WO2014123972A1 - Procédé de production de propylène - Google Patents

Procédé de production de propylène Download PDF

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Publication number
WO2014123972A1
WO2014123972A1 PCT/US2014/014823 US2014014823W WO2014123972A1 WO 2014123972 A1 WO2014123972 A1 WO 2014123972A1 US 2014014823 W US2014014823 W US 2014014823W WO 2014123972 A1 WO2014123972 A1 WO 2014123972A1
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Prior art keywords
metathesis
butene
stream
propylene
ethylene
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PCT/US2014/014823
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English (en)
Inventor
Steven T. Coleman
Gary A. Sawyer
Robert S. Bridges
Shaotian Wang
Lawrence M. Candela
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Lyondell Chemical Technology, L.P.
Equistar Chemicals, Lp
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Priority claimed from US13/774,723 external-priority patent/US20130172647A1/en
Application filed by Lyondell Chemical Technology, L.P., Equistar Chemicals, Lp filed Critical Lyondell Chemical Technology, L.P.
Publication of WO2014123972A1 publication Critical patent/WO2014123972A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/10—Catalytic processes with metal oxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/30—Tungsten

Definitions

  • the present invention generally relates to methods and systems of forming propylene.
  • Metathesis reactions to produce propylene generally include feeding a metathesis feed stream comprising butene, generally a mixture of 1-butene and 2-butene, to a metathesis reactor loaded with a mixture of metathesis catalyst and an isomerization catalyst.
  • a metathesis feed stream comprising butene, generally a mixture of 1-butene and 2-butene
  • a metathesis reactor loaded with a mixture of metathesis catalyst and an isomerization catalyst.
  • Such process provide for efficiencies by utilizing a single process for the production of propylene from available feedstocks.
  • reaction of 1-butene can cause side reactions, forming undesirable byproducts, such as pentene and hexene, for example.
  • the present invention is directed to resolving, or at least reducing, one or all of the problems mentioned above.
  • Various embodiments of the present invention include processes of forming propylene.
  • the processes generally include separating a butene feed stream in a butene fractionation system that, in operation, separates 1 -butene from 2-butene; recovering 2-butene from the butene fractionation system and utilizing the 2-butene to form a metathesis feed stream including at least 95 wt.% 2-butene; reacting the metathesis feed stream with ethylene in the presence of a metathesis catalyst to form a metathesis product stream including propylene; and recovering propylene from the process.
  • One or more embodiments include the process of the preceding paragraph, wherein the metathesis feed stream reacts with the ethylene in the absence of an amount of isomerization catalyst sufficient to isomerize butene.
  • One or more embodiments include the process of the preceding paragraph, wherein the metathesis feed stream reacts with the ethylene in the absence of an isomerization catalyst.
  • One or more embodiments include the process of the preceding paragraph, wherein the metathesis feed stream is formed essentially of 2-butene.
  • One or more embodiments include the process of any preceding paragraph, wherein the metathesis feed stream includes at least 98 wt.% 2-butene.
  • One or more embodiments include the process of any preceding paragraph, wherein the metathesis feed stream includes a molar ratio of 2-butene: 1 -butene of at least 49: 1.
  • One or more embodiments include the process of any preceding paragraph, wherein the metathesis feed stream includes less than 5 wt.% 1 -butene.
  • One or more embodiments include the process of any preceding paragraph further including contacting a first feed stream including ethylene with a dimerization catalyst to form a dimerization product stream including 2-butene, wherein the butene feed stream includes the dimerization product stream.
  • One or more embodiments include the process of any preceding paragraph, wherein the dimerization catalyst is selected from metal oxides, nickel complexes, aluminum complexes and combinations thereof.
  • One or more embodiments include the process of any preceding paragraph, wherein the metathesis catalyst includes a transition metal oxide.
  • One or more embodiments include the process of any preceding paragraph, wherein the metathesis catalyst includes tungsten oxide.
  • One or more embodiments include the process of any preceding paragraph, wherein the metathesis product stream includes less than 1 mol.% pentene.
