EP3652273A1 - Procédé d'élimination de composés azotés à partir d'une charge d'hydrocarbures - Google Patents

Procédé d'élimination de composés azotés à partir d'une charge d'hydrocarbures

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Publication number
EP3652273A1
EP3652273A1 EP18729710.6A EP18729710A EP3652273A1 EP 3652273 A1 EP3652273 A1 EP 3652273A1 EP 18729710 A EP18729710 A EP 18729710A EP 3652273 A1 EP3652273 A1 EP 3652273A1
Authority
EP
European Patent Office
Prior art keywords
solvent
nitrogen
hydrocarbon
containing compounds
zsm
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Withdrawn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
EP18729710.6A
Other languages
German (de)
English (en)
Inventor
Blaise H. BRIDIER
Paul Hamilton
Marcel Janssen
Pierre J. Osterrieth
Christopher Taylor
Luc Martens
Bee YAP
Geraldine Tosin
John Houben
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.)
ExxonMobil Chemical Patents Inc
Original Assignee
ExxonMobil Chemical Patents Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by ExxonMobil Chemical Patents Inc filed Critical ExxonMobil Chemical Patents Inc
Publication of EP3652273A1 publication Critical patent/EP3652273A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/16—Oxygen-containing compounds
    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/28—Recovery of used solvent
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/30—Controlling or regulating
    • 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
    • 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
    • C10G45/68—Aromatisation of hydrocarbon oil fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • 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
    • C10G2300/1088—Olefins
    • 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
    • C10G2300/1088—Olefins
    • C10G2300/1092—C2-C4 olefins
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins

Definitions

  • This invention relates to a process for removing nitrogen-containing compounds from a hydrocarbon feed, in particular from a hydrocarbon feed containing C3 to C6 olefins.
  • the present invention also relates to a process for converting a hydrocarbon feed contaminated with at least one nitrogen-containing compound into a hydrocarbon product, said process comprising a step of removal of nitrogen-containing compounds from the hydrocarbon feed.
  • Hydrocarbon feed streams containing light olefins are used in catalytic oligomerisation processes to obtain oligomers and/or polymers, typically heptenes, octenes, nonenes and dodecenes. These products may be converted to further products such as alcohols, plasticisers, adipates, mercaptans and solvents.
  • the hydrocarbon feed steams derive from various sources including refinery operations such as catalytic or steam cracking and are known to contain certain amounts of impurities including, but not limited to, nitrogen-containing compounds such as nitriles.
  • impurities may have an adverse effect on the catalysts used in the oligomerisation process such as phosphoric acid- based catalyst, zeolite-based catalyst and supported metal catalysts.
  • nitrogen- containing compounds may act as catalyst poisons (contaminants) reducing the activity and life of the catalyst and/or inducing unsustainable operation conditions and should be removed from these hydrocarbon feed streams.
  • Prior art approaches to remove nitrogen-containing compounds include removal via liquid- liquid extraction techniques or adsorption techniques using a so-called guard bed.
  • Liquid-liquid extraction is disclosed for example in WO 2009/058229 and WO 2012/078218.
  • the latter document discloses removal of nitriles and/or pyrroles from a feed stream comprising olefins and paraffins by contacting the feed stream with a solvent and removing at least a portion of the nitriles and the pyrroles from the feed stream.
  • the process conditions are based on the distribution coefficient of the nitrogen-containing compounds in the feed stream and the solvent.
  • Solvents such as sulfone compounds or alkyl/alkenyl/aryl carbonates, typically propylene carbonate, are generally used.
  • Such solvents may be recycled or reused in the extraction process but generally after a regeneration process such as vacuum and steam distillation, back extraction, adsorption and anion-cation exchange resin column.
  • Regeneration processes include contacting the solvent after use in an extraction process with an inert gas or light hydrocarbons.
