hydrogen chloride consumption can be followed by measuring the pressure decrease. Preferably, the addition of hydrogen chloride is done in regular steps, while measuring the pressure in between each addition step. By adding the hydrogen chloride in small steps the creation of an undesired hydrogen chloride gas cap upon saturation is reduced. To follow the hydrogen chloride pressure it is preferred that a means for measuring the pressure is provided in the catalyst recycle or the reactor unit.
  • catalyst phase comprising added hydrogen chloride.
  • Reference, herein to spent acidic ionic liquid catalyst is to an acidic ionic liquid catalyst, which has been used as a catalyst in a chemical reaction and has not yet been rejuvenated with hydrogen chloride.
  • the spent acidic ionic liquid catalyst may be
  • the catalyst phase recycle means allow part of the ionic liquid catalyst to bypass the rejuvenation and subsequently mix the rejuvenated and bypassed streams.
  • solids may be formed. As the reaction progresses, these solids may accumulate in the reaction mixture in the reactor unit.
  • the present invention also provides a third method for revamping an HF or sulphuric acid alkylation unit to an ionic liquid alkylation unit, wherein the HF or sulphuric acid alkylation unit comprise at least:
  • a fractionator unit for fractionating the alkylate- comprising hydrocarbon phase into at least one stream comprising alkylate
  • the accumulation of solids in the reaction mixture may be prevented.
  • the solids predominantly consist out of metals, metal compounds and/or metal salts, which were originally comprised in the acidic liquid catalyst. Additionally, the solids may comprise compounds, which were formed by a chemical reaction including any of the above-mentioned compounds. Typically, the solids comprise at least 10wt% metal, i.e. either in metallic, covalently bound or ionic form, based the total weight of the solids, wherein the metal is a metal that was introduced to the process as part of the acidic ionic liquid catalyst. The solids may also comprise components, which were introduced into the reaction mixture as contaminants in the hydrocarbon mixture or the acidic ionic liquid.
  • the solids may have any size, however it was found that the solids typically have an average size of in the range of from 0.1 to lO ⁇ m. In particular, at least 50% of the solids have a particle size below 5 ⁇ m, more
  • the solids have a particle size below 5 ⁇ m based on the total number of solid particles.
  • the solids may be dispersed, upon the alkylation reaction in the reactor unit.
  • the solids i.e. to a large extent, accumulate in the IL catalyst. This is due to the high density of the solids.
  • the IL catalyst is subsequently recycled to the reactor unit together with the solids.
  • the solids accumulate in the reactor unit, resulting in undesirable solids content in the reactor unit, but also in the reactor effluent.
  • a high solids content in the reaction mixture may for instance result in blockage of pathways or valves in the reactor unit and pipes to and from the separator unit, due to
  • the solids may agglomerate to from large
  • a second separator unit suitable for the separation of solids from liquids.
  • a second separator unit may be any separator unit suitable for the separation of a solid from a liquid, including but not limited to filtration, precipitation and
  • the second separator unit may be comprised of two or more similar or different separation sub-units suitable for the separation of a solid from a liquid.
  • the second separator unit comprises one or more centrifugal separator units.
  • the removal of the solids is performed at such a temperature that the IL catalyst is liquid.
  • the second separator unit can be operated at a temperature in the range of from 5 to 80 0 C, more preferably of from 20 to 60 0 C.
  • a temperature in the range of from 5 to 80 0 C, more preferably of from 20 to 60 0 C.
  • the second separator unit may be provided at any suitable place in the HF or SA alkylation unit, which is revamped.
  • the second separator unit may be integrated with the reactor unit to remove the solids directly from the reaction mixture inside the reactor. However, preferably, the second separator unit is provided
  • the reactor unit downstream of the reactor unit.
  • the first separator unit i.e. the settler unit for separation the hydrocarbon phase from the catalyst.
  • the reactor effluent may be treated to remove the solids.
  • the solids accumulate in the catalyst phase in the settler unit. Therefore, it is more preferred to remove the solids from the catalyst prior to
  • alkylation unit this can be done by adapting the catalyst phase recycle means by providing a second separator unit suitable for separating solids from a liquid.
  • the reactor unit comprises at most 5wt%, preferably in the range of from 0.05 to 5wt%, more preferably of from 0.1 to 2wt% of solids based on the total weight of the ionic liquid catalyst in the reactor unit.
  • the solids may be removed from the process in any form, typically the solids will be removed in the form of a slurry of solids.
