EP3959187A1 - Isomérisation et activation catalytique de mélanges d'hydrocarbures enrichis en pentane - Google Patents

Isomérisation et activation catalytique de mélanges d'hydrocarbures enrichis en pentane

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Publication number
EP3959187A1
EP3959187A1 EP20795065.0A EP20795065A EP3959187A1 EP 3959187 A1 EP3959187 A1 EP 3959187A1 EP 20795065 A EP20795065 A EP 20795065A EP 3959187 A1 EP3959187 A1 EP 3959187A1
Authority
EP
European Patent Office
Prior art keywords
activation
fraction
feed stream
effluent
isomerization
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.)
Pending
Application number
EP20795065.0A
Other languages
German (de)
English (en)
Other versions
EP3959187A4 (fr
Inventor
Anthony O. BALDRIDGE
Neal D. Mcdaniel
James A. SUTTIL
Jianhua Yao
Edward C. WEINTROB
Matthew J. WULFERS
Bruce B. Randolph
Maziar Sardashti
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.)
Phillips 66 Co
Original Assignee
Phillips 66 Co
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
Priority claimed from US16/855,367 external-priority patent/US10988696B2/en
Priority claimed from US16/855,312 external-priority patent/US10870808B2/en
Priority claimed from US16/855,350 external-priority patent/US10975314B2/en
Priority claimed from US16/855,333 external-priority patent/US10865168B2/en
Application filed by Phillips 66 Co filed Critical Phillips 66 Co
Publication of EP3959187A1 publication Critical patent/EP3959187A1/fr
Publication of EP3959187A4 publication Critical patent/EP3959187A4/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
    • C07C5/2708—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • 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
    • C10G7/00—Distillation of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11

Definitions

  • the present disclosure generally relates to processes and systems that converts at least a portion of the n-pentane in a light hydrocarbon feed stream to isopentane, followed by an activation step and subsequent upgrading to larger hydrocarbons in either an alkylation reactor or oligomerization reactor.
  • the processes and systems produce hydrocarbons suitable for use as a blend component of a liquid transportation fuel.
  • inventive processes disclosed herein provide an improved upgrading route for pentane-rich fuel blend-stocks and other pentane-rich streams that do not meet government specifications for a transportation fuel.
  • inventive processes and systems provide enhanced yields of upgraded products that may be suitable for use as transportation fuels or other value- added chemical products.
  • Some embodiments comprise a method for converting a hydrocarbon feed stream comprising pentanes to produce a liquid transportation fuel, the method comprising: a) providing a hydrocarbon feed stream comprising at least 50 wt.% pentanes, optionally at least 70 wt.% pentanes, including both n-pentane and isopentane; b) at least partially separating the hydrocarbon feed stream in a separator to produce: a first fraction that comprises at least 80% of the isopentane present in the hydrocarbon feed stream (on a molar basis), and that further comprises at least 90% of hydrocarbons present in the hydrocarbon feed stream (on a molar basis) that are characterized by a vapor pressure equal to or greater than the vapor pressure of isopentane, and a second fraction that comprises at least 80% of the n-pentane content of the hydrocarbon feed stream (on a molar basis) and at least 90% of hydrocarbons from the hydrocarbon feed stream that contain six
  • Some embodiments comprise a method for converting a hydrocarbon feed stream comprising pentanes to produce a liquid transportation fuel, the method comprising: a) providing a hydrocarbon feed stream comprising at least 50 wt.% pentanes, including both n-pentane and isopentane; b) at least partially separating the hydrocarbon feed stream in a separator to produce: a first fraction that comprises at least 80% of the isopentane present in the hydrocarbon feed stream, and that further comprises at least 90% of hydrocarbons present in the hydrocarbon feed stream (on a molar basis) that are characterized by a vapor pressure equal to or greater than the vapor pressure of isopentane, and a second fraction that comprises at least 80% of the n-pentane content of the hydrocarbon feed stream (on a molar basis) and at least 90% of hydrocarbons content from the hydrocarbon feed stream that contains six or more carbons (on a molar basis); c) contacting the first fraction with
  • Some embodiments further comprise splitting the upgrading reactor effluent to produce a heavy hydrocarbons fraction comprising at least 80 wt.% hydrocarbons that contain at least five carbon atoms, and a light hydrocarbons fraction comprising hydrogen and further comprising at least 80 wt.% hydrocarbons that contain four or fewer carbon atoms, wherein the light hydrocarbons fraction is separated to produce a hydrogen stream and a light paraffins stream comprising paraffins containing four or less carbon atoms.
  • Some embodiments further comprise separating the liquid hydrocarbons fraction into an aromatics fraction and an unreacted C5/C6 hydrocarbons fraction, wherein the aromatics fraction comprises monocyclic aromatics that meet specifications for a blend component of gasoline, wherein the unreacted C5/C6 hydrocarbons fraction comprises alkanes and olefins containing from five to six carbons, and optionally, is mixed with the hydrocarbon feed stream of a).
  • the activation catalyst facilitates carbon-hydrogen bond activation that leads to at least one of olefmation, dimerization, oligomerization and aromatization of the first fraction, wherein the activation catalyst optionally comprises one or more zeolites characterized by a Si/Al ratio ranging from 12 to 80, wherein the activation catalyst optionally comprises ZSM-5 zeolite.
  • the activation reactor is maintained at a temperature in the range from 500°C to 625°C, optionally in the range from 550 °C to 600 °C, wherein the activation reactor is maintained at a pressure in the range from 15 psig to 100 psig, optionally in the range from 20 psig to 60 psig.
  • Some embodiments further comprise adding a diluent to the first fraction prior to the contacting of part c), wherein the diluent inhibits catalytic activation of the first fraction by the activation catalyst at the conditions of temperature and pressure that are maintained in the activation reactor.
  • the diluent is characterized as chemically non-reactive with the activation catalyst at the conditions of temperature and pressure that are maintained in the activation reactor.
  • the diluent is added in an amount that alters the specificity of the activation catalyst to increase the production of olefins, decrease the production of aromatics, or combinations thereof, thereby increasing the ratio of olefins to aromatics in the activation effluent.
  • the diluent is added in an amount that is effective to produce an activation effluent that is characterized by an olefins to aromatics ratio in the range from 0.5 to 2.0, optionally in the range from 0.5 to 2.0.
  • the diluent is selected from at least one of methane, ethane, propane and butane isomers.
  • at least a portion of the light paraffins stream serves as the diluent.
  • Certain embodiments comprise a system for converting a feedstock comprising pentanes to produce a liquid transportation fuel, the system comprising: a) a first separator operable to at least partially separate a plurality of constituents in a hydrocarbon feed stream according to characteristic vapor pressure of each constituent, wherein the hydrocarbon feed stream comprises at least 50 wt.% pentanes, including both n-pentane and isopentane, wherein the separator is operable to produce: a first fraction comprising at least 80% of the isopentane present in the hydrocarbon feed stream, and further comprising at least 90% of hydrocarbons present in the hydrocarbon feed stream that are characterized by a vapor pressure equal to or greater than the vapor pressure of isopentane, and a second fraction that comprises at least 80% of the n-pentane present in the hydrocarbon feed stream and at least 90% of any hydrocarbons containing six or more carbon atoms that were present in the hydrocarbon feed stream; b) an isomer
  • Certain embodiments comprise a system for converting a hydrocarbon feedstock comprising pentanes to produce a liquid transportation fuel, the system comprising: a) a first separator operable to at least partially separate a plurality of constituents in a hydrocarbon feed stream according to characteristic vapor pressure of each constituent, wherein the hydrocarbon feed stream comprises at least 50 wt.% pentanes, including both n-pentane and isopentane, wherein the separator is operable to produce: a first fraction comprising at least 80% of the isopentane present in the hydrocarbon feed stream, and further comprising at least 90% of hydrocarbons present in the hydrocarbon feed stream that are characterized by a vapor pressure equal to or greater than the vapor pressure of isopentane, and a second fraction that comprises at least 80% of the n-pentane present in the hydrocarbon feed stream and at least 90% of any hydrocarbons containing six or more carbon atoms that were present in the hydrocarbon feed stream; b) an is
  • Some embodiments of the system further comprise a second separator operable to receive and split the oligomerization effluent, or optionally, the alkylating effluent, into a heavy hydrocarbons fraction comprising at least 50 wt.% hydrocarbons containing at least five carbon atoms, including olefins, monocyclic aromatics and unreacted molecules from the hydrocarbon feed stream and a light hydrocarbons fraction comprising hydrogen and at least 80 wt.% hydrocarbons containing from one to four carbon atoms.