  • the present invention solves the above problem(s) by providing a process for the removal of nitrogen-containing compounds from a hydrocarbon feed, preferably from a hydrocarbon feed comprising at least one olefin selected from C3, C4, C5 and optionally C6 olefins and mixtures thereof, the process comprising the steps of:
  • step (b) subjecting the hydrocarbon phase obtained in step (b) to a distillation step to separate a heavy phase containing the solvent and optionally heavy hydrocarbon compounds, from a light hydrocarbon fraction containing the at least one olefin selected from C3, C4 and C5 olefins and mixtures thereof;
  • step (b) optionally subjecting the light fraction to further processing; and e) subjecting the solvent phase obtained in step (b), optionally with the heavy phase from step (c), to a regeneration step;
  • said process further comprising monitoring the degradation of the solvent by
  • the degradation of the solvent may also be monitored by
  • the regeneration step (e) is preferably operated in a stripping column by using an inert gas such as nitrogen or one or more of the Group 18 inert gases of the Periodic Table of the Elements (Wikipedia -2017) or a light hydrocarbon as defined below.
  • an inert gas such as nitrogen or one or more of the Group 18 inert gases of the Periodic Table of the Elements (Wikipedia -2017) or a light hydrocarbon as defined below.
  • the present invention relates to a process for converting a hydrocarbon feed comprising at least one olefin selected from C3, C4, C5, and optionally C6 olefins and mixtures thereof, contaminated with at least one nitrogen-containing compound into a hydrocarbon product, said process comprising the steps of:
  • Figure 1 is a schematic representation of steps (a) to (e) of the present invention including monitoring of the solvent degradation.
  • Figure 2 is a schematic representation of a preferred distillation column layout used in step (c).
  • Figure 3 shows the content of different nitrogen compounds in the different process streams in a process according to the present invention.
  • the present invention solves the problems of the accumulation of degradation products and heavy hydrocarbon compound in a solvent recycled loop by providing a process for the removal of nitrogen-containing compounds from a hydrocarbon feed, preferably a hydrocarbon feed comprising preferably at least one olefin selected from the C3, C4, C5 and optionally C6 olefins and mixtures thereof comprising the steps of:
  • step (b) contacting the hydrocarbon feed with an extracting solvent containing propylene carbonate to obtain a hydrocarbon phase of reduced nitrogen-containing compounds content and a solvent phase containing dissolved nitrogen-containing compounds; b) separating the hydrocarbon phase of reduced nitrogen-containing compounds content from solvent phase containing dissolved nitrogen-containing compounds; c) subjecting the hydrocarbon phase from step (b) to a distillation step to separate a heavy phase containing the solvent and optionally heavy hydrocarbon compounds and from a light fraction containing the C3, C4 and C5 olefins;
  • said process further monitoring the degradation of the solvent by
  • the recycled solvent is stored in a reservoir located in the solvent recycle loop after its regeneration and before being recycled to step (a).
  • a reservoir located in the solvent recycle loop after its regeneration and before being recycled to step (a).
  • such reservoir is equipped with skimming device to ensure that any accumulation of hydrocarbons material on the top of said reservoir can be removed.
  • the accumulation of solvent degradation products and heavy hydrocarbons in the recycling loop can be avoided or at least minimized by one or more of the following steps
  • degradation of the solvent is preferably limited by at least one of preventing oxygen and/or air intake in the equipment used to operate the processes according to this invention, keeping the water content in the solvent recycle loop below 1 wt%, more preferably below 0.6 wt%, or operating the regeneration process at temperature below 140°C, preferably below 135 °C.
  • the hydrocarbon feed used in this invention can be any hydrocarbon feed.
  • the hydrocarbon feed contains at least one olefin selected from C3, C4, C5 and optionally C6 olefins and is contaminated with nitrogen-containing compounds. More preferably the hydrocarbon feed contains at least one olefin selected from C3, C4, C5 and C6 olefins and nitrogen- containing compounds.
  • olefins refers to any unsaturated hydrocarbons having the formula C n H2 n .
  • the feed may also comprise one or more paraffins.
  • paraffins refers to any of the saturated hydrocarbons having the formula C n H2 n +2-
  • the paraffins that may be present in the olefin feed typically have from 1 to 15 carbon atoms, conveniently at least 3 and no more than 6 carbon atoms. Examples of suitable paraffins include methane, ethane, propane, butane, pentane, hexane, isomers thereof and mixtures thereof. If present, the paraffin usually acts as a diluent.
  • the olefin feed may comprise at least 10%, at least 25%o, at least 30%>, at least 35%, or at least 40%> paraffin, based upon the total volume of the feed.