  • One or more embodiments include the process of any preceding paragraph, wherein the metathesis product stream further includes C2 to Ce olefins and wherein recovering the propylene includes fractionating within a propylene fractionation system the metathesis product stream to form a propylene stream, a recycle stream including olefins selected from butene, ethylene and combinations thereof, and optionally a bottoms stream including olefins selected from C5 olefins, C + olefins and combinations thereof.
  • One or more embodiments include the process of the preceding paragraph further including passing the recycle stream from the propylene fractionation system to the metathesis reaction without passing the recycle stream through an isomerization reaction.
  • One or more embodiments include the process of the preceding paragraph, wherein the propylene fractionation system includes a first stage that, in operation, separates ethylene from other components present in the metathesis product stream to form a de-ethenized product stream; and a second stage that, in operation, separates propylene from C 4 and heavier olefins in the de-ethenized product stream.
  • One or more embodiments include the process of any preceding paragraph, wherein th e process produc es at least 100 MM Ibs./yr of propylene.
  • One or more embodiments include the process of any preceding paragraph, wherein the metathesis reaction exhibits a propylene selectivity of at least 95%, wherein "propylene selectivity" is defined as the propylene production divided by the propylene plus C5 and heavier olefins produced in the metathesis reaction, expressed as a percentage.
  • One or more embodiments include a process for forming propylene including reacting a first feed stream including ethylene with a dimerization catalyst to form a dimerization product stream; fractionating the dimerization product stream to form a 2-butene stream; reacting the 2- butene stream with ethy lene in the presence of a metathesis catalyst to form a metathesis product stream including propylene, wherein the 2-butene stream reacts with the ethylene in the absence of an amount of isomerization catalyst sufficient to isomerize butene; and recovering propylene from the process, wherein the process produces at least 100 MM lbs/yr of propylene.
  • Figure 1 illustrates a simplified process flow diagram for various embodiments described herein.
  • Figure 2 illustrates a specific embodiment of a propylene production process.
  • Figure 3 illustrates an alternative embodiment of a propylene production process.
  • Processes for forming propylene are described herein.
  • the processes generally include reacting a metathesis feed stream including 2-butene with ethylene in the presence of a metathesis catalyst to form a metathesis product stream including propylene.
  • the metathesis feed stream may be formed by contacting a first feed stream including ethylene with a dimerization catalyst to form a dimerization product stream including 2-butene.
  • dimerization refers to a chemical reaction in which two identical molecular entities react to form a single dimer.
  • the identical molecular entities are generally ethylene, while the dimer is generally butene.
  • the dimerization catalyst may include catalyst known in the art to be capable of converting ethylene to linear C 4 olefins (i.e., n-butene) upon reaction.
  • dimerization catalysts may include homogenous catalyst compounds including nickel.
  • Many catalysts containing nickel are known to dimerize ethylene to butenes (e.g., U.S. Letters Patent 4,528,415, U.S. Letters Patent 3,513,218 and U.S. Letters Patent 3,452, 1 15).
  • the dimerization catalyst may include an organoaluminum compound of the formula R n AlXv n , wherein R is selected from a Iky Is, such as butyl, ethyl and methyl, X is selected from halogens, such as chlorine and n is 0, 1 or 2, for example.
  • the dimerization may be carried out in any reactor type, such as a loop reactor, for example.
  • the dimerization may be earned out under moderate conditions, such as temperatures of from 20°C to 400°C, or from 25°C to 150°C or from 30°C to 55°C and pressures of from 200 psig to 400 psig, or from 250 psig to 350 psig or from 265 psig to 315 psig, for example.
  • the dimerization product stream and/or an isomerization product stream generally include n-butenes, including 1 -butene and 2-butene.
  • the processes described herein includes embodiments wherein the metathesis feed stream includes primarily 2-butene.
  • the metathesis feed stream includes less than 5 wt.%, or less than 4 wt.%, or less than 3 wt.%, or less than 2 wt.% or less than 1 wt.% 1 -butene.
  • the metathesis feed stream may include at least 95 wt.%, or least 97 wt.%, or at least 98 wt.% or at least 99 wt.% 2-butene, for example.
