WO2015051028A1 - Procédés et systèmes pour la préparation de 1,3-butadiène - Google Patents

Procédés et systèmes pour la préparation de 1,3-butadiène Download PDF

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Publication number
WO2015051028A1
WO2015051028A1 PCT/US2014/058678 US2014058678W WO2015051028A1 WO 2015051028 A1 WO2015051028 A1 WO 2015051028A1 US 2014058678 W US2014058678 W US 2014058678W WO 2015051028 A1 WO2015051028 A1 WO 2015051028A1
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Prior art keywords
butene
raffinate
stream
feed
butadiene
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PCT/US2014/058678
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English (en)
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Jr. William M. Cross
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Invista Technologies S.A.R.L.
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Publication of WO2015051028A1 publication Critical patent/WO2015051028A1/fr

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    • 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
    • C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
    • C07C7/08—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by extractive distillation
    • 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
    • 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
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • BACKGROUND Methods for the oxidative dehydrogenation of butenes can be used for the production of 1 ,3-butadiene.
  • Typical feedstocks have traditionally involved either steam cracker C4 Raffinate II or refinery based feedstock, produced via the extraction of the n- butenes from a Refinery Fluid Catalytic Cracking (FCC) methyl fe/f-butyl ether (MTBE) Raffinate.
  • FCC Fluid Catalytic Cracking
  • MTBE methyl fe/f-butyl ether
  • oxidative dehydrogenation utilizes feedstocks of n-butenes (typically mixtures of 1-butene, cis-2-butene, and trans-2-butene) with relatively high n-butene purities.
  • the remaining C4's (ranging from 5 to 20%) are primarily composed of C4 paraffins, such as isobutane, n-butane, and/or mixtures thereof.
  • C4 paraffins are often considered to be essentially nonreactive under typical oxidative dehydrogenation conditions for n-butenes.
  • many known processes traditionally employ a once-through operation of the oxidative dehydrogenation unit (ODU) where the resulting ODU raffinate, a mixture of unconverted n-butenes and C4 paraffins, is sold as a separate stream and consumed in downstream units-outside the scope of oxidative dehydrogenation.
  • ODU oxidative dehydrogenation unit
  • a method of manufacturing 1 ,3-butadiene is described. This method can include dimerizing ethylene via a dimerization step to produce a first product stream including n-butene.
  • the n-butene can be converted via an oxidative dehydrogenation step to produce a second product stream including 1 ,3-butadiene.
  • the second product stream which includes 1 ,3-butadiene, can be distilled via a first extractive distillation step to produce a 1 ,3-butadiene fraction and a first feed.
  • the first feed obtained from the first extractive distillation step can be partitioned to produce an n-butene raffinate A stream and an n-butene raffinate B stream.
  • the n-butene raffinate A stream can be recycled to the oxidative dehydrogenation step.
  • this method can include dimerizing ethylene via a dimerization step to produce a first product stream including n-butene.
  • the n-butene can be converted via an oxidative dehydrogenation step to produce a second product stream including 1 ,3- butadiene.
  • the second product stream which includes 1 ,3-butadiene, can be distilled via a first extractive distillation step to produce a 1 ,3-butadiene fraction and a raffinate A stream.
  • the raffinate A stream can include n-butane and butene, where butene can include -butene, cis/trans 2-butene, or mixtures thereof.
  • a feed from the raffinate A stream which can include n-butane and butane, can be recycled to the oxidative dehydrogenation step.
  • the n-butane in the feed can be present at a first concentration less than or equal to about 2 weight percent before recycling and can be allowed to build-up in the recycled feed to an extent greater than the first concentration and less than about 40 weight percent.
  • Such build-up can occur by cyclic recycling of the feed from the first extractive distillation step to the oxidative dehydrogenation process step.
  • a system for manufacturing 1 ,3-butadiene can include a dimerization unit configured to dimerize ethylene into a first product stream including n-butene.
  • the system can also include an oxidative dehydrogenation unit configured to receive the first product stream including n-butene and to convert the n-butene into a second product stream including 1 ,3-butadiene.
  • the system can include a first extractive distillation unit configured to receive the second product stream including 1 ,3-butadiene and to produce a 1 ,3-butadiene fraction and a first feed.
  • a partition module can be included, which is configured to receive the first feed and to produce an n-butene raffinate A stream and an n-butene raffinate B stream.
  • a recycle line can also be included that is configured to recycle at least a portion of the raffinate A stream from the partition module to the oxidative dehydrogenation unit.
  • FIG. 1 is a flow chart of a 1,3-butadiene manufacturing process.
  • FIG. 2 is a flow chart of another 1 ,3-butadiene manufacturing process.
  • FIG. 3 is a flow chart of a 1,3-butadiene manufacturing process in accordance with one embodiment of the present disclosure.
  • FIG. 4 is a flow chart of a 1 ,3-butadiene manufacturing process in accordance with one embodiment of the present disclosure.