  • the diluent may be present in the olefin feed in the range from 10% to 40%, alternatively, from 10% to 35%, and alternatively, from 20% to 35% based upon the total volume of the feed.
  • the diluent may also be fed to the reactor(s) separately from the olefin feed. When fed separately, the diluent may be fed in amounts equivalent to those mentioned above, where the diluent is co-fed with the feed.
  • the olefin containing feed comprises olefins selected from propene, butenes, pentenes, optionally hexenes, their isomers, and mixtures thereof.
  • the process of this invention is especially useful for the oligomerization of feeds comprising propene, butenes, pentenes, their isomers, and mixtures thereof.
  • “isomers” refers to compounds having the same molecular formula but different structural formula.
  • the feed may comprise an oligomer (higher olefin), for example, a dimer, such as one provided by recycling a part of an olefin oligomerization product stream.
  • oligomer(s) or “oligomer product” refers to an olefin (or a mixture of olefins) made from a few light olefins.
  • oligomers include dimers, trimers, and tetramers, obtained from two, three or four light olefins of the same number of carbon atoms, and mixed oligomers, obtained from 2 or more olefins having different numbers of carbon atoms and mixtures thereof.
  • oligomers are olefins or mixture of olefins having 20 carbon atoms or less, alternatively, 15 carbon atoms or less, such as 9 carbon atoms or less, and conveniently, 8 carbon atoms or less.
  • the hydrocarbon feed preferably comprises 30 wt% or more olefins, such as 40 wt% or more olefins, alternatively, 50 wt% or more olefins, alternatively, 60 wt% or more olefins, alternatively, 70 wt% or more olefins, and alternatively, 80 wt% or more olefins, based upon the total weight of the feed.
  • any of the above-described feeds may further contain at least one of diolefins and/or cyclic olefins.
  • Typical cyclic compounds are cyclopentene, methylcyclohexene, cyclohexene and cycloheptene.
  • the feed should be totally free, or at least substantially free, of aromatic hydrocarbon compounds that consist solely of hydrogen and carbon atoms.
  • substantially free means that the olefin feed contains 25 wt% or less, preferably 15 wt% or less, more preferably 10 wt% or less, such as 5 wt% or less, and most preferably 1 wt% or less aromatic hydrocarbon, based upon the total weight of the olefin feed.
  • Suitable olefin feeds include untreated refinery streams such as Fluidized Catalytic Cracking (FCC) streams, steam cracker streams, coker streams, pyrolysis gasoline streams or reformates.
  • FCC Fluidized Catalytic Cracking
  • C3 olefin-containing feeds include untreated C3 rich refinery streams such as "dilute” or “refinery grade” propylene from a Fluidized Catalytic Cracker (FCC), C3 rich stream from a steam cracker, from the production of "chemical grade” or “polymer grade” propylene, from refinery gas recovery units, from Propane Dehydrogenation Units, from Gas to Olefin (GTO) Units, or from Fisher-Tropsch Units, and C3 rich return streams from polypropylene producing units.
  • FCC Fluidized Catalytic Cracker
  • GTO Gas to Olefin
  • Fisher-Tropsch Units Fisher-Tropsch Units
  • These C3 streams may contain for example from 50 to 60 wt% of propylene, or 65 wt% or more, or 70 wt% or above such as 72 wt % or 75 wt % or even up to 79 wt %.
  • C4 olefin containing feeds examples include refinery feeds often referred to as Raffmate-1 (RAF-1), Raffmate-2 (RAF-2) or Raffmate-3 (RAF-3).
  • Raffmate-1, Raffmate-2 and Raffmate-3 may be regarded as streams obtainable at various stages in the processing of crude C4 streams obtained from petroleum refining processes. These streams are well known by the person skilled in the art.
  • C5 olefin feeds include FCC Light Naphtha streams, steam cracker C5 rich streams that have been treated for diene removal, C5 olefin containing streams from Gas to Olefin (GTO) Units, or Fisher-Tropsch Units.
  • Light Naphtha is understood to mean a stream having a specific gravity in the range 0.65 to 0.73, An ASTM-D86 boiling point range between 35 and 125 °C and that contains a range of olefin, paraffin, diolefms and cyclic hydrocarbon compounds with carbons numbers typically in the range C5 to C8.