  • a slurry may comprise next to the solids for instance some residual acidic ionic liquid.
  • means are provided to further treat the slurry by extracting the residual acidic ionic liquid. This is preferably done using a liquid-liquid extraction process with a suitable solvent. Due to the virtual absence of an ionic liquid vapour pressure, the solvent can be easily recovered by for instance
  • the recovered solvent can be reused.
  • alkylation unit may not provide sufficient separation capacity for separation the hydrocarbon and catalyst phases.
  • catalyst remains in the hydrocarbon phase and vice versa.
  • catalyst consumption increases and additionally, the hydrocarbon phase is contaminated with catalyst.
  • hydrocarbon recycle volumes may increase due to the higher
  • the isoparaffin to olefin molar ratios used is in the range of 1 to 10.
  • the isoparaffin to olefin molar ratios used are preferably above 20 or even above 100.
  • the present invention also provides a fourth method for revamping an HF or sulphuric acid alkylation unit to an ionic liquid alkylation unit, wherein the HF or sulphuric acid alkylation unit comprise at least:
  • a separator unit for separating a reactor effluent into a catalyst phase and an alkylate-comprising hydrocarbon phase; a fractionator unit for fractionating the alkylate- comprising hydrocarbon phase into at least one stream comprising alkylate;
  • settler units are provided to separate the HF or SA catalyst and the hydrocarbon phase from the reactor effluent.
  • existing settlers designed to separate HF or SA from hydrocarbons, for separating IL catalyst and the
  • alkylate-comprising hydrocarbon phase from the reactor effluent after the HF or SA alkylation unit has been revamped to and IL alkylation unit may result in several undesired effects, including:
  • a cyclone unit is provided downstream of the reactor unit and means are provided to provide at least part of the reactor effluent to the cyclone unit to enhance separation of the catalyst phase and hydrocarbon phase.
  • the cyclone unit may comprise one or more cyclone sub-units in series.
  • the cyclone unit may comprise one or more cyclone sub-units in series.
  • hydro-cyclones comprises one or more hydro-cyclones.
  • Reference herein to a hydro-cyclone is to a cyclone designed for the
  • the cyclone unit comprises two or more cyclones or hydro-cyclones in series, wherein the low density predominantly alkylate-comprising hydrocarbon phase effluent of the first (hydro-) cyclone is provided to the next (hydro-) cyclone .
  • the one or more cyclone units are provided in addition to the existing settler unit.
  • the one or more cyclone units are provided upstream of the settler unit and means are provided to pass the lower density, predominantly alkylate-comprising hydrocarbon phase effluent from the cyclone unit to the settler unit.
  • the separator unit of the HF or SA alkylation unit to be revamped is replaced by one or more cyclone units.
  • the higher density effluent of the cyclone unit which comprises predominantly catalyst phase, can be recycled to the reactor unit, optionally after being combined with catalyst phase obtained in the settler unit, if present.
  • two or more cyclones units can be applied in parallel to increase the capacity.
  • These parallel cyclones units can be combined in series with one or more settlers.
  • the ionic liquid fraction in lower density, predominantly alkylate-comprising hydrocarbon, effluent may be lowered even further by subjecting the lower density, predominantly alkylate-comprising hydrocarbon phase effluent to a further physical separation
  • a settler unit may be relatively large in volume compared to e.g. a cyclone, if a settler unit is used downstream of a cyclone unit, the invention still provides an advantage as the settler unit will be much smaller than a settler unit in a conventional process, which is used to separate the reactor effluent.
  • the method according to the present invention may also include a combination of the first method with the second, third and/or fourth method according to the invention and described herein above.
  • the method according to the present invention may also include combinations of the second method with the third and/or fourth method according to the invention and described herein above.
  • the second and third method according to the invention means are provided to, during operation of an IL alkylation process, replace any chlorine that is lost with the formation and removal of the solids by the addition of hydrogen chloride during rejuvenation. It is a particular advantage that both the second separator unit for removing solids and the means for acid injection can be provided in the same catalyst recycle means.
  • method according to the present invention may also include a combination of the third method with the fourth method according to the invention and described herein above.
  • a synergistic effect may be obtained, which may further increase the suitability of the revamped alkylation unit for IL alkylation.