  • FIG. 5 is a flow chart of a 1 ,3-butadiene manufacturing process in accordance with one embodiment of the present disclosure.
  • FIG. 6 is a flow chart of a 1 ,3-butadiene manufacturing process in accordance with one embodiment of the present disclosure.
  • FIG. 7 is a flow chart of a 1 ,3-butadiene manufacturing process in accordance with one embodiment of the present disclosure.
  • FIG. 8 is an extractive distillation tower section used in a 1 ,3-butadiene manufacturing process in accordance with one embodiment of the present disclosure.
  • FIG. 9 is an extractive distillation tower section used in a 1 ,3-butadiene manufacturing process in accordance with one embodiment of the present disclosure. It should be noted that the figures are merely exemplary of several embodiments of the present disclosure and no limitations on the scope of the present invention are intended thereby. DETAILED DESCRIPTION
  • compositions includes, “including,” and the like, and are generally interpreted to be open ended terms.
  • the term “consisting of” is a closed term, and includes only the components, structures, steps, or the like specifically listed, and that which is in accordance with U.S. Patent law.
  • Consisting essentially of or “consists essentially” or the like when applied to methods and compositions encompassed by the present disclosure refers to compositions like those disclosed herein, but which may contain additional structural groups, composition components or method steps. Such additional structural groups, composition components or method steps, etc., however, do not materially affect the basic and novel characteristic(s) of the compositions or methods, compared to those of the corresponding compositions or methods disclosed herein.
  • ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges
  • a concentration range of "about 0.1 % to about 5%” should be interpreted to include not only the explicitly recited concentration of about 0.1 wt% to about 5 wt%, but also include individual concentrations (e.g., 1 %, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1 %, 2.2%, 3.3%, and 4.4%) within the indicated range.
  • the term "about” can include traditional rounding according to significant figures of the numerical value.
  • the phrase "about 'x' to 'y'" includes “about 'x' to about 'y'".
  • the steps can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Furthermore, specified steps can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed step of doing X and a claimed step of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.
  • fractionation refers to a distillation step whereby a feed stream is separated into a light and heavy boiling fraction.
  • the term "extractive distillation” refers to a distillation step whereby a solvent is added to a fractionation step, for the purpose of changing the relative volatility of the constituent components within the feed, which is to be
  • Embodiments of the present disclosure employ, unless otherwise indicated, techniques of chemistry, and the like, which are within the skill of the art. Typically, such techniques are explained fully in the literature.
  • the disclosures herein relate to a method for the production of 1 ,3-butadiene (BD) and to the independent extractive distillation of n-butenes from paraffins.
  • One method of manufacturing 1 ,3-butadiene is illustrated in FIG. 1.
  • This method can use a fluid catalytic cracking (FCC) raffinate, wherein the raffinate is passed through an n- butene extractive distillation unit to remove n-butanes from the system or process prior to the oxidative dehydrogenation step.
  • FCC fluid catalytic cracking
  • the n-butene-rich first product stream 101 can be fed to an oxidative dehydrogenation unit to produce a second product stream 102 of crude C4s that includes 1 ,3-butadiene.
  • This product stream can be purified via a 1 ,3-butadiene extractive distillation unit, where the 1 ,3-butadiene fraction is removed and collected and the raffinate stream 103 can be discarded.
  • a 1 ,3-butadiene extractive distillation unit without incorporating the n-butene extractive distillation unit before the oxidative
  • n-butane build-up can require an increase in the overall oxidative dehydrogenation equipment size, particularly in the recovery section, which increases utilities usage for its processing.
  • good control of n-butane is of significant interest, particularly where feed n-butenes are intended to be recycled, rather than wasted by straight purging.
  • a subsequent recycle step can also be employed.
  • this configuration uses a separate n-butene extractive distillation column to purify the n- butenes from the dilute FCC C4 Raffinate feed, it can inherently provide an internal process means for the separation of the C4 paraffins from C4 olefins.
  • FIG. 2 Similar to FIG. 1 , the n-butene-rich first product stream 201 can be fed to an oxidative dehydrogenation unit to produce a second product stream 202 of crude C4s that includes 1 ,3-butadiene.
  • This product stream can be purified via a 1 ,3- butadiene extractive distillation unit, where the 1 ,3-butadiene fraction is removed and collected and a recycle raffinate stream 203 can be recycled back to the n-butene extractive distillation step.
  • the raffinate purge 204 can be discarded.
  • n-butene feedstocks One alternative to this process is to utilize higher purity n-butene feedstocks.
  • High purity n-butenes can be produced via ethylene dimerization technologies.
  • two isomers are possible, 1- butene and cis/trans 2-butene.
  • dimerization processes can also produce an n-butene stream which contains minor portions of C4 paraffin components that must be dealt with.