  • a second separator operable to receive and split the oligomerization effluent, or optionally, the alkylating effluent, into a heavy hydrocarbons fraction comprising at least 50 wt.% hydrocarbons containing at least five carbon atoms, including olefins, monocyclic aromatics and unreacted molecules from the hydrocarbon feed stream and a light hydrocarbons fraction comprising hydrogen and at least 80 wt.% hydrocarbons containing from one to
  • Some embodiments of the system further comprise a third separator operable to receive and separate the heavy hydrocarbons fraction to produce a liquid hydrocarbon product comprising aromatic hydrocarbons containing at least six carbon atoms, and an unreacted C5/C6 fraction comprising alkanes and olefins containing from five to six carbon atoms, wherein the third separator is optionally a naphtha stabilizer.
  • Some embodiments of the system further comprise a first conduit operably connected to convey the unreacted C5/C6 fraction from the compressor-condenser and further operable to combine the unreacted C5/C6 fraction with the hydrocarbon feed stream.
  • Some embodiments of the system further comprise a fourth separator operable to receive and separate the light hydrocarbons fraction to produce a hydrogen stream and a light paraffins stream comprising paraffins containing from one to four carbon atoms, wherein the fourth separator comprises an outlet for the hydrogen stream, wherein the system additionally comprises a second conduit operably connected to convey the light paraffins stream from the fourth separator and combine the light paraffins stream with the first fraction at a point that is upstream from the activation reaction zone.
  • Some embodiments of the system further comprise a storage vessel operable to receive the second fraction from the first separator and to divert at least a portion of the second fraction to produce a blending fraction having the characteristics of a liquid hydrocarbon transportation fuel blend stock wherein the storage vessel is further operable to convey the remainder of the second fracation to the isomerization reactor.
  • Figure 1 is a diagram depicting a first embodiment of the inventive processes and systems.
  • Figure 2 is a diagram depicting a second embodiment of the inventive processes and systems.
  • Figure 3 is a diagram depicting a third embodiment of the inventive processes and systems.
  • Figure 4 is a bar graph depicting product selectivity resulting from catalytic activation of either n-pentane or iso-pentane at two different temperatures.
  • Figure 5 is a bar graph showing the effect of isomerization of the feed stream on the total conversion and product yield for a first feed stream comprising a 1 : 1 ratio of n-C5 to i-C5, and a second feed stream comprising a 7:3 ratio of n-C5 to i-C5.
  • Figure 6 is a bar graph showing the effect of isomerization of the feed stream on the total conversion and product selectivity for a first feed stream comprising a 1 : 1 ratio of n-C5 to i-C5, and a second feed stream comprising a 7:3 ratio of n-C5 to i-C5.
  • the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings. The drawings may not be to scale. It should be understood that the drawings are not intended to limit the scope of the invention to the particular embodiment illustrated.
  • the present disclosure provides processes and systems for converting a mixture of light hydrocarbons to liquid transportation fuels. More specifically, it pertains to the conversion of any hydrocarbon mixture that predominantly comprises pentanes to generate upgraded products that may be sold as a value-added chemical or utilized as a blend component of a liquid transportation fuel.
  • the inventive processes and systems described herein utilize a hydrocarbon feed stream that comprises both isopentane (i-C5) and n-pentane (n-C5).
  • the process performs an initial separation of the hydrocarbon feed stream to produce a first fraction that predominantly comprises i-C5 and a second fraction that predominantly comprises n-C5 and C6+ hydrocarbons.
  • the first fraction is then catalytically-activated in an activation reactor to convert at least a portion of the i-C5 to olefins and aromatics.
  • a portion of the second fraction is either diverted to blended into liquid transportation fuels or isomerized in an isomerization reactor to convert at least a portion of the n-C5 in the second fraction to i-C5, and a portion of any n-hexane (n-C6) in the second fraction to iso-hexane isomers.
  • the resulting isomerization effluent is then recycled to the initial separation step to allow separation of the additional i-C5 produced in the isomerization reactor, which is then directed to the activation reactor along with the first fraction.
  • the inventive processes and systems allow an increased percentage of the hydrocarbon feed stock to be catalytically activated to produce predominantly olefins and aromatics, while minimizing the percentage of the feed stock that is converted to less desirable C1-C4 paraffins.
  • the resulting isomerization effluent is then catalytically activated under conditions of temperature and pressure (typically measured at the inlet of the activation reactor) that maximize the catalytic conversion of the isomerization effluent to olefins and aromatics, while minimizing the undesirable production of C1-C4 light hydrocarbons, often referred to as fuel gas.
  • Some embodiments of the inventive processes and systems further upgrade the resulting activation effluent by contacting the activation effluent with an oligomerization and/or alkylation catalyst at a temperature and pressure that facilitates conversion of the activation effluent to value-added chemicals and/or products suitable for use as a liquid transportation fuel blend component.
  • This additional upgrading may be preceded by compressing (and optionally, partially condensing) the activation effluent in order to facilitate the subsequent oligomerization and/or alkylation step.
  • the hydrocarbon feed stream predominantly comprises a mixture of pentane isomers (C5).
  • the hydrocarbon feed stream may additionally comprise C2-C4 hydrocarbons, C6-C7 hydrocarbons, or both.
  • the hydrocarbon feed stream generally comprises both i-C5 and n-C5 pentane isomers.
  • the hydrocarbon feed stream comprises at least 10 wt.% of a mixture of pentane isomers; optionally, at least 20 wt. %, optionally, at least 30 wt.%, optionally, at least 40 wt.%, optionally at least 50 wt.%, optionally, at least 60 wt.%, or optionally, at least 70 wt.%.
  • the hydrocarbon feed stream may be obtained by processing a stream of natural gas liquids to remove lighter components (i.e., C1-C4) by way of conventional natural gas processing technologies that are well-characterized, such as de-methanizer, de-ethanizer, de propanizer and de-butanizer fractionation columns, although such separation is not essential.
  • lighter components i.e., C1-C4
  • a typical result of such processes is commonly characterized as natural gasoline, comprising about 72 wt.% pentanes, with the remainder predominantly comprises hexane.
  • the hydrocarbon feed stream comprises less than 30 wt.%, optionally, less than 20 wt.%, optionally, less than 10 wt.% of hydrocarbons containing four or fewer carbon atoms.
  • a first embodiment of the inventive processes and systems is illustrated by the process flow-diagram of Figure 1.
  • a hydrocarbon feed stream 101 comprising both n-pentane (nC5) and isopentane (iC5) is converted in a system 10.
  • the hydrocarbon feed stream 101 is received by a first separator 110 that operates to separate the feed stream 101 into a first fraction 119 that comprises an increased wt. % of isopentane (i-C5) relative to the feed stream 101, and a second fraction 117 that comprises an increased wt. % of n-pentane relative to the feed stream 101.
  • the second fraction further comprises a large majority of any C6 and larger (C6+) hydrocarbons originally present in the hydrocarbon feed stream 101.
  • the first separator 110 may operate using conventional separation technology 115 to separate the i-C5 isomer from the remaining compounds present within the C5-rich hydrocarbon feed stream.
  • any other separation technology may be used to assist in separating i-C5 from n-C5 to produce the first fraction and the second fraction.
  • the first fraction 119 is conveyed to an activation reactor 133 containing an activation catalyst 135.
  • the activation reactor 133 is operable to maintain a temperature and pressure that is suitable to facilitate conversion of the first fraction 119 to a first effluent 136.