  • the first and fourth method it is possible to revamp the existing SA or HF alkylation unit by providing a recycle of hydrocarbons from the separator unit back to the reactor unit to allow for a high isoparaffin to olefin molar ratios in the reactor during operation of a IL alkylation process, while providing a cyclone unit as the separator unit to allow continuous fast separation of hydrocarbons and IL catalyst during operation of the IL alkylation process. By doing so the need to maintain a large
  • both the second separator unit for removing solids and the means for acid injection can be provided in the same catalyst recycle means.
  • a hydrocarbon mixture comprising olefin and isoparaffin is provided to reactor unit 100, e.g. a Stratco contactor, via conduit (e.g. a pipe) 105, through reactant inlet 107.
  • Catalyst, SA or IL is also provided to reactor unit 100 through conduit 110 and catalyst inlet 113.
  • the hydrocarbon mixture and catalyst are contacted under alkylation conditions.
  • a reactor effluent comprising catalyst and hydrocarbons is withdrawn from reactor unit 100 and supplied via conduit 115 to settler unit 120 through reactor effluent inlet 122.
  • an alkylate-comprising hydrocarbon phase and a catalyst phase separate under influence of gravity.
  • the hydrocarbon phase is withdrawn from separator unit 120 via alkylate-comprising hydrocarbon phase outlet 123 and provided to fractionator unit 125 through conduit 130 and alkylate-comprising hydrocarbon phase inlet 133.
  • an alkylate-comprising product is retrieved through conduit 135.
  • the alkylate product can for instance be used for fuel blending purposes.
  • an isoparaffin product is retrieved from fractionator unit 125, which is recycled via conduit 140 to become part of the hydrocarbon mixture in conduit 105.
  • Other hydrocarbon-comprising streams may also be retrieved from fractionator 125.
  • the catalyst phase is withdrawn from separator unit 120 through catalyst phase outlet 143 and can be recycled via catalyst phase recycle conduit 145 to reactor unit 100.
  • a spent catalyst fraction may be withdrawn from the process via conduit 150. Additional fresh catalyst can be provided to reactor unit 100 via conduit 155
  • FIG 2A a schematic representation is given of a SA alkylation unit as described in Figure 1, which was revamped using the method according to the invention, wherein the reactor effluent is recycled to the inlet for reactants of reactor unit 100.
  • the arrow indicates the flow direction in reactor unit 100.
  • conduit 105 for providing the reactants to reactor unit 100 is split to provide reactants to both first reactant inlet 205 via conduit 207 and via conduit 210 to second
  • reactant inlet 212 located downstream of first reactant inlet 205. Overlapping with and extending downstream of reactant inlet 205, first static mixer 215 is placed and overlapping with and extending downstream of reactant inlet 210, second static mixer 220 is placed.
  • a reactor effluent is withdrawn from reactor unit 100 via reactor effluent outlet 114.
  • a part of the reactor effluent is provided to separator unit 120 via conduit
  • reactor effluent recycle conduit 225 Another part of the reactor effluent is recycled to reactor inlet 205 via reactor effluent recycle conduit 225.
  • the recycled reactor effluent is combined with the reactants in reactant conduit 207, however it is also possible to supply the recycled reactor effluent directly to reactant inlet 205 or a separate recycled reactor effluent inlet (not shown) Circulation pump 230 has been provided in reactor
  • effluent recycle conduit 225 to assist the recycling of reactor effluent to reactor unit 100.
  • reactor effluent recycle conduit 225 has been replaced by alkylate-comprising hydrocarbon phase recycle conduit 240.
  • an alkylate- comprising hydrocarbon phase is withdrawn from separator unit 120 via alkylate-comprising hydrocarbon phase outlet 123.
  • a part of the alkylate-comprising hydrocarbon phase is provided to fractionator unit 125 via conduit 130.
  • Another part of the alkylate-comprising hydrocarbon phase is recycled to reactor inlet 205 via alkylate-comprising hydrocarbon phase recycle conduit 240.
  • the recycled alkylate-comprising hydrocarbon phase is
  • Circulation pump 230 has been provided in reactor effluent recycle conduit 240 to assist the recycling of alkylate-comprising hydrocarbon phase to reactor unit 100.
  • FIG 2C a schematic representation is given of a SA alkylation unit as described in Figure 1, which was revamped using the method according to the invention, wherein reactor unit 100 is replaced by loop reactor unit 200.
  • the arrows indicate the flow direction in loop reactor unit 200.