  • LLCN Light Light Catalytic Naphtha
  • Such stream is characterized by a boiling point range of, for example, from 25 to 70 °C at atmospheric pressure and a specific gravity between 0.63 and 0.68 and contains at least 60 wt% C5 hydrocarbons.
  • the hydrocarbon feed is characterized by comprising a certain level of nitrogen-containing compounds and, optionally, certain levels of other compounds such as oxygen-containing compounds, sulphur-containing compounds, water, diolefins, cyclic olefins and mixtures thereof.
  • the levels (concentrations) of both the nitrogen-containing compounds and said other compounds are usually in a range referred to as impurities or at least as minor components of the stream.
  • the concentrations of these types of compounds will usually be in the range of from 0.1 to several hundred weight ppm (wt ppm), typically in a range of from 10 to 500 wt ppm, relative to the total weight of the stream.
  • wt ppm weight ppm
  • non-heteroatom- containing compounds such as dienes
  • the concentrations of these types of compounds will typically be in the range of from 0.01 to 5 or 10 weight % (wt%) relative to the total weight of the feed.
  • the process of this invention is capable of reducing the content of nitrogen-containing compounds in the hydrocarbon feed from an initial range of from 10 to 500 wt ppm to the range of from 20 to 500 wt ppb relative to the weight of the feed.
  • any of the above-described feeds contains nitrogen-containing compounds and other impurities acting as catalyst contaminants which must be removed to an acceptable level before the hydrocarbon feed undergoes a catalyzed reaction.
  • the nitrogen-containing compounds comprise nitriles, pyrroles or mixtures thereof, typically nitriles.
  • pyrroles are chemical compounds of formula C4H5N optionally substituted by alkyl radical(s) containing from 1 to 3 carbon atoms.
  • nitrile is any organic compound that has a nitrile group (or -C ⁇ N functional group).
  • acetonitrile (ACN) is the chemical compound with formula CH3CN. This colorless liquid is the simplest organic nitrile.
  • nitrile As used herein, "propanenitrile”, “propionitrile”, or “ethyl cyanide” is a nitrile with the molecular formula C2H5CN and the terms may be used interchangeably. It is also a clear liquid.
  • the nitriles removed are a C2 to C5 nitrile.
  • the nitrile to be removed is propionitrile and butyl nitrile, C3H7CN.
  • a hydrocarbon feed (1) is introduced into an extraction separation unit (2) where it is contacted with an extracting solvent (3) to obtain as overhead stream a hydrocarbon phase (4) of reduced nitrogen-containing compounds content and at the bottoms a solvent phase (5) containing dissolved nitrogen-containing compounds.
  • the solvent comprises, consist essentially of propylene carbonate ("PC").
  • the content of propylene carbonate in the solvent is of at least 95 wt%, preferably at least 98 wt%. Content of above 99 % are provide good results.
  • the solvent consists of propylene carbonate comprising traces of water.
  • the extraction is preferably carried out in an extraction column, more preferably a counter current column.
  • the temperature and pressure of the extraction column are not critical provided that they ensure that both the hydrocarbon feed and the solvent remain in the liquid phase.
  • the temperature is usually between 0 and 90 °C, preferably between 10 and 70 °C.
  • the pressure may be between 0 and 10 bara, more preferably between 1 and 5 bara.
  • the operating parameters are selected to produce a hydrocarbon phase containing preferably between 1000 and 15,000 wt ppm of carbonates, more preferably between 3000 and 10,000 wt ppm of carbonates.
  • the solvent to hydrocarbon feed weight ratio typically ranges from between 0.05 and 2; preferably this ratio is between 0.1 and 1, more preferably about 0.3.
  • the level of nitrogen-containing compounds in the hydrocarbon phase having a reduced nitrogen-containing compound content is below 1 ppm, preferably below 0.6 ppm, more preferably below 0.3 ppm by weight.
  • the hydrocarbon phase (4) having a reduced nitrogen- containing compound content is transferred to a distillation column (6) in order to separate a heavy phase (7) containing the solvent and optionally heavy hydrocarbon compounds present in the feed, including any C6 olefins, if present in the feed, from a light fraction (8) containing the at least one olefin selected from C3, C4, and C5 olefins and mixtures thereof.