  • the temperature within the activation reactor (typically measured at, or proximal to, the inlet of the activation reactor) is maintained in the range from 500°C to 650°C; optionally, within the range from 525°C to 625°C; optionally, within the range from 525°C to 600°C; optionally, within the range from 550°C to 600°C; optionally, within the range from 550°C to 575°C; optionally, within the range from 575°C to 600°C.
  • the pressure maintained within the activation reactor generally ranges from 15 psia (103 kpa) to 165 psia (1138 kpa); Optionally, in the range from 15 psig to 100 psig.; Optionally, in the range from 15 psig to 75 psig.; Optionally, in the range from 20 psig to 60 psig.; Optionally, in the range from 20 psig to 50 psig.
  • the activation catalyst may comprise a single catalyst, or a mixture of different catalysts that contact the alkanes present in a given feed stream and facilitates at least one of dehydrogenation, cracking, and aromatization of the alkanes, thereby producing upgraded products including olefins and aromatics.
  • catalysts include supported or unsupported solid acids, metals, metal chalcogenides, or metal pnictogenides, including (but not limited to) structured and amorphous silica-aluminas, structured and amorphous solid phosphoric acids, clays, other metal oxides, metal sulfates, or metal phosphates, and graphite-supported materials.
  • ZSM-5 zeolite catalysts are utilized that are characterized by Si/Al ratios ranging from 12-80, optionally ranging from 35 to 50.
  • one or more elements may optionally be impregnated on the zeolite catalyst, including one or more of Ga, Pt, Ni, Mn, Mg, Fe, Cr, P, Cu, La, Sr and F, but are not required for operability of the invention.
  • dehydrogenation catalysts are not utilized for paraffin activation in the instant inventive process.
  • a sufficient concentration of intermediate olefins can be generated through a combination of thermal dehydrogenation and catalytic cracking such that typical dehydrogenation metals can be avoided without significantly decreasing product yield.
  • Known dehydrogenation catalysts are prone to fouling by sulfur and nitrogen contaminants that are often present in hydrocarbon feed streams derived from petroleum, so the ability to operate in the absence of sensitive catalytic materials is highly advantageous.
  • the inventive process generally takes advantage of the large reactivity difference to catalytic activation of n-C5 relative to i-C5. For example, when contacted with a solid acid catalyst at a temperature in excess of 550 °C, the measured activation rate of i-C5 is up to four fold that of n-C5, even when both isomers are simultaneously present in the same reactor.
  • an at least partial separation of the mixed pentanes feed stream to form a first fraction that largely comprises i-C5 and a second fraction that retains a large majority of the n-C5 in the feed stream which allows the iC5 to be selectively activated at conditions comprising a lower temperature (e.g., 550°C versus 600°C) and a pressure that decreases selectivity to C1-C4 light paraffins during catalytic activation, while maximizing the selectivity of the activation toward the production of value-added products (such as olefins and aromatics).
  • Table 1 (below) illustrates the difference in the activation reactivity of i-C5 versus n- C5 over a microporous silica-alumina catalyst. Feed streams comprising either 100 wt.% i-C5 or 100 wt.% n-C5 were each catalytically activated in separate experiments utilizing temperatures of either 600°C or 550°C. The conversion and product distribution for i-C5 are shown in Table 1, columns 2 and 3, while similar results for the activation of n-C5 are shown in Table 1, columns 4 and 5.
  • the ability to separate the i-C5 isomer from n-C5 isomer (and any C6+ hydrocarbons), and separately activate the i-C5 enriched mixture at relatively reduced temperature results in approximately equivalent total conversion of the hydrocarbon feed stream, while decreasing the formation of undesired C1-C4 light paraffins.
  • the second fraction 117 is directed to a storage vessel 120 that is operable to both receive the second fraction, and to optionally divert at least a portion of the second fraction to produce a blending fraction 125 that may be blended directly into a liquid hydrocarbon transportation fuel (e.g., gasoline).
  • a liquid hydrocarbon transportation fuel e.g., gasoline
  • the remainder of the second fraction is conveyed from the storage vessel 120 to a isomerization reactor 127 that contains an isomerization catalyst 130 and is operable to receive a flow of hydrogen gas 131, and further operable to maintain a temperature and pressure suitable to facilitate the conversion of the second fraction 117 to a isomerization effluent 132 comprising an increased wt.% of i-C5 and a decreased wt. % of n-C5 relative to the second fraction.
  • the second vessel is not required, and a portion of the second fraction is simply diverted via a valve (not depicted) to produce the blending fraction 125.
  • the quantity of the second fraction that is diverted (if any) is determined by the molecular composition of the second fraction 117 and the quantity of the second fraction that is to be fed to isomerization reactor 127.
  • the isomerization reactor contains an isomerization catalyst and is operable to maintain a temperature and a pressure that facilitates the isomerization of at least a portion of the nC5 in the second fraction to iC5 by the isomerization catalyst.
  • the isomerization reaction occurring in the isomerization reactor produces an isomerization effluent that is characterized by an increased ratio of iC5 to nC5 (relative to the corresponding ratio of the hydrocarbon feed stream).
  • the isomerization process is designed primarily for continuous catalytic isomerization of the n-C5 present in the second fraction.
  • the process is conducted in an isomerization reactor in the presence of an isomerization catalyst.
  • the isomerization catalyst may comprise more than one isomerization catalyst.
  • isomerization may be conducted in more than one isomerization reactor arranged in series configuration, with each reactor containing a different isomerization catalyst (or mixture of isomerization catalysts).
  • Each isomerization reactor maintains a partial pressure of hydrogen and operating conditions of temperature and pressure in the isomerization reaction zone that facilitate isomerization by the isomerization catalyst while minimizing hydrocracking.
  • the isomerization catalyst facilitates the conversion of n- pentane to the higher octane-number isopentane, while any C6 hydrocarbons present may be converted to higher octane 2-3 dimethyl butane (and similar molecules).
  • the isomerization reaction is equilibrium-limited. For this reason, any n-pentane that is not converted on its first pass through the isomerization reactor may optionally be recycled to the isomerization reactor, or converted in multiple isomerization reactors, arranged in series configuration, thereby further increasing the ratio of i-C5 to n-C5 in the product.
  • the relative efficiency of separation of pentane isomers by distillation is poor. Thus, recycling may be more effectively accomplished by a molecular sieve, which selectively adsorbs n-pentane due to its smaller pore diameter relative to isopentane.
  • the activity of the isomerization catalyst may be decreased in the presence of sulfur, thereby decreasing the isomerization rate and, consequently, the octane number of the final product.
  • the hydrocarbon feed stream is hydrotreated to remove sulfur prior to being conveyed to the isomerization reactor.
  • the isomerization catalyst may comprise any known isomerization catalyst.
  • three basic families of light naphtha isomerization catalysts are known. The first are termed super-acidic catalysts such as, for example, chlorinated alumina catalysts with platinum.
  • super-acidic catalysts such as, for example, chlorinated alumina catalysts with platinum.
  • super acidic isomerization catalysts are highly active and have significant activity at temperatures as low as 265°F (130°C) using a lower H2/HC ratio (less than 0.1 at the outlet of the reactor).
  • maintaining the high acidity of these catalysts requires the addition of a few ppm of chloriding agent to the feedstock. At the inlet of the isomerization reactor, this chloriding agent reacts with hydrogen to form HC1, which inhibits the loss of chloride from the catalyst.
  • the acidic sites on a super-acidic catalyst are irreversibly deactivated by water. These catalysts are also sensitive to sulfur and oxygenate contaminants, so the feed stream is generally hydrotreated and dried to remove residual water contamination.
  • chlorided-alumina catalysts include, but are not limited to, IS614A, AT-2, AT-2G, AT-10 and AT-20 (by Akzo Nobel) and ATIS-2L (by Axens). Due to their chlorinated nature, these are very sensitive to feed impurities, particularly water, elemental oxygen, sulfur, and nitrogen.
  • the reactor operating temperature generally ranges from 14 °C to 175°C, while the operating pressure is generally in the range from 200 psig to 600 psig, preferably in the range from 425 psig to 475 psig.