  • conduit 105 for providing the reactants to reactor unit 100 is split to provide reactants to both first reactant inlet 205 via conduit 207 and via conduit 210 to second reactant inlet 212, located downstream of first reactant inlet 205.
  • first static mixer 215 is placed and extending downstream of reactant inlet 210, second static mixer 220 is placed.
  • a reactor effluent is withdrawn from loop reactor unit 200 via reactor effluent outlet 245 and conduit 115.
  • Circulation pump 230 has been provided to circulate the reactants and catalyst in loop reactor unit 200.
  • FIG 3 a schematic representation is given of a SA alkylation unit as described in Figure 1, which was revamped using the method according to the invention, wherein a means for acid injection into the catalyst recycle means acid is provided.
  • means 305 for injecting an acid e.g. a gas injector
  • Injector means 305 is fluidly connected to storage vessel 310, wherein an acid such as hydrogen chloride is stored. If required, a part of the recycled catalyst phase may bypass means 305 via bypass conduit 315.
  • Bypass conduit 315 recombines with catalyst phase recycle conduit 145 downstream of acid injection means 305.
  • FIG 4A a schematic representation is given of a SA alkylation unit as described in Figure 1, which was revamped using the method according to the invention, wherein a second separator unit suitable for the
  • part or all of the catalyst phase can be diverted from catalyst phase recycle conduit 145 by conduit 405 to centrifuge 410.
  • centrifuge 410 solids are removed from the IL catalyst phase under influence of the
  • the remaining IL catalyst phase exits centrifuge 410 via conduit 420, which is in fluid connection with catalyst phase recycle conduit 145.
  • FIG 4B a schematic representation is given of a SA alkylation unit as described in Figure 1, which was revamped using the method according to the invention comparable to that in Figure 4A.
  • centrifuge 410 was incorporated directly in catalyst phase recycle conduit 145.
  • FIG 5A a schematic representation is given of a SA alkylation unit as described in Figure 1, which was revamped using the method according to the invention, wherein a cyclone unit is provided between the reactor unit and separator unit.
  • the reactor effluent is provided via conduit 115 to cyclone unit 505.
  • the lower density, predominantly alkylate-comprising hydrocarbon, phase from the cyclone unit is provided to settler unit 120 via conduit 510.
  • the higher density, predominantly catalyst, phase is provided to catalyst recycle conduit 145 via conduit 515.
  • a more detailed representation of a possible cyclone unit 505 is given in Figure 5B, wherein reactor effluent enters first cyclone sub-unit 550 in cyclone unit 505 via conduit 115.
  • the lower density phase exits first cyclone sub-unit 550 via conduit 555 and is provided to second cyclone sub-unit 560 for further separation of catalyst phase from the alkylate-comprising hydrocarbon phase.
  • a lower density alkylate-comprising hydrocarbon phase exits second cyclone sub-unit 560 via conduit 565 and is provided to settler unit 120.
  • a higher density catalyst phase is obtained from both first cyclone sub-unit 550 and second cyclone sub-unit 560 via respectively conduit 570 and 575 and may be provided to catalyst recycle conduit 145.
  • an alkylate-comprising hydrocarbon phase recycle conduit is provided;
  • Static mixing devices are provided in reactor unit 100;
  • a cyclone unit is provided between the reactor unit and separator unit.
  • the catalyst used was an ionic liquid catalyst comprising a coordinate anion derived from aluminium (III) chloride and copper (I) chloride) (ex China University of Petroleum Beijing) .
  • a hydrocarbon mixture of isobutane and butenes was provided together with the acidic ionic liquid catalyst to the alkylation reactor.
  • the reactor had a volume of 0.4 litre.
  • the effluent of the alkylation reactor was separated in a settler and part of the hydrocarbon phase was sent to a fractionator, while the remainder of the hydrocarbon phase was recirculated to the reactor.
  • the alkylate was obtained from the bottom of the fractionator and tested to determine the motor RON and MON values.
  • An isobutane-comprising stream was recycled from the fractionator back to the hydrocarbon mixture.
  • the acidic ionic liquid catalyst phase obtained from the settler was recycled to the reactor. Periodically, i.e. between the runs, the acidic ionic liquid catalyst phase obtained from the settler was redirected to a disk centrifuge and centrifuged at 20000 rpm for 1 hour at a temperature of 50 0 C. The weight of solids produced was recorded. Following the solids removal, hydrogen chloride gas was added to the treated acidic ionic liquid catalyst at a pressure of approximately 5 bar at a temperature of 35°C, until no hydrogen chloride was consumed any more. The amount of hydrogen chloride consumed was recorded. The reaction condition and obtained results are listed in Table 1.