  • Heavy hydrocarbon compounds preferably refer to C6 olefins, C6+ olefins and hydrocarbon compounds with boiling point equal or above C6 olefin boiling point. Polycarbonate and cyclopentene are considered as heavy hydrocarbons.
  • the distillation is usually carried out through the use of columns with trays, packed columns including structured packing, random packing or a combination of both.
  • the final boiling point of the light fraction (8) is preferably below 60°C, more preferably below 55°C.
  • the light fraction (8) may be considered as a clean feed and may be used in any downstream process. Additional treatments may be required by said downstream process
  • reboiler technology is preferably used at the bottom of the distillation column (6). Also at the top of the extraction column the level instrument tapping is preferably oriented to allow free draining of any PC that might be carried into the pipe work.
  • FIG.2 An example of a preferred distillation column layout is represented in Fig.2. As shown, the hydrocarbon phase (4) is preheated before being introduced in a middle zone of the distillation column (6). The top of the distillation column is equipped with a condenser (14). A separator (15), typically a settling tank, at the bottom of the column, separates the heavier phase from the lighter phase that is sent to a reboiler (16) optionally after purging. The separator (15) may be replaced by a pump.
  • a separator typically a settling tank
  • the solvent phase (7) removed from the distillation column (6) is subjected to regeneration to remove undesired materials described hereabove and comprising solvent degradation products and/or heavy hydrocarbon compounds from the feed before being returned back to the extraction / separation unit with the hydrocarbon feed.
  • Methods to remove undesired materials from the solvent phase (7) include but are not limited to, vacuum and steam distillation, back extraction, adsorption (e.g. using a solid sorbent) and anion-cation exchange resin columns.
  • regeneration is preferably performed in a stripping unit (9), typically a stripping column, by stripping the solvent phase with a stream of stripping gas (12) whereby the undesired materials are taken out overhead and regenerated solvent (10) is taken as bottoms.
  • the solvent phase (5) separated at the bottoms of the extraction unit is routed to the stripping column as well as the solvent phase (7) but preferably via a different feed point.
  • the stripping gas (12) may be selected from inert gas, typically nitrogen from light hydrocarbons having from 1 to 6 carbon atoms, preferably from 1 to 5 carbon atoms or mixture thereof.
  • the stripping gas is typically free of nitrogen-containing compounds, i.e. contains preferably less than 0.3, more preferably less than 0.1 wt% of nitrogen-containing compounds.
  • the stripping gas comprises at least 98, preferably at least 99, and more preferably at least 99.5 wt% of one or more hydrocarbons.
  • the stripping gas is preferably a fraction of the light fraction (8) produced at step (c).
  • the contacting of the solvent phase with the stripping gas is preferably carried out at a pressure of from 1 to 5 bars.
  • the weight ratio of the stripping gas to the crude product is from 50: 1 to 125: 1 determined at the temperature and pressure used in the stripping unit.
  • the stripper column includes inert solid surfaces or trays to facilitate contact between the liquid and gas phases.
  • the stripping column is equipped with an overhead reflux resulting in a column configuration comprising a stripping portion in the bottom and a distillation portion at the top.
  • Such configuration also further allows control of the solvent lost to the stripping tower meaning that the amount in the overheads could be increased to allow for solvent purging if required by the overall process. Also such configuration allows for better separation of the heavy hydrocarbons.
  • the reflux rate is usually fixed relative to the net hydrocarbon feed to the stripping tower, the net hydrocarbon feed being the sum of the stripping gas with the extractor and distillation bottoms streams.
  • the stream (13) recovered at the top of the stripper column is suitable for Mogas blending.
  • the regenerated solvent (10) is transferred back to the extraction tower, preferably at the top of the extraction tower (2), thereby closing the solvent recycle loop.
  • control device (17) adapted to the analytical method step described below.
  • the content of one or more alkyl, alkenyl, or aryl carbonate is measured by gas chromatography using a 6890 gas chromatograph from Agilent using a HP-FFAP polyethylene glycol TPA column using 3.3 ml*min of carrier gas.
  • the operating temperature is between room temperature and 220°C. Flame Ionization Detector (FID) is used as detector.