  • Zeolitic isomerization catalysts require a higher operating temperature and are effective at isomerization at temperatures ranging from 220°C to about 315°C, preferably at a temperature ranging from 230°C to 275°C.
  • Pressures utilized for isomerization with zeolitic isomerization catalysts typically range from 300 psig to 550 psig with a LHSV from 0.5 to 3.0 hr 1 .
  • Zeolitic catalysts react as bifunctional catalysts and require hydrogen at a Fh/HC ratio ranging from about 1.5 to about 3.
  • Zeolitic catalysts have advantages over chlorided-alumina catalysts due to zeolitic catalyst tolerance for typical catalyst poisons sulfur, oxygenates and water.
  • Zeolitic catalysts also do not require the injection of a chi ori ding agent in order to maintain catalyst activity.
  • a third type of conventional isomerization catalyst that may be useful in some embodiments comprises sulfated zirconia/metal oxide catalysts. These catalysts are active at relatively low temperatures (e.g., 100°C) with the advantage of providing enhanced isoparaffin yield. Their biggest drawback is their relative sensitivity to catalyst poisons, especially water. Certainly, other examples of isomerization catalysts that are suitable for use with the present processes and systems described herein are known by those having experience in the field, and thus, require no further disclosure here.
  • the isomerization effluent 132 is conveyed via conduit to be combined with the hydrocarbon feed stream 101 at a location that is upstream of the first separator 110. This allows the additional i-C5 that is produced in the isomerization reactor 127 to be redirected to the activation reactor 133 where it is catalytically activated by the activation catalyst 135.
  • the hydrocarbon feed stream includes C6 hydrocarbons
  • at least a portion of any n-C6 present in the second fraction is isomerized to i-C6 in the isomerization reactor and comprises a portion of the isomerization effluent.
  • This i-C6 is routed between the first separator and the isomerization reactor until it eventually leaves the system as a component of the blending fraction 125 that is diverted from the second fraction upstream from the isomerization reactor.
  • This serves as an additional advantage of the inventive processes and systems, since i-C6 has a significantly higher octane rating than n-C6 and therefore is a value-added product that can be directly blended into a liquid transportation fuel.
  • a further advantage is that any n-C6 present in the hydrocarbon feed stream is predominantly upgraded by isomerization, which is a more cost-effective method (than catalytic activation) for upgrading n-C6 to higher octane products that are suitable as blend components of a liquid transportation fuel.
  • the activation catalyst may comprise a single catalyst, or a mixture of different catalysts that contacts the alkanes present in the isomerization effluent and facilitates at least one of dehydrogenation, cracking, and aromatization of the alkanes, thereby converting at least a portion of hydrocarbons present in the isomerization effluent to produce the activation effluent.
  • the activation effluent comprises products that may be utilized as a commodity chemical, an intermediate amenable to further catalytic upgrading, or a transportation fuel (or a component thereof).
  • Activation catalysts suitable for use with the processes and systems described herein may comprise any catalyst capable of cracking and/or aromatizing hydrocarbons.
  • catalysts include supported or unsupported solid acids, metals, metal chalcogenides, or metal pnictogenides, including (but not limited to) structured and amorphous silica-aluminas, structured and amorphous solid phosphoric acids, clays, other metal oxides, metal sulfates, or metal phosphates, and graphite-supported materials.
  • ZSM-5 zeolite catalysts are utilized that are characterized by Si/Al ratios ranging from 12-80, optionally ranging from 35 to 50.
  • one or more elements may be impregnated on the zeolite catalyst, including one or more of Ga, Pt, Ni, Mn, Mg, Fe, Cr, P, Cu, La, Sr and F.
  • dehydrogenation is not a prerequisite for paraffin activation in the present inventive process.
  • a sufficient concentration of intermediate olefins can be generated through a combination of thermal dehydrogenation and catalytic cracking such that typical dehydrogenation catalyst metals (such as platinum, zinc, molybdenum, or gallium) can be avoided without significantly decreasing product yield.
  • typical dehydrogenation catalyst metals such as platinum, zinc, molybdenum, or gallium
  • Conventional dehydrogenation catalysts are prone to deactivation by sulfur and nitrogen contaminants that are often present in hydrocarbon feed streams derived from petroleum, so the ability to operate in the absence of these sensitive catalytic materials is highly advantageous to the process.
  • Isopentane exhibits catalyst- dependent activation reactivity that is typically greater than that of n-pentane (n-C5), and the optimal activation reactor conditions for the two isomers are therefore distinct.
  • i-C5 can be activated at lower temperatures than n-C5, while maintaining high yields of desired products (such as olefins and aromatics) and decreasing the yield of C1-C4 paraffins (i.e. fuel gas).
  • the measured activation rates differ by up to 4 fold in favor of i-C5, when each isomer is contacted with the same catalyst under identical conditions (even in the same reactor simultaneously).
  • an initial isomerization of the hydrocarbon feed stream to increase i-C5 content, followed by activating the resulting effluent in catalytic activation zone maximize the yield of value-added, upgraded products (such as olefins and/or aromatics).
  • Increasing conversion of pentane isomers to i-C5 also was found to unexpectedly decrease selectivity of the activation reaction to C1-C4 light gases, which typically have little value other than as fuel gas. This helps maximize the conversion of the feed to upgraded products, which is one of many advantages of the process and systems.
  • Table 1 (below) illustrates the difference in the activation reactivity of i-C5 versus n- C5 over a microporous silica-alumina activation catalyst.
  • Feed streams comprising either 100 wt.% i-C5 or 100 wt.% n-C5 were each catalytically activated in separate experiments utilizing temperatures of either 600°C or 550°C.
  • the conversion and product distribution for i-C5 are shown in Table 1, columns 2 and 3, while similar results for the activation of n-C5 are shown in Table 1, columns 4 and 5.
  • the ability to separate the i-C5 isomer from n-C5 isomer (and any C6+ hydrocarbons) and activate the i-C5 enriched mixture at relatively reduced temperature results in approximately equivalent total conversion of the overall feed stream, while decreasing the formation of undesired C1-C4 light paraffins.
  • the inventive systems and processes take advantage of this reactivity difference between C5 isomers by first isolating, then catalytically-activating predominantly the i-C5 portion of a hydrocarbon feed stream, while simultaneously isomerizing the n-C5/C6+ portion (second fraction) of the feed stream in a first isomerization step.
  • the isomerization effluent that contains an increased wt. % of i-C5 relative to the second fraction. This maximizes both the conversion yield and selectivity of the activation step to form useful products, including (but not limited to) olefins and aromatics, while minimizing the selectivity of the process to form fuel gas.
  • the activation effluent 136 is conveyed into a second separator 150 that separates a light hydrocarbons 151 containing four or fewer carbons and hydrogen from a heavy hydrocarbons fraction 152 that predominantly comprises C5 olefins, single-ring aromatics as well as unreacted pentanes and larger C6+ components originally present in the hydrocarbon feed stream 101.
  • the second separator 150 is a two-phase splitter and separation of the activation effluent 136 is achieved by partial condensation.
  • light hydrocarbons 151 predominantly comprises hydrogen as well as C1-C4 hydrocarbons that were not converted in the activation reactor 133.
  • Light hydrocarbons fraction 151 is conveyed to a fourth separator 153 that typically utilizes a conventional separation technology (such as, but not limited to, pressure swing adsorption technology, membrane separation technology, etc.) to separate hydrogen from light hydrocarbons fraction 151 to produce a hydrogen stream 154 and a light paraffins stream 155 that predominantly comprises paraffins containing four or less carbons atoms.
  • a conventional separation technology such as, but not limited to, pressure swing adsorption technology, membrane separation technology, etc.
  • the light paraffins stream 155 is optionally conveyed and mixed with the first fraction to serve as a diluent during catalytic activation of the first fraction 119.
  • the light paraffins stream 155 is mixed with the first fraction 119 at a point that is upstream from the point where the first fraction 119 contacts the activation catalyst 135 in the activation reactor 133.
  • the heavy hydrocarbons fraction 152 is conveyed to a third separator 160 that is optionally a naphtha stabilizer.