  • the ionic liquid catalyst was intermittently rejuvenated, by reacting with hydrogen chloride. As a result catalyst activity and the alkylate quality remains high.
  • isobutane/butene ratio i.e. the isobutane/butene ratio in the mixture of fresh feed and the isobutane recycled from the fractionator
  • Example 2 Using the same reactor set-up and conditions as in Example 1, a fourth run was performed using an ionic liquid catalyst intake of 52.46 kg. Corrected for the loss of catalyst due to sampling, the average ionic liquid catalyst inventory during run 4 was 47.25 kg.
  • the catalyst consisted of 79wt%% of fresh ionic liquid, see example 1, and 21wt% of used ionic liquid obtained from run 3, following acid injection and solids removal.
  • An isobutane/butene mixture was introduced at 25 0 C with an average molar ratio of 14 based on a mixture of the recycled excess of isobutane from the fractionator and fresh feed of isobutane and butene, as used in
  • Example 1 The isobutane/butene mixture was introduced at a feed rate between 2 and 4 kg/h.
  • the acidic ionic liquid catalyst phase obtained from the settler was recycled at an average rate of 270kg/h.
  • An average of 80 kg/h of hydrocarbon phase obtained from the settler was recycled to reactor. No solids were removed during the run .
  • a breakthrough of butenes was detected in the reactor outlet after 195 kg of butenes, i.e. 4.13 kg of butenes per kg of ionic liquid catalyst (based on the average catalyst inventory) , had been fed to the
  • the average ionic liquid catalyst inventory during run 4 was 50.28 kg.
  • the ionic liquid catalyst consisted 28wt% of fresh ionic liquid, see example 1, 21wt% of ionic liquid of used ionic liquid obtained from run 3 following acid injection and solids removal and 51wt% of used ionic liquid obtained from run 4 following acid injection and solids removal.
  • Run 5 was conduct over a period of 7 days. Every 24 hours, approximately 10 kg of ionic liquid was separated off from the ionic liquid catalyst phase obtained from the settler. The separated ionic liquid catalyst was treated by dissolving HCl in the ionic liquid and the resulting ionic liquid catalyst was reinjected in the ionic liquid recycle to the reactor. In total 0.48 kg of HCl were added to the catalyst:
  • deactivated ionic liquid catalyst may be reactivated or rejuvenated by addition of an acid such as HCl.
  • a sample reactor effluent comprising a mixture of hydrocarbon reactants and products and ionic liquid catalyst was separated using a cyclone .
  • the sample reactor effluent comprises hydrocarbons and ionic liquid catalyst in a volume ratio of 1:1.05.
  • the operating temperature was maintained between 30 and 50 0 C and the operating pressure was maintained between 0.1 to 0.5 MPa.
  • the maximum feed rate of sample reactor effluent to the cyclone was 2 m 3 /hr.
  • the higher density, predominantly catalyst, phase comprised:
  • the size of volume of the settler unit is only 40% of a settler unit used to separate the whole reactor effluent.
  • the sample reactor effluent was separated into a lower density, predominantly alkylate- comprising hydrocarbon, phase and a higher density, predominantly catalyst, phase using two separation steps.
  • the obtained separation results are below.
  • the intermediate phase comprised:
  • the higher density, predominantly catalyst, phase comprised:
  • the obtained intermediate phase was retrieved as an intermediate product and subjected to a second cyclone separation step.
  • 85vol% of the intermediate phase was retrieved from the cyclone as, lighter density, hydrocarbon phase effluent and the remaining 15 vol% of the intermediate phase was retrieved as a higher density phase effluent, also referred to a (an) other effluent.
  • the lower density, predominantly alkylate- comprising hydrocarbon, phase comprised:
  • the other effluent comprised:
  • the lower density, predominantly alkylate- comprising hydrocarbon, phase comprises only 79 vol% of the hydrocarbons originally present in the reactor effluent.
  • Example Ib however, 86 vol% of the
  • hydrocarbons in the reactor effluent were retrieved in the hydrocarbon effluent, comprising less ionic liquid.
  • the higher density, predominantly catalyst, phase comprised less hydrocarbons compared using only one separator, even in the case it is combined with the (an) other effluent.