  • the metathesis feed stream may mclude a molar ratio of 2-butene: 1 -butene of at least 20: 1, or at least 49: 1, or at least 100: 1, for example.
  • One or more embodiments mclude separating the dimerization product stream via a separation process.
  • the separation process may include those known in the art, such as fractionation.
  • fractionation refers to processes for the separation of components based on the relative volatility and/or boiling point of the components.
  • the fractionation processes may include those known in the art and the term “fractionation” can be used interchangeably with the terms “distillation” and “fractional distillation” herein.
  • the dimerization product stream may be separated in a butene fractionation system.
  • the butene fractionation system may include a first section and a second section.
  • the first section may include a column or columns adapted to separate butene from other components present in the isomerization product stream, such as unreacted ethylene and trimers and heavier oligomers of ethylene, for example.
  • the second section may include a column adapted to separate 1-butene from 2-butene.
  • the 2-butene is generally recovered from the separation process and passed to the metathesis feed stream.
  • 1-butene is recovered from the separation process utilized as a high value feed stream for other chemical processes.
  • Embodiments described herein include reacting the metathesis feed stream with ethylene in the presence of a metathesis catalyst to form a metathesis product stream (i.e., a metathesis reaction).
  • a metathesis reaction refers to an equilibrium reaction between two olefins where the double bond of each olefin is broken to form intermediate reactants. These intermediates recombine to form new olefin products.
  • the two olefins include ethylene and butene and the new olefin product is propylene.
  • the butene preferably 2-butene
  • the ethylene may be fed to the reactor by methods known to one skilled in the art.
  • the ethylene may be fed to the metathesis reaction via an inlet separate from an inlet utilized to feed the metathesis feed stream.
  • the ethylene may be combined with the metathesis feed stream prior to the metathesis feed stream passing through such inlet.
  • all references referring to the amount/concentration of 2-butene or 1 -butene in the metathesis feed stream refer to such prior to contact/mixing with ethylene.
  • the molar ratio of ethylene to butene contacting the metathesis catalyst may range fr m 0.1 : 1 to 2.5: 1 , or from 0.8: 1 to 2: 1 or from 1.5: 1 to 2: 1, for example.
  • the metathesis reaction includes contacting the butene with ethylene in the presence of a metathesis catalyst.
  • Metathesis catalysts are well known in the art (see, e.g., U.S. Letters Patent 4,513,099 and U.S. Letters Patent 5, 120,894).
  • the metathesis catalyst includes a transition metal oxide, such as transition metal oxides of cobalt, molybdenum, rhenium, tungsten, ruthenium, and combinations thereof, for example.
  • the metathesis catalyst includes tungsten oxide.
  • the metathesis catalyst may be supported on a carrier, such as silica, alumina, titania, zirconia, zeolites, clays and mixtures thereof, for example.
  • the carrier is selected from silica, alumina and combinations thereof.
  • the catalyst may be supported on a earner by methods known in the art, such as adsorption, ion-exchange, impregnation or sublimation, for example.
  • the metathesis catalyst may include from 1 wt.% to 30 wt.% or from 5 wt.% to 20 wt.% transition metal oxide, for example.
  • the metathesis reaction also included contacting the butene with ethylene in the presence of an isomerization catalyst.
  • the isomerization catalyst was adapted to convert 1 - butene present in the metathesis feed stream to 2-butene for subsequent reaction to propylene, thereby improving the reaction yield of propylene (e.g., conversion rates of from 65% to 70% and selectivity rates of from 90% to 98%).
  • conversion rates e.g., conversion rates of from 65% to 70% and selectivity rates of from 90% to 98%.
  • contact with the isomerization catalyst often resulted in the formation of more undesirable by-products such as pentene and hexene, for example.
  • Isomerization catalysts may include zeolites, metal oxides, mixed metal oxides and combinations thereof, for example.
  • the isomerization catalyst includes a basic double-bond isomerization catalyst, such as a metal oxide (e.g., magnesium oxide, tungsten oxide, calcium oxide, barium oxide, lithium oxide and combinations thereof;.