  • the third separator 160 is operable to remove an unreacted C5/C6 fraction 172 comprising predominantly alkanes and olefins containing five to six carbon atoms from the heavy hydrocarbons fraction 152 in order to decrease Reid vapor pressure and increase octane rating of the resulting liquid hydrocarbon product 163, which predominantly comprises hydrocarbon molecules (predominantly monocyclic aromatics) that are characterized by a boiling-point in the range of a liquid transportation fuel, such as, but not limited to, gasoline, diesel and jet fuel.
  • a liquid transportation fuel such as, but not limited to, gasoline, diesel and jet fuel.
  • the unreacted C5/C6 fraction 172 may be used directly as a blend component 168 of a liquid transportation fuel, may be mixed with hydrocarbon feed stream 101 at a point that is upstream from first separator 110, or may be mixed with the first fraction 119 (not depicted).
  • Some embodiments of the inventive processes and systems convey an activation effluent to an oligomerization reactor containing at least one oligomerization catalyst.
  • the activation effluent contacts the oligomerization catalyst and is converted to larger hydrocarbon products that can be utilized as a component of a liquid transportation fuel, such as, but not limited to: gasoline, diesel and jet fuel.
  • a second embodiment of the inventive processes and systems that includes an oligomerization reactor and additional inventive features is illustrated by the process flow-diagram of Figure 2.
  • a hydrocarbon feed stream 201 comprising both n- pentane (nC5) and isopentane (iC5) is converted in a system 20.
  • the hydrocarbon feed stream 201 is received by a first separator 210 that operates to separate the feed stream 201 into a first fraction 219 that comprises an increased wt. % of isopentane (i-C5) relative to the hydrocarbon feed stream 201, and a second fraction 217 that comprises an increased wt. % of n-pentane relative to the hydrocarbon feed stream 201.
  • the second fraction 217 further comprises a large majority of any C6 and larger (C6+) hydrocarbons that were originally present in the hydrocarbon feed stream 201.
  • the first separator 210 is operable to separate the i-C5 isomer from the remaining compounds present within the C5-rich hydrocarbon feed stream using conventional separation technology (e.g., distillation).
  • Any separation technology may be used to assist in separating i-C5 from n-C5 to produce the first fraction and the second fraction, and such separation is not considered critical to the inventive process and systems.
  • the first fraction 219 is conveyed to an activation reactor 233 containing an activation catalyst 235.
  • the activation reactor 233 is operable to maintain a temperature and pressure that is suitable to facilitate conversion of the first fraction 219 to an activation effluent 236.
  • the activation effluent 236 leaves the activation reactor 233, and is conveyed to compressor/condenser 237, which may comprise one or more functions including a condenser, splitter, compressor and pump.
  • Compressor/condenser 237 is operable to receive and condense at least a portion of the activation effluent 236 to produce a liquid hydrocarbons fraction 238 comprising C6 and larger hydrocarbons including paraffins, olefins and aromatics.
  • the liquid hydrocarbons fraction 238 is removed and may be used as blend stock for a liquid hydrocarbon transportation fuel, while the remaining fraction of the activation effluent 236 is compressed by the compressor/condenser 237 to produce a compressed light hydrocarbons fraction 239 predominantly comprising C1-C5 alkanes and olefins that remains in gaseous phase.
  • the compressed light hydrocarbons fraction comprises at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, or at least 80 wt.% of alkanes and olefins containing five or less carbon atoms.
  • the compressed light hydrocarbons fraction 239 is next conveyed to an oligomerization reactor 240 that contains an oligomerization catalyst 245.
  • the compressed light hydrocarbons fraction 239 contacts and is catalytically transformed by the oligomerization catalyst 245 to produce an oligomerization effluent 247 that comprises an increased quantity of hydrocarbon molecules that are characterized by a boiling-point in the range of a liquid transportation fuel (e.g., gasoline and diesel).
  • a liquid transportation fuel e.g., gasoline and diesel
  • the oligomerization catalyst may comprise any solid catalyst (or mixture of catalysts) characterized as possessing either B runs ted or Lewis acidic properties.
  • the oligomerization catalyst is a zeolite or mixture of zeolites, or a reactive transition metal oxide.
  • the oligomerization catalyst is ZSM-5, although many zeolites are well-characterized as possessing oligomerization properties and may be suitable for use (either alone or in combination) with the inventive processes and systems described herein.
  • oligomerization catalysts include, but are not limited to: nickel oxides, aluminum alkyls, aluminum halides, perfluoroaryl boranes, oligomeric methyl aluminoxanes (including supported), perfluoroaryl boranes, fluoroarylanes, trityl borate, ammonium borate (and aluminate salts thereof), supported PhNMe2H+B(C6F5)4- and borate anions and superacidic solid Bronsted acids, among others.
  • the oligomerization reactor is maintained at a temperature and pressure suitable to facilitate oligomerization of olefins present in the gaseous activation effluent, thereby producing larger hydrocarbons comprising at least six carbons that are preferably characterized by a boiling point that is in the boiling point range of a liquid transportation fuel (e.g., gasoline or diesel).
  • the oligomerization reactor is generally maintained at a total pressure in a range from 14 psia to 800 psia, optionally in the range from 50 psia to 300 psia.
  • the oligomerization reactor is typically maintained at a temperature (measured within the oligomerization reactor inlet) in the range from 200°C to 420°C, optionally in the range from 200°C to 350°C.
  • a temperature measured within the oligomerization reactor inlet
  • flow thorough the oligomerization reactor is maintained at a weight hourly space velocity (WHSV) in the range from 0.5 hr 1 to 10 hr 1 .
  • the WHSV is in the range from 0.5 hr 1 to 2.0 hr 1 . While higher overall throughput is desirable, ideally the chosen WHSV allows for conversion of at least 85% of olefins present in the gaseous activation effluent at the selected operating temperature and pressure.
  • the catalytic conversion occurring in the oligomerization reactor produces an oligomerization effluent that typically comprises an increased quantity of hydrocarbon molecules that are characterized by a boiling-point in the range of a liquid transportation fuel (e.g., gasoline and diesel).
  • a liquid transportation fuel e.g., gasoline and diesel.
  • the combination of isomerization, activation and oligomerization converts at least 30 wt.% of the original hydrocarbon feed stream to hydrocarbon molecules that are characterized by a boiling point that is in the boiling point range of gasoline.
  • the oligomerization effluent 247 produced in the oligomerization reactor 240 is conveyed to a second separator 250 that separates the oligomerization effluent 247 into two fractions: a light hydrocarbons fraction 251 comprising C1-C4 hydrocarbons and hydrogen, and a heavy hydrocarbons fraction 252 comprising hydrocarbons containing at least five carbon atoms (C5+) that may be utilized directly as a blend component of a liquid transportation fuel or an intermediate product that may be additionally processed prior to blending into a liquid transportation fuel.
  • a light hydrocarbons fraction 251 comprising C1-C4 hydrocarbons and hydrogen
  • a heavy hydrocarbons fraction 252 comprising hydrocarbons containing at least five carbon atoms (C5+) that may be utilized directly as a blend component of a liquid transportation fuel or an intermediate product that may be additionally processed prior to blending into a liquid transportation fuel.
  • light hydrocarbons fraction 251 predominantly comprises hydrogen as well as C1-C4 hydrocarbons that remained unconverted in the oligomerization reactor 240.
  • Light hydrocarbons fraction 251 leaves the second separator 250 and is optionally conveyed to a fourth separator 253 that utilizes a conventional separation technology (such as, but not limited to, pressure swing adsorption technology, membrane separation technology, etc.) to separate hydrogen from the light hydrocarbons to produce a hydrogen stream 254 and a light paraffins stream 255 comprising paraffins containing four or less carbon atoms.
  • a conventional separation technology such as, but not limited to, pressure swing adsorption technology, membrane separation technology, etc.
  • the light paraffins stream 255 is optionally recycled to serve as a diluent during catalytic activation of the first fraction 219.