  • the size of volume of the settler unit is only 42.5% of a settler unit used to separate the whole reactor effluent.

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Abstract

La présente invention concerne un procédé pour remodeler une unité d'alkylation de HF ou d'acide sulfurique en une unité d'alkylation de liquide ionique. L'unité d'alkylation de HF ou d'acide sulfurique comprend au moins: une unité de réaction pour mettre en contact le catalyseur et les réactifs d'hydrocarbures; une unité de séparation pour séparer un effluent de réacteur en une phase de catalyseur et une phase d'hydrocarbures comprenant un alkylate; une unité de fractionnement pour fractionner la phase d'hydrocarbures comprenant un alkylate en au moins un flux comprenant un alkylate. Lequel procédé comprend une ou plusieurs des étapes qui consistent: i) à utiliser un moyen pour recycler au moins une partie de l'effluent de réacteur vers l'unité de réaction; ii) à utiliser un moyen pour recycler au moins une partie de la phase d'hydrocarbures comprenant l'alkylate dans l'unité de réaction; et/ou iii) à remplacer l'unité de réacteur par une réacteur à boucle. L'invention concerne également trois autres procédés pour remodeler une unité d'alkylation de HF ou d'acide sulfurique.
PCT/EP2010/061513 2009-08-06 2010-08-06 Procédé pour remodeler une unité d'alkylation de hf ou d'acide sulfurique WO2011015662A2 (fr)

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CN102807493A (zh) * 2012-05-30 2012-12-05 中国石油大学(北京) 一种离子液体催化甲苯二胺烷基化合成二乙基甲苯二胺的方法
US20130066133A1 (en) * 2011-09-12 2013-03-14 Chevron U.S.A. Inc. Conversion of hf alkylation units for ionic liquid catalyzed alkylation processes
WO2013039581A2 (fr) * 2011-09-12 2013-03-21 Chevron U.S.A. Inc. Systèmes et procédés d'alkylation au moyen d'un liquide ionique utilisé à titre de catalyseur
WO2013039584A1 (fr) * 2011-09-12 2013-03-21 Chevron U.S.A. Inc. Conversion d'unités d'alkylation d'acide sulfurique pour des procédés d'alkylation catalysés par un liquide ionique
US20130068849A1 (en) * 2011-09-15 2013-03-21 Susanne Birkel Aerosol Hairspray Product for Styling and/or Shaping Hair
WO2015085438A1 (fr) 2013-12-09 2015-06-18 Orell Füssli Sicherheitsdruck Ag Document de sécurité ayant un élément en feuille avec compensation de contrainte
WO2016094183A3 (fr) * 2014-12-11 2016-07-28 Uop Llc Procédés de récupération de fines liquides uniques depuis un flux de traitement
US9669377B2 (en) 2014-12-12 2017-06-06 Uop Llc Ionic liquid reactor with heat exchanger
US9950970B2 (en) 2014-12-12 2018-04-24 Uop Llc Ionic liquid reactor with heat exchanger
US9956504B2 (en) 2016-08-30 2018-05-01 Chevron U.S.A. Inc. Integrated coalescing system for separating dispersed ionic liquid from liquid hydrocarbon
US10584079B2 (en) 2015-07-23 2020-03-10 Uop Llc Modified HF alkylation reaction zone for ionic liquid alkylation
US10722861B2 (en) 2015-12-10 2020-07-28 Uop Llc Reactor system for use with an ionic liquid catalyst
US11148115B2 (en) 2017-08-31 2021-10-19 Refining Technology Solutions, Llc Sulfuric acid alkylation reactor system and conversion of a hydrogen fluoride alkylation unit to a sulfuric acid alkylation unit

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AU2012309139B2 (en) * 2011-09-12 2015-12-17 Chevron U.S.A. Inc. Conversion of HF alkylation units for ionic liquid catalyzed alkylation processes
WO2013039584A1 (fr) * 2011-09-12 2013-03-21 Chevron U.S.A. Inc. Conversion d'unités d'alkylation d'acide sulfurique pour des procédés d'alkylation catalysés par un liquide ionique