  • a metal oxide e.g., magnesium oxide, tungsten oxide, calcium oxide, barium oxide, lithium oxide and combinations thereof
  • Metal oxides supported on a carrier may be used. Suitable carriers include silica, alumina, titania, silica-alumina and combinations thereof, for example.
  • Isomerization catalysts capable of converting 1 -butene to 2-butene may generally include metal oxides (e.g., alumina, zirconia, sulfated zirconia), mixed oxides (e.g., silica- alumina, zirconia-silica), acidic zeolites, acidic clays (see, e.g., U.S. Letters Patent 5,153,165; U.S. Letters Patent 4,992,613; U.S. Patent Publication 2004/0249229 and U.S. Patent Publication 2006/0084831).
  • the catalyst is magnesium oxide.
  • the magnesium oxide may have a surface area of at least 1 m 2 /g or at least 5 m 2 /g, for example.
  • Various embodiments of the present invention are capable of forming propylene at high selectivity/productivity without the use of the isomerization catalyst.
  • some embodiments include reaction of the metathesis feed stream and the ethylene in the absence of an isomerization catalyst.
  • the embodiments described herein are capable of forming a metathesis product stream including less that 2 mol.%, or less than 1.5 mol.%, or less than 1 mol.% or less than 0.5 mol.% pentene, f r example.
  • the metathesis reactions generally occur at more severe reaction conditions than the dimerization and/or isomerization reaction.
  • the metathesis reaction may occur at a pressure of from 150 psig to 600 psig, or from 200 psig to 500 psig, for example.
  • the metathesis reaction may occur at a temperature of from 100°C to500°C, or from 200°C to 400°C or from 300°C to 350°C, for example.
  • the metathesis reaction may occur at a WHSV of from 3 hr "1 to 200 hr "1 or from 25 hr ' to 40 hr "1 , for example.
  • the propylene production process produces at least 100 MM lbs/year, or at least 300 MM lbs/year, or at least 500 MM lbs/year or at least 800 MM lbs/year of propylene, for example.
  • the contact time needed to obtain a desirable yield of metathesis reaction products depends upon several factors, such as the activity of the catalyst, temperature and pressure, for example. However, in one or more embodiments, the length of time during which the metathesis feed stream and the ethylene are contacted with the catalyst can vary from 0.1 s to 4 hours or from .5 s to 0.5 hours, for example.
  • the metathesis reaction may be conducted batch-wise or continuously with fixed catalyst beds, slumed catalyst, fluidized beds, or by using any other conventional contacting techniques, for example.
  • One or more embodiments include utilizing the isomerization catalyst that historically had been utilized in the metathesis reaction as an isomerization catalyst for use in the propylene or butene fractionation systems, for example. Such processes provide for the utilization of more ideal conditions (i.e., temperature and pressure) for the isomerization catalyst than possible when utilized in the metathesis reaction.
  • the metathesis product stream generally includes ethylene, propylene, C olefins, C5 olefins and C + olefins. Therefore, the process may further include separating the metathesis product stream into an ethylene stream, a propylene product stream, a C 4 stream and a C 5+ olefins stream. Such separation is known in the art (see, U.S. Letters Patent 7,214,841).
  • the metathesis product stream is separated within a propylene fractionation system.
  • the propylene fractionation system generally separates the metathesis product stream into a propylene stream, one or more recycle streams and a bottoms stream.
  • the bottoms stream may include the C5 and Ce + olefins, for example.
  • the recycle stream(s) may include olefins selected from butene, ethylene and combinations thereof, for example.
  • the recycle stream(s) may pass from the propylene fractionation system to the metathesis reaction downstream of any dimerization reaction, to the extent a dimerization reaction takes place, and without contacting isomerization catalyst.
  • the propylene fractionation system may include a first stage and a second stage.
  • the first stage is generally adapted to separate ethylene from other components present in the metathesis stream.
  • the second stage is generally adapted to separate propylene from C4 and heavier olefins, for example.
  • the recycle stream(s) may include olefins selected from butene, ethylene and combinations thereof, for example.