  • the light paraffins stream 255 is mixed with the first fraction 219 at a point that is upstream from the point where the first fraction 219 contacts the activation catalyst 235 in the activation reactor 233.
  • the heavy hydrocarbons fraction 252 is conveyed to a third separator 260 that is optionally a naphtha stabilizer.
  • the third separator 260 is operable to remove an unreacted C5/C6 fraction 272 comprising predominantly alkanes and olefins containing five to six carbon atoms from the heavy hydrocarbons fraction 252 in order to decrease Reid vapor pressure and increase octane rating of the resulting liquid hydrocarbon product 263, which predominantly comprises hydrocarbon molecules (predominantly, monocyclic aromatics) that are characterized by a boiling-point in the range of a liquid transportation fuel, such as, but not limited to, gasoline, diesel and jet fuel.
  • a liquid transportation fuel such as, but not limited to, gasoline, diesel and jet fuel.
  • the unreacted C5/C6 fraction 272 may be used directly as a blend component 268 of a liquid transportation fuel, or alternatively, is mixed with hydrocarbon feed stream 201 at a point that is upstream from separator 210.
  • at least a portion of the blending fraction 225 as well as the liquid hydrocarbons fraction 238 derived from the condenser/compressor 237 may be combined with the liquid hydrocarbon product 263.
  • the liquid hydrocarbon product of the process may be hydrotreated in a hydrotreating reactor containing a hydrotreating catalyst in order to reduce olefin and aromatic content in the liquid hydrocarbon product, as well as to remove any nitrogen-containing and sulfur-containing compounds that may be present.
  • the hydrotreating reactor contains at least one hydrotreating catalyst (such as, for example, NiMo, CoMo, etc.) or a precious metal catalyst (such as Pt/AbCh, Pd/AbCh, or Pd/C, etc) and is maintained at a pressure and temperature suitable for facilitating hydrotreating catalytic reactions.
  • hydrotreating catalyst such as, for example, NiMo, CoMo, etc.
  • a precious metal catalyst such as Pt/AbCh, Pd/AbCh, or Pd/C, etc
  • the second fraction 217 is directed to a storage vessel 220 that is operable to both receive the second fraction 217, and to optionally divert at least a portion of the second fraction 217 to produce a blending fraction 225 that may be blended directly into a liquid hydrocarbon transportation fuel (e.g., gasoline).
  • a liquid hydrocarbon transportation fuel e.g., gasoline
  • Diverting may be accomplished in a number of conventional ways (e.g., an outlet comprising an adjustable valve) that are well-understood in the art, and thus, will not be discussed further here.
  • the remainder of the second fraction 217 passes through the storage vessel 220 and is next conveyed to a isomerization reactor 227 that contains an isomerization catalyst 230 and is operable to receive a flow of hydrogen gas 231, and further operable to maintain a temperature and pressure that are suitable to facilitate the conversion of the second fraction 217 by the isomerization catalyst 230 to produce an isomerization effluent 232 that comprises an increased wt.% of i-C5 and a decreased wt. % of n-C5 relative to the second fraction 217.
  • some embodiments of the inventive system and process do not comprise a storage vessel, and a portion of the second fraction is simply diverted via a valve (not depicted) to produce the blending fraction.
  • the quantity of the second fraction that is diverted (if any) is determined by the molecular composition of the second fraction and the percentage of the second fraction that is to be fed to the isomerization reactor.
  • Some embodiments of the inventive processes and systems convey the activation effluent to an aromatic alkylation reactor containing at least one alkylation catalyst. This produces larger hydrocarbon products that can be utilized as either gasoline or diesel transportation fuel, or a component thereof.
  • a third embodiment of the inventive processes and systems that includes an alkylation reactor and additional inventive features is illustrated by the process flow-diagram of Figure 3.
  • a hydrocarbon feed stream 301 comprising both n-pentane (nC5) and isopentane (iC5) is converted in a system 30.
  • the hydrocarbon feed stream 301 is received by a first separator 310 that operates to separate the feed stream 301 into a first fraction 319 that comprises an increased wt.% of isopentane (i-C5) relative to the hydrocarbon feed stream 301, and a second fraction 317 that comprises an increased wt.% of n-pentane relative to the hydrocarbon feed stream 301.
  • the second fraction 317 further comprises a large majority of any C6 and larger (C6+) hydrocarbons that were originally present in the hydrocarbon feed stream 301.
  • the first separator 310 is operable to separate the i-C5 isomer from the remaining compounds present within the C5-rich hydrocarbon feed stream using conventional separation technology (e.g., distillation).
  • Any separation technology may be used to assist in separating i-C5 from n-C5 to produce the first fraction and the second fraction, and such separation is not considered critical to the inventive process and systems.
  • the first fraction 319 is conveyed to an activation reactor 333 containing an activation catalyst 335.
  • the activation reactor 333 is operable to maintain a temperature and pressure that is suitable to facilitate conversion of the first fraction 319 to an activation effluent 336.
  • the activation effluent 336 leaves the activation reactor 333, and is conveyed to compressor-condenser 337, which may comprise one or more functions including condensing, splitting, compressing and pumping.
  • compressor-condenser 337 is operable to receive and condense a portion of the activation effluent 336 to produce a liquid hydrocarbons fraction 338 comprising C6 and larger hydrocarbons including paraffins, olefins and aromatics.
  • the liquid hydrocarbons fraction 338 is removed from the system via an outlet in the compressor-condenser 337 and is has the physical and chemical characteristics meeting requirements for a liquid hydrocarbon transportation fuel, or a component thereof.
  • the compressor-condenser 337 does not operate to condense the activation effluent.
  • the entire activation effluent 336 is compressed by compressor-condenser 337.
  • the remaining fraction of the activation effluent 336 is compressed by the compressor-condenser 337 to produce a compressed alkylation feed stream 339 comprising gas-phase aromatics (that were not condensed by the compressor-condenser 337) as well as C1-C5 alkanes and olefins.
  • the compressed alkylation feed stream 339 is next conveyed to an alkylation reactor 340 that contains an alkylation catalyst 345.
  • the compressor-condenser 337 does not condense all aromatics present in the activation effluent 336, but instead retains at least a portion of the aromatics to subsequently be alkylated by olefins in the alkylation reactor 340.
  • the compressed alkylation feed stream 339 contacts the alkylation catalyst, producing an alkylation effluent that comprises an increased wt.% of alkylated aromatics, especially monocyclic alkylated aromatics.
  • the alkylation reactor is maintained at a feed inlet temperature and a pressure that are suitable to facilitate the catalytic alkylation of aromatics that are present in the compressed alkylation feed stream.
  • the aromatics that are alkylated may be produced by aromatization that takes place in the activation reactor or may be a constituent of the hydrocarbon feed stream.
  • Olefins that are used to alkylate the aromatics are mostly produced by the activation of alkanes in the activation reactor.
  • Alkylation of aromatics with light olefins in the alkylation reactor produces an alkylation effluent comprising larger hydrocarbons comprising at least seven carbons that are preferably characterized by a boiling point that is in the boiling point range of a liquid transportation fuel (e.g., gasoline or diesel).
  • a liquid transportation fuel e.g., gasoline or diesel.
  • the alkylation effluent comprises an increased percentage of alkylated aromatic compounds comprising from seven to nine carbon atoms.
  • the larger hydrocarbons also are characterized by a lower Reid vapor pressure and an increased octane number.
  • the alkylation reactor is generally maintained at a pressure (measured at the feed inlet) in a range from 14 psia to 800 psia, optionally in the range from 50 psia to 600 psia.
  • the alkylation reactor is typically maintained at a temperature (measured at the alkylation reactor inlet) in a range from 150°C to 350°C, optionally between 200°C to 350°C.
  • flow thorough the alkylation reactor is maintained at a weighted hourly space velocity (WHSV) in the range from 0.5 hr 1 to 10 hr 1 on a hydrocarbon basis.
  • the WHSV is in the range from 0.5 hr 1 to 2.0 hr 1 .
  • the chosen WHSV allows for conversion of at least 85% olefmic of hydrocarbons present in the mixed effluent at the selected operating temperature and pressure.