GB2507456B (en) * 2011-09-12 2019-11-13 Chevron Usa Inc Conversion of HF alkylation units for ionic liquid catalyzed alkylation processes
WO2013039581A2 (fr) * 2011-09-12 2013-03-21 Chevron U.S.A. Inc. Systèmes et procédés d'alkylation au moyen d'un liquide ionique utilisé à titre de catalyseur
CN103781746B (zh) * 2011-09-12 2016-05-18 雪佛龙美国公司 改造hf烷基化单元用于离子液体催化烷基化方法
GB2508108B (en) * 2011-09-12 2019-11-13 Chevron Usa Inc Conversion of sulfuric acid alkylation units for ionic liquid catalyzed alkylation processes
WO2013039581A3 (fr) * 2011-09-12 2013-05-10 Chevron U.S.A. Inc. Systèmes et procédés d'alkylation au moyen d'un liquide ionique utilisé à titre de catalyseur
GB2507456A (en) * 2011-09-12 2014-04-30 Chevron Usa Inc Conversion of HF alkylation units for ionic liquid catalyzed alkylation processes
CN103781746A (zh) * 2011-09-12 2014-05-07 雪佛龙美国公司 改造hf烷基化单元用于离子液体催化烷基化方法
CN103781762A (zh) * 2011-09-12 2014-05-07 雪佛龙美国公司 改造硫酸烷基化单元用于离子液体催化烷基化方法
GB2508108A (en) * 2011-09-12 2014-05-21 Chevron Usa Inc Conversion of sulfuric acid alkylation units for ionic liquid catalyzed alkylation processes
KR101796230B1 (ko) * 2011-09-12 2017-11-10 셰브런 유.에스.에이.인크. 이온성 액체 촉매화된 알킬화 공정들을 위한 황산 알킬화 장치들의 전환
US8920755B2 (en) 2011-09-12 2014-12-30 Chevron U.S.A. Inc. Conversion of HF alkylation units for ionic liquid catalyzed alkylation processes
KR101753078B1 (ko) * 2011-09-12 2017-07-04 셰브런 유.에스.에이.인크. 이온성 액체 촉매화된 알킬화 공정을 위한 불산 알킬화 장치의 전환
WO2013039567A1 (fr) * 2011-09-12 2013-03-21 Chevron U.S.A. Inc. Conversion d'unités d'alkylation par hf pour des procédés d'alkylation catalysée par un liquide ionique
US20130066133A1 (en) * 2011-09-12 2013-03-14 Chevron U.S.A. Inc. Conversion of hf alkylation units for ionic liquid catalyzed alkylation processes
US8921636B2 (en) 2011-09-12 2014-12-30 Chevron U.S.A. Inc. Conversion of HF alkylation units for ionic liquid catalyzed alkylation processes
CN103781762B (zh) * 2011-09-12 2017-03-29 雪佛龙美国公司 改造硫酸烷基化单元用于离子液体催化烷基化方法
US20130068849A1 (en) * 2011-09-15 2013-03-21 Susanne Birkel Aerosol Hairspray Product for Styling and/or Shaping Hair
CN102807493A (zh) * 2012-05-30 2012-12-05 中国石油大学(北京) 一种离子液体催化甲苯二胺烷基化合成二乙基甲苯二胺的方法
WO2015085438A1 (fr) 2013-12-09 2015-06-18 Orell Füssli Sicherheitsdruck Ag Document de sécurité ayant un élément en feuille avec compensation de contrainte
WO2016094183A3 (fr) * 2014-12-11 2016-07-28 Uop Llc Procédés de récupération de fines liquides uniques depuis un flux de traitement
US9669377B2 (en) 2014-12-12 2017-06-06 Uop Llc Ionic liquid reactor with heat exchanger
US9950970B2 (en) 2014-12-12 2018-04-24 Uop Llc Ionic liquid reactor with heat exchanger
US10584079B2 (en) 2015-07-23 2020-03-10 Uop Llc Modified HF alkylation reaction zone for ionic liquid alkylation
US10722861B2 (en) 2015-12-10 2020-07-28 Uop Llc Reactor system for use with an ionic liquid catalyst
US9956504B2 (en) 2016-08-30 2018-05-01 Chevron U.S.A. Inc. Integrated coalescing system for separating dispersed ionic liquid from liquid hydrocarbon
US10610809B2 (en) 2016-08-30 2020-04-07 Chevron U.S.A. Inc. Process using an integrated coalescing system for separating dispersed ionic liquid from liquid hydrocarbon
US11148115B2 (en) 2017-08-31 2021-10-19 Refining Technology Solutions, Llc Sulfuric acid alkylation reactor system and conversion of a hydrogen fluoride alkylation unit to a sulfuric acid alkylation unit

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