  • the recycle stream (or streams) may pass from the propylene fractionation system to the metathesis reaction without passing through a dimerization reactor or isomerization reactor. While described as "a recycle stream" exiting the propylene fractionation system, it is contemplated that the recy le stream may include multiple recycle streams.
  • first recycle stream exiting the first stage that includes ethylene
  • second recycle stream exiting the second stage that includes unreacted butene.
  • the "recycle stream” may not be recycled back to the propylene production process at all, but utilized in other chemical processes, for example.
  • Figure 1 a simplified process flow diagram of a process 100 for producing propylene according to embodiments disclosed herein is illustrated.
  • Figure 1 illustrates a process 100 including introducing a metathesis feed stream 102A to a metathesis reactor 104 having metathesis catalyst 105 disposed therein to form metathesis product stream 106.
  • Figure 1 illustrates a specific embodiment wherein ethylene 121 is mixed with the metathesis feed stream 102 via line 108 to form metathesis feed stream 102A.
  • a first feed stream 1 10 is introduced into a dimerization reactor 1 12 having dimerization catalyst 1 15 disposed therein to form dimerization product stream 1 14.
  • the dimerization product stream 1 14 (or a portion thereof) is generally utilized as the metathesis feed stream 102. However, this is not necessary for the practice of the invention and may vary in alternative embodiments as the feed stream 102 may be obtained in other ways in other embodiments.
  • FIG. 2 A specific embodiment is illustrated in Figure 2 wherein the embodiment includes the dimerization reactor 1 12 and the metathesis reactor 104.
  • Figure 2 illustrates a process 200 wherein the dimerization product stream 1 14 is passed to a butene fractionation system 116.
  • the butene fractionation system 116 includes a first column 118 adapted to separate butene present in the dimerization product stream 1 14 from other components to form a stream 120 including butene and a first column bottoms stream 122.
  • the stream 120 is passed to a second column 124 adapted to separate 1 -butene from 2- butene, forming a stream 128 including 2-butene and a stream 126 including 1 -butene.
  • the stream 128 feeds into the metathesis feed stream 102A which includes stream 128, ethylene 121 (via line 108), optionally stream 134 discussed in detail below, and optionally stream 142, also discussed in detail below.
  • the metathesis feed stream 102A undergoes reaction within the metathesis reactor 104, which contains metathesis catalyst 105, to form the metathesis product stream 106. It is significant to note that process 200 includes reaction within the metathesis reactor 104 in the absence of isomerization catalyst. In the specific embodiment illustrated in Figure 2, the metathesis product stream 106 is passed to a propylene fractionation system 130.
  • the propylene fractionation system 130 includes a first stage 132 adapted to separate ethylene from other components present in the metathesis product stream 106, thereby forming a stream 134 including ethylene and a first stage bottoms stream 136.
  • the first stage bottoms stream 136 is generally passed to a second stage 138 adapted to separate propylene from C4 and heavier olefins.
  • the propylene is recovered via stream 140, the C 4 olefins are recovered via stream 142.
  • the ethylene stream 134 may be recycled back to the metathesis feed stream 102A or directly to the metathesis reactor 104, while the C 4 olefins in stream 142 may be recycled back to the second column 124 via line 143, directly to the metathesis reactor 104 or to the metathesis feed stream 102A as shown. While the second stage 138 is adapted to separate propylene, C4 olefins and C5+ olefins (heavier olefins), Figure 2 does not illustrate the removal of the C5+ olefins from the second stage 138 or stream 142.
  • Separation and removal of heavier olefins is known in the art and may occur within the second stage 138 via a separate stream or may include further separation of stream 142 to remove the heavier olefins therefrom. Such separation could be achieved by recycling all or a portion of stream 142 to the butene fractionation system 1 18, for example.
  • Figure 3 illustrates a process 300 wherein the dimerization product stream 1 14 is passed to a catalyst quench system 302.
  • the catalyst quench system 302 cools the effluent in the dimerization product stream 1 14 and provides the ability to recover dimerization catalyst 1 15 present in the dimerization product stream 1 14.