  • the catalytic conversion occurring in the alkylation reactor produces an aromatic alkylation reactor effluent that typically comprises at least 30 wt.% (preferably, at least 40 wt%) of hydrocarbon molecules that are characterized by a boiling-point in the range of a liquid transportation fuel.
  • the alkylation catalyst may comprise any catalyst characterized as either Bronsted or Lewis acidic.
  • a wide variety of catalysts have been found to promote aromatic alkylation including, but not limited to, aluminum chloride, phosphoric acid, sulfuric acid, hydrofluoric acid, silica, alumina, sulfated zirconia, zeolites (including, for example, ZSM- 5, ZSM-3, ZSM-4, ZSM-18, ZSM-20, zeolite-beta, H-Y, MCM-22, MCM-36 and MCM-49).
  • the alkylation catalyst simultaneously promotes alkylation of aromatics and oligomerization of olefins present in the mixed effluent.
  • the alkylation effluent 347 produced in the alkylation reactor 340 is conveyed to a second separator 350 that separates the alkylation effluent 347 into two fractions: a light hydrocarbons fraction 351 comprising C1-C4 hydrocarbons and 3 ⁇ 4 and a heavy hydrocarbons fraction 352 comprising hydrocarbons containing at least five carbon atoms (C5+) that may be utilized directly as a blend component of a liquid transportation fuel or additionally processed prior to blending into a liquid transportation fuel.
  • the alkylation effluent preferably comprises an increased quantity (or increased wt%) of alkylated aromatics containing from seven to nine carbon atoms.
  • these alkylated aromatics are monocyclic aromatic hydrocarbons.
  • light hydrocarbons fraction 351 predominantly comprises hydrogen as well as C1-C4 hydrocarbons that remained unconverted in the alkylation reactor 340.
  • Light hydrocarbons fraction 351 leaves the second separator 350 and is optionally conveyed to a fourth separator 353 that utilizes a conventional separation technology (such as, but not limited to, pressure swing adsorption technology, membrane separation technology, etc.) to separate hydrogen from the light hydrocarbons to produce a hydrogen stream 354 and a light paraffins stream 355 comprising paraffins continuing four or less carbon atoms.
  • the light paraffins stream 355 is optionally recycled to serve as a diluent during catalytic activation of the first fraction 319.
  • the light paraffins stream 355 is mixed with the first fraction 319 at a point that is upstream from the point where the first fraction 319 contacts the activation catalyst 335 in the activation reactor 333.
  • the heavy hydrocarbons fraction 352 is conveyed to a third separator 360 that is optionally a naphtha stabilizer.
  • the third separator 360 is operable to remove a unreacted C5/C6 fraction 372 (comprising predominantly alkanes and olefins containing four to six carbon atoms) from the heavy hydrocarbons fraction 352 in order to decrease the Reid vapor pressure and increase the octane rating of the resulting liquid hydrocarbon product 363 that predominantly comprises hydrocarbons (predominantly monocyclic aromatics) that are characterized by a boiling-point in the range of a liquid transportation fuel, such as, but not limited to, gasoline, diesel and jet fuel.
  • a liquid transportation fuel such as, but not limited to, gasoline, diesel and jet fuel.
  • the unreacted C5/C6 fraction 372 may optionally be used directly as a blend component 368 of a liquid transportation fuel, or alternatively, is mixed with hydrocarbon feed stream 301 at a point that is upstream from the separator 310.
  • at least a portion of the blending fraction 325 and at least a portion of the liquid hydrocarbons fraction 338 derived from the condenser/compressor 337 may be combined with the liquid hydrocarbon product 363.
  • the liquid hydrocarbon product may be hydrotreated in a hydrotreating reactor containing a hydrotreating catalyst in order to reduce olefin and aromatic content in the liquid hydrocarbon product, as well as to remove nitrogen- containing and sulfur-containing compounds.
  • the hydrotreating reactor contains at least one hydrotreating catalyst (such as, for example, NiMo, CoMo, etc.) or a precious metal catalyst (such as Pt/A1203, Pd/A1203, or Pd/C, etc) and is maintained at a pressure and temperature suitable for facilitating hydrotreating catalytic reactions.
  • hydrotreating catalyst such as, for example, NiMo, CoMo, etc.
  • a precious metal catalyst such as Pt/A1203, Pd/A1203, or Pd/C, etc
  • Some embodiments comprise mixing a diluent with the first fraction prior to contacting the resulting mixture with an activation catalyst in the activation reactor.
  • the diluent may be added in a ratio ranging from 10: 1 to 1 : 10 molar ratio relative to the quantity of isomerization effluent fed to the activation reactor.
  • the diluent may be added at any point that is upstream from, or within, the activation reactor, but prior to contacting the activation catalyst.
  • the diluent may comprise any substance that is less chemically-reactive with the activation catalyst than the constituents that are present in the first fraction at the conditions of temperature and pressure that are maintained within the activation reactor. This prevents the diluent from reacting with the activation catalyst. Such properties are found in a large number of substances that are fully within the grasp of a person who is knowledgeable in the field.
  • the diluent may comprise C1-C4 light paraffins, including recycling C1-C4 light paraffins produced by the inventive processes and systems described herein.
  • the diluent may comprise any of methane, ethane, propane, butanes, benzene, toluene, xylenes, alkyl- or dialkyl-benzenes, naphthenes, C2-C5 olefins, and combinations thereof.
  • diluent during catalytic activation provides numerous advantages.
  • it effectively decreases the concentration of the isomerization effluent within the activation reactor. This results in a small increase in the total conversion of alkanes to olefins or aromatics within the activation reactor.
  • it also increases the selectivity toward the production of olefins, while slightly decreasing the selectivity toward the production of aromatics.
  • Adjusting the ratio of diluent to isomerization effluent changes the ratio of olefins to aromatics in the resulting activation effluent, thereby providing a valuable point of operational control for downstream processes.
  • the optimal molar production ratio of olefins to aromatics ranges from about 0.5: 1 to about 1.5: 1, in order to maximize the value captured in the olefin intermediates during the alkylation in the alkylation reactor.
  • Mono- alkylated aromatics exhibit beneficial (increased) octane rating and vapor pressure for application as blending components in some transportation fuels such as gasoline.
  • di alkyl and tri-alkyl aromatics comprising more than nine carbon atoms are not well-suited for blending into gasoline, and exhibit nonoptimal cetane number for blending into diesel.
  • Addition of a diluent also advantageously favors the production of value-added olefins relative to C1-C4 light paraffins, and also mitigates dimerization of C5 hydrocarbons to form durene (1,2,4,5-tetramethylbenzene), a problematic byproduct that often precipitates from gasoline blends.
  • This example demonstrates the preliminary rationale for isomerizing at least a portion of the n-C5 found in a given hydrocarbon feed stream to i-C5 prior to contacting the pentane with an activation catalyst.
  • the graphs below illustrate differences in activation reactivity for n- C5 and i-C5.
  • Feed streams were utilized that comprised either 100 wt.% i-C5 (i-C5), 100 wt.% n-C5 (n-C5), or a 70 wt.% iC5/ 30 wt.% n-C5 mixture (i/n [7:3]) that represents an isomerized pentanes stream that has been contacted with an isomerization catalyst to increase the ratio of i- C5 to n-C5.
  • the catalyst utilized was 1 ⁇ 2" extrudate consisting of 50 wt.% alumina binder and 50 wt.% ZSM-5 zeolite, and experiments were conducted at a WHSV of 1.3 hr 1 at 1 atm. Results were averaged over the total time on stream of 16 hr.
  • Figure 4 is a bar graph depicting the results of catalytically activating each feed stream at either 550°C or 600°C.
  • the graph depicts, as percentages, the total catalytic conversion of each feed stream (first column), the yield to light olefins as product (second column), the yield to aromatics as product (third column) and the yield to C1-C4 light paraffins (defined as non-olefin hydrocarbons containing from one to four carbon atoms), fourth column. Yield was calculated on a wt.% basis, relative to the weight of the feed stream.