  • FID Flame Ionization Detector
  • the TAN of the recycled solvent is determined according to ISO 1843/2
  • the distribution coefficient of the nitrogen-containing compounds between the solvent and the hydrocarbon feed is obtained by contacting at room temperature equal volumes of the hydrocarbon feed and solvent and manual shaking the obtained mixture in a separation funnel at ambient temperature for 1 minute. After settling, the two phases are separated and the obtained hydrocarbon phase is further extracted with equal amount of solvent under the same shaking conditions. This manipulation is repeated at least 3 times under the same conditions and the content of nitrogen-containing compound in the different phases are measured by gas chromatography using a Free Fatty Acid Phase (FFAP ) column equipped with a FID detector or with a nitrogen chemo luminescence detector.
  • the distribution coefficient is the slope of the straight line obtained by plotting the nitrile concentration in the hydrocarbon phase versus the one in the solvent.
  • the interfacial tension is measured via the Ring Tear Off (RTO) method BS-EN 14370:2004
  • the measurement of surface tension of the solvent is performed by the Du Nouy Ring method BS-EN 14370:2004
  • the settling time is measured on different aged solvent recycling phase.
  • the settling time of the recycled solvent in the hydrocarbon feed should be kept below 200 % of the settling time of the raw propylene carbonate, preferably below 150 % under the same settling conditions.
  • the settling time is preferably measured by mixing 10 ml of the polycarbonate stream with 10 ml of the hydrocarbon fee during 15 sec at 20°C.
  • the settling time of recycled solvent measured under these conditions is preferably kept below 20 s.
  • the present invention relates to a process for converting a hydrocarbon feed comprising at least one olefin selected from the C3, C4, C5 and optionally C6 olefins and mixtures thereof contaminated with at least one nitrogen-containing compound into a hydrocarbon product, said process comprising the steps of:
  • the process for converting the hydrocarbon feed into a hydrocarbon product concerned by this invention may be an isomerization, an alkylation, a hydrogenation, an aromatization or an oligomerization process; preferably such process is an isomerization or an oligomerization process.
  • oligomerization process refers to any process by which light olefins are linked together to form the oligomer(s) as defined herein.
  • oligomerization conditions refers to any and all those variations of equipment, conditions (e.g. temperatures, pressures, weight hourly space velocities etc.), materials, and reactor schemes that are suitable to conduct the oligomerization process to produce the oligomer(s) as known and applied in the art.
  • the hydrocarbon feed comprises an olefin, wherein the olefin is preferably selected from the group consisting of C3, C4, C5 and C6 olefins and mixtures thereof, in particular C3, C4 and C5 olefins.
  • the hydrocarbon product comprises an oligomerization product and the catalyst is an oligomerization catalyst comprising a material selected from the group consisting of zeolites, phosphoric acids, supported metal oxides and combinations thereof.
  • the oligomerization catalyst comprises a zeolite, in particular a zeolite selected from the group consisting of ZSM-5, ZSM-1 1 , ZSM-12, ZSM-18, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-50, ZSM-57, ITQ-39 and mixtures thereof.
  • Exemplary methods and materials utilized in the oligomerization process are provided in WO2012/033562, US 4,973,790 and US-A-2012/0022224.
  • the invention is particularly, but not exclusively, concerned with processes suitable for the production of C5 to C20 olefins boiling in the range of 30° to 310°C, preferably 30° to 300°C, more preferably 30° to 250°C, from propylene and/or butene and/or pentene containing feedstocks or their mixtures, though ethylene may be present as well.
  • the oligomer product may be fractionated in a series of discrete products.
  • the invention is concerned with the production of the olefins shown in the following table. Typical values are indicate in table below.
  • the oligomer products are useful in many applications and are the starting material for further processes.
  • the oligomer product may be polymerized to produce polyolefms that have application in the plastic industry and synthetic basestocks for lubricants.
  • the oligomer product may be used in alkylation reactions for the product of surfactants.
  • the oligomer products may be reacted with sulphur containing compounds to produce mercaptans.
  • the oligomer product may undergo hydroformylation and subsequently hydrogenation to produce alcohols.
  • the alcohols may be used in industry such as, for example, solvents, or be incorporated into the production of detergents/surfactants.
  • the alcohols may further be used in many other areas of industry such as, for example, undergoing esterification to produce esters that have application as plasticizers.
  • Oligomer products may be hydrogenated to produce a predominately paraffin product such as ISOPARTM.