  • the product from the catalyst quench system passes via line 304 to a butene recovery tower 306, which is adapted to separate butene present in the dimerization product stream 1 14 from other components to form a stream 308 including butene and a bottoms stream 310.
  • the bottoms stream 310 generally includes heavy components capable for use in gasoline, for example.
  • the stream 308 is passed to a butene dryer 312 to form stream 314, which is subsequently passed to a butene splitter 316 adapted to separate 1-butene from 2-butene, forming a stream 318 including 2-butene and a stream 320 including 1-butene.
  • the stream 318 feeds into the metathesis feed stream 102A which includes ethylene 121 (via line 108).
  • the metathesis feed stream 102A undergoes reaction within the metathesis reactor 104, which contains metathesis catalyst 105, to form the metathesis product stream 106.
  • process 300 includes reaction within the metathesis reactor 104 in the absence of an amount of isomerization catalyst sufficient to isomerize butene.
  • the metathesis product stream 106 is passed to a de-ethenizer 322 adapted to separate ethylene from other components present in the metathesis product stream 106, thereby forming a stream 328 including ethylene and a bottoms stream 324.
  • the bottoms stream 324 is generally passed to a de-propenizer 326 adapted to separate propylene from C 4 and heavier olefins.
  • the propylene is recovered via stream 330 and the C 4 olefins are recovered via stream 332.
  • the ethylene stream 328 may be recycled back to the metathesis feed stream 102A or optionally passed through a feed conditioning system 325 to form conditioned ethylene in line 336, which passes to feed stream 102A.
  • the C 4 olefins in stream 332 may be recycled back to the metathesis reactor 104.
  • the de-propenizer 326 is adapted to separate propylene, C 4 olefins and C5+ olefins (heavier olefins)
  • Figure 3 does not illustrate the removal of the C5+ olefins from the de-propenizer 326. Separation and removal of heavier olefins is known in the art and may occur within the de-propenizer 326 via a separate stream or may include further separation of stream 332 to remove the heavier olefins therefrom.
  • Metathesis reactions were compared by feeding various feedstocks, along with ethylene into a metathesis reactor with either a mixed catalyst system (i.e., MgO + WO 3 ) or a metathesis catalyst (WO 3 ) in the absence of an isomerization catalyst.
  • a mixed catalyst system i.e., MgO + WO 3
  • WO 3 metathesis catalyst
  • WHSV was calculated from reactant Bl or B2 over tungsten catalyst.
  • B2 refers to 2-butene
  • C 2 refers to ethylene
  • C 3 refers to formed propylene
  • WHSV was calculated from reactant Bl or B2 over tungsten catalyst.
  • 7.5 g tungsten catalyst and 30 g magnesium catalyst were used.
  • Example 1 and Example 2 utilized 7.5 g tungsten catalyst alone.
  • 1006 1 It was observed that the level of C5+ olefins formed significantly decreased when the isomerization catalyst (MgO) was eliminated from the metathesis reaction. In fact, the amount of C5+ olefins produced was negligible (e.g., less than 1 mol.%).

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Abstract

L'invention concerne des procédés et des systèmes pour la formation de propylène. Les procédés comprennent généralement la réaction d'un courant d'alimentation de métathèse comprenant au moins 95 % en poids de 2-butène avec de l'éthylène en présence d'un catalyseur de métathèse pour former un courant de produit de métathèse comprenant du propylène et récupérer le propylène à partir du procédé.
PCT/US2014/014823 2013-02-08 2014-02-05 Procédé de production de propylène WO2014123972A1 (fr)

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US201361762427P 2013-02-08 2013-02-08
US61/762,427 2013-02-08
US13/774,723 2013-02-22
US13/774,723 US20130172647A1 (en) 2010-10-13 2013-02-22 Propylene production process

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Publication number Priority date Publication date Assignee Title
EP3536678A1 (fr) * 2018-03-06 2019-09-11 Lyondell Chemical Technology, L.P. Procédé pour la production de propylène et d'alkylate
US10737992B2 (en) 2018-03-06 2020-08-11 Lyondell Chemical Technology, L.P. Methods of forming propylene and alkylate

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