  • This experiment demonstrates that isopentane (i-C5) is advantageously converted by both an activation catalyst and a subsequent oligomerization catalyst to produce a high percentage of product that is suitable for use as a liquid transportation fuel.
  • a 100 wt.% i-C5 feed stream was upgraded by first contacting it with a zeolite activation catalyst, followed by contacting a zeolite oligomerization catalyst. Activation was conducted by contacting the feed stream with 1 ⁇ 2 in. diameter catalyst extrudate consisting of 50 wt.% alumina binder and 50 wt.% ZSM-5 zeolite catalyst at a temperature of 579°C, and a WHSV of 2.6 hr 1 at 1 atm.
  • Oligomerization was conducted by contacting the activation effluent with a ZSM-5 zeolite catalyst in a reactor where the inlet temperature for the activation effluent was maintained at 250°C, the pressure was 1 atm, and the WHSV for the feed stream was 1.3 hr 1 . Results were time-averaged over 16 hours.
  • the table shows the product distribution following conversion along with the selectivity to olefins and liquid product.
  • the term“selectivity” indicates the percentage of the catalytically converted feed stream that was converted to a particular product.
  • Table 2 Upgrading pentanes by activation alone or activation plus oligomerization.
  • This experiment demonstrates that isopentane (i-C5) is advantageously converted by both an activation catalyst and a subsequent alkylation catalyst to produce a high percentage of product that is suitable for use as a liquid transportation fuel.
  • a 100 wt.% i-C5 feed stream was upgraded by first contacting it with a zeolite activation catalyst, followed by contacting the activation effluent with a zeolite alkylation catalyst. Activation was conducted by contacting the feed stream with a 1 ⁇ 2 in. diameter catalyst extrudate consisting of 50 wt.% alumina binder and 50 wt.% ZSM-5 zeolite catalyst in an activation reactor.
  • the temperature of the activation reactor at the inlet for the feed stream was 579°C, the pressure was 1 atm, and the WHSV for the feed stream was 2.6 hr 1 .
  • Alkylation was then conducted by contacting the effluent with a ZSM-5 catalyst in a reactor where the temperature at the inlet for the feed stream was 230 °C, the pressure was maintained at 15 psig and the WHSV of the feed stream was 1.3 hr 1 at 1 atm. Results were time-averaged over 16 hours.
  • the table shows the product distribution following conversion along with the selectivity to olefins and liquid product.
  • the term“selectivity” indicates the percentage of the catalytically converted feed stream that was converted to a particular product.
  • the final product only comprised 16.3 wt.% of light olefins.
  • These olefins may be recycled to the activation reactor, used as a diluent in the alkylation reactor, or diverted to be utilized in any of a variety of conventional processes.
  • results shown in the above table may underestimate the total percentage of a mixed pentanes feed stream that would be available for blending into a liquid transportation fuel, as a typical hydrocarbon feed stream (such as, but not limited to, natural gasoline) may also include an excess quantity of C5/C6+ that would not be either catalytically-cracked or introduced into the alkylation reactor, but would partition into the second fraction and leave the system via an outlet located upstream from the isomerization reactor. This excess quantity of C5/C6+ is suitable for direct blending into the liquid hydrocarbon product.
  • a typical hydrocarbon feed stream such as, but not limited to, natural gasoline
  • nC5/C6+ fraction is diverted when necessary to achieve the desired 0.5: 1 to 1.5: 1 olefin to aromatic ratio that maximizes production of mono-alkylated aromatics in the alkylation reactor.
  • the final product comprises a high wt. percentage of monocyclic aromatics that are an exceptional blend stock for a gasoline (see calculated Research Octane and Motor Octane Numbers, above). Only a small quantity of paraffins remain, which can be recycled to process, used as diluent for the activation step, or combusted to produce at least a portion of the heat required for the process.
  • This example demonstrates the effect that a methane diluent has on catalytic activation and conversion of two different hydrocarbon feed streams: 1) a simulated“natural gasoline” comprising 50 wt.% i-C5 and 50 wt.% n-C5 isomers, and 2) a simulated“first fraction” comprising 70 wt.% i-C5 and 30 wt.% n-C5.
  • a simulated“natural gasoline” comprising 50 wt.% i-C5 and 50 wt.% n-C5 isomers
  • a simulated“first fraction” comprising 70 wt.% i-C5 and 30 wt.% n-C5.
  • the temperature of the reactor (at the inlet for the feed stream) was maintained at 600°C and 20 psig (2.4 Bar) and results were time-averaged for 16.5 hr.
  • methane diluent was co-fed along with each feed stream at a methaneTeed stream molar ratio of 2: 1.
  • the reaction produced an effluent comprising light olefins, aromatics and light paraffins.
  • Table 5 shows the effect of the methane diluent on the total conversion of the 1 : 1 and 7:3 feed streams, respectively, as well as the selectivity of each conversion toward light olefins, aromatics, and byproduct C1-C4 fuel gas.
  • Table 5 Catalytic activation of a 1:1 i-C5:n-C5 feed stream and a 7:3 1 i-C5:n-C5 feed stream in both the absence and presence of methane diluent.
  • diluent is added to the activation feed stream at a ratio that maximizes light olefin production, providing an advantageous feed stream for the oligomerization catalyst.
  • diluent can be added to the activation feed stream at a ratio that produces a first effluent comprising olefins and aromatics at a ratio (typically between 0.5:1 and 1.5: 1 by mole) that provides an advantageous feed stream for an aromatic alkylation process.
  • conversion is defined as any of the chemical reactions that occur during upgrading of hydrocarbons to liquid transportation fuels. Examples of such reactions include, but are not limited to: oligomerization, aromatization, dehydrogenation, alkylation, hydrogenation and cracking.

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Abstract

L'invention concerne des systèmes pouvant être utilisés pour produire des carburants liquides pour le transport par conversion d'un flux d'alimentation en hydrocarbures comprenant à la fois de l'isopentane et du n-pentane. Le système comprend un premier séparateur pouvant être utilisé pour séparer un flux d'alimentation en hydrocarbures en une première fraction qui comprend majoritairement de l'isopentane et une seconde fraction qui comprend majoritairement du n-pentane et des paraffines en C6. Un réacteur d'isomérisation réalise une isomérisation de la seconde fraction pour convertir au moins une partie du n-pentane en isopentane. L'effluent d'isomérisation résultant est combiné avec le flux d'alimentation en hydrocarbures, permettant à l'isopentane produit dans le réacteur d'isomérisation d'être séparé en une première fraction dans le premier séparateur. Un réacteur d'activation active de manière catalytique la première fraction pour produire un effluent d'activation comprenant des oléfines et des composés aromatiques. Certains modes de réalisation comprennent en outre soit un réacteur d'oligomérisation soit un réacteur d'alkylation pouvant fonctionner pour valoriser encore l'effluent d'activation, ce qui permet d'améliorer les rendements.
EP20795065.0A 2019-04-24 2020-04-24 Isomérisation et activation catalytique de mélanges d'hydrocarbures enrichis en pentane Pending EP3959187A4 (fr)

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US16/855,367 US10988696B2 (en) 2019-04-24 2020-04-22 Systems for isomerization and catalytic activation of pentane-enriched hydrocarbon mixtures
US16/855,312 US10870808B2 (en) 2019-04-24 2020-04-22 Isomerization and catalytic activation of pentane-enriched hydrocarbon mixtures
US16/855,350 US10975314B2 (en) 2019-04-24 2020-04-22 Isomerization, catalytic activation and alkylation of pentane-enriched hydrocarbon mixtures
US16/855,333 US10865168B2 (en) 2019-04-24 2020-04-22 Isomerization, catalytic activation and oligomerization of pentane-enriched hydrocarbon mixtures
PCT/US2020/029702 WO2020219797A1 (fr) 2019-04-24 2020-04-24 Isomérisation et activation catalytique de mélanges d'hydrocarbures enrichis en pentane

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US20140171704A1 (en) * 2012-12-13 2014-06-19 Uop Llc Methods and apparatuses for producing ethylene and propylene from naphtha feedstock
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