  • Products could be streams suitable for blending into fuels dispositions including Mogas, distillate, diesel, jet fuel etc. from processes like EMOGAS (ExxonMobil Olefins to Gasoline) , MODG (Mobil Olefins to Diesel and Gasoline).
  • EMOGAS ExxonMobil Olefins to Gasoline
  • MODG Mobil Olefins to Diesel and Gasoline
  • a LLCN hydrocarbon feed is first sent to an extraction tower, where it is contacted with PC as extraction solvent. Any nitriles present in the hydrocarbon feed are absorbed into the PC phase.
  • the overheads of the extractor tower are routed to a distillation column where any PC that is present in the purified hydrocarbon stream is separated into the bottoms along with any undesired hydrocarbons.
  • the overhead stream is the desired purified hydrocarbon stream.
  • the bottoms of the distillation are routed to a stripping tower.
  • the bottom of the extractor is routed to the same stripping tower as the distillation bottoms, possibly via a different feed point. In the stripping the stripping medium is heated pentane coming from higher olefin process which uses the clean LLCN.
  • Any liquid in the overheads of the stripper is condensed and routed to the refinery mogas pool.
  • the process according to the present invention can be operated at low corrosion rate typically less or equal than 2.6 mil/yr allowing low cost carbon steel to be used for the unit construction.
  • the data in table 1 represents the model predicted compositions of the various streams in the process using PRO II simulation model based on measured physical properties of the stream components. Key points to note are the very low levels of nitrile in the clean C5 stream and the high levels of nitrile in the extractor bottoms and stripper overheads.
  • Table 1 Flow rate, temperature and compositions generated using PRO 2 for the pilot plant case.
  • the hydrocarbon feed in this case is LLCN an the stripping gas is pentane.
  • PCN represents propionitrile and Py is pyrrole.
  • the amount of propionitrile in the tower bottoms indicates the effectiveness of the tower in stripping contaminants whereas the PC in the overheads demonstrates the effectiveness of the reflux in limiting PC loss.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract

L'invention concerne un procédé d'élimination de composés azotés à partir d'une charge d'hydrocarbures comprenant au moins une oléfine choisie parmi les oléfines C3, C4, C5 et éventuellement C6 et des mélanges de celles-ci, comprenant l'extraction de solvant et comprenant la surveillance de la dégradation du solvant.
EP18729710.6A 2017-07-13 2018-06-15 Procédé d'élimination de composés azotés à partir d'une charge d'hydrocarbures Withdrawn EP3652273A1 (fr)

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PCT/EP2018/065955 WO2019011582A1 (fr) 2017-07-13 2018-06-15 Procédé d'élimination de composés azotés à partir d'une charge d'hydrocarbures

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US11466149B2 (en) 2018-07-23 2022-10-11 Exxonmobil Chemical Patents Inc. Preparation of bimodal rubber, thermoplastic vulcanizates, and articles made therefrom
BE1027176B1 (nl) 2019-09-19 2020-10-28 Agrofrost Nv Een apparaat en methode voor het bestrijden van gewassen met een verwarmde luchtstroom

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US4973790A (en) 1989-11-16 1990-11-27 Mobil Oil Corporation Process for upgrading light olefinic streams
EP0671455A3 (fr) * 1994-03-11 1996-01-17 Standard Oil Co Ohio Procédé pour l'élimination sélective de composés azotés à partir de mélanges d'hydrocarbures.
US6358402B1 (en) * 1999-12-28 2002-03-19 Exxonmobil Research And Engineering Company Extractive distillation process for the reduction of sulfur species in hydrocarbons streams
US8343336B2 (en) 2007-10-30 2013-01-01 Saudi Arabian Oil Company Desulfurization of whole crude oil by solvent extraction and hydrotreating
US20120022224A1 (en) 2010-07-22 2012-01-26 Geraldine Tosin Particles Including Zeolite Catalysts And Their Use In Oligomerization Processes
WO2012033562A1 (fr) 2010-09-07 2012-03-15 Exxonmobil Chemical Patents Inc. Extrudats comprenant des catalyseurs zéolites et leur utilisation dans des procédés d'oligomérisation
CN103237872B (zh) 2010-12-07 2015-12-09 埃克森美孚化学专利公司 利用溶剂萃取的方法

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