  • These paraffins, particularly n-butane can build-up in a process configuration intended to obtain high overall n-butene conversion, such that an appropriate and economic process solution should be developed to handle these constituents.
  • a method of manufacturing 1 ,3-butadiene is described. This method can include dimerizing ethylene via a dimerization step to produce a first product stream including n-butene.
  • the n-butene can be converted via an oxidative dehydrogenation step to produce a second product stream including 1 ,3-butadiene.
  • the second product stream which includes 1 ,3-butadiene, can be distilled via a first extractive distillation step to produce a 1 ,3-butadiene fraction and a first feed.
  • the first feed obtained from the first extractive distillation step can be partitioned to produce an n-butene raffinate A stream and an n-butene raffinate B stream.
  • the n-butene raffinate A stream can be recycled from the partitioning step to the oxidative dehydrogenation step.
  • Dimerizing ethylene to produce a product stream that includes n-butene is generally known in the art. Any suitable method of dimerizing ethylene to produce a product stream that includes n-butene is contemplated as useful in the present technology.
  • ethylene can be passed over a supported catalyst including a metal or combinations of metals from Group VIII of the Periodic Table and an oxide of a metal or combination of metals from group VIIB of the Periodic Table.
  • palladium and molybdenum oxide can be included in the supported catalyst.
  • Optimal flow rates can depend on temperature, pressure, catalyst particle size and surface area, and other process considerations. All of these parameters can be optimized to achieve desirable yields. Such optimization parameters are known in the art.
  • Other methods of dimerizing ethylene are known in the art and can likewise be used in the present technology.
  • Oxidative dehydrogenation is also generally known in the art. Any suitable oxidative dehydrogenation method to convert n-butene to a second product stream that includes 1 ,3-butadiene is contemplated as part of the current technology. Oxidative dehydrogenation can use a variety of catalysts, such as mixed oxides including ferrites and bismuth molybdate. Additionally, a variety of temperatures, pressures, and flow rates can be used to optimize the oxidative dehydrogenation reaction. Such conditions are known in the art and are contemplated as part of the current technology.
  • Extractive distillation and fractionation are also generally known in the art. Any suitable extractive distillation or fractionation method is contemplated as part of the current technology.
  • One such method can use solvents such as acetonitrile, methyl ethyl ketone, dimethylformamide, furfural, N-methyl-2-pyrrolidone, acetone, sulfalone, dimethylacetamide, water, other suitable solvents, and combinations thereof to facilitate the separation of 1 ,3-butadiene from the other components of the second product stream.
  • solvents such as acetonitrile, methyl ethyl ketone, dimethylformamide, furfural, N-methyl-2-pyrrolidone, acetone, sulfalone, dimethylacetamide, water, other suitable solvents, and combinations thereof to facilitate the separation of 1 ,3-butadiene from the other components of the second product stream.
  • the current technology can employ a variety of additional partition steps and subsequent recycling steps.
  • the partition step can be used to partition the first feed obtained from the first extractive distillation step to produce an n-butene raffinate A stream and an n-butene raffinate B stream. Specific embodiments illustrating a variety of these partition steps are described in greater detail below, but an initial overview is provided here.
  • the partition step can include a second extractive distillation step.
  • the partition step can include a fractionation step.
  • the fractionation step can also include purging the n-butene raffinate B stream.
  • the n-butene raffinate A stream can be recycled from the partitioning step to the oxidative dehydrogenation step via any suitable recycling step.
  • the partition step can include distilling the first feed from the first extractive distillation step via a second extractive distillation step to produce a second feed and a n-butene raffinate A stream. Additionally, the second feed from the second extractive distillation step can be fractionated via a fractionation step to produce an n-butene raffinate B stream. In this case, both the raffinate A stream and the raffinate B stream can be recycled to the oxidative dehydrogenation step.
  • one such embodiment can include dimerizing ethylene via a dimerization step to produce a first product stream including n-butene.
  • the n-butene can be converted via an oxidative dehydrogenation step to produce a second product stream including 1 ,3-butadiene.
  • the second product stream, including 1 ,3-butadiene can be distilled via a first extractive distillation step to produce a 1 ,3-butadiene fraction and a first feed.
  • the first feed from the first extractive distillation step can be further distilled via a second extractive distillation step to produce an n-butene raffinate A stream and an n-butene raffinate B stream.
  • the n-butene raffinate A stream from the second extractive distillation step can be recycled to the oxidative dehydrogenation step.
  • This embodiment is illustrated in FIG. 3.
  • dimerization of ethylene can produce a first product stream 301 , including n-butene, which can be transferred to an oxidative dehydrogenation step.
  • the oxidative dehydrogenation process can produce a second product stream 302 of crude C4s, including 1 ,3-butadiene.
  • the second product stream 302 can be passed to a first extractive distillation step to produce a 1 ,3-butadiene fraction and a first feed.
  • the 1.3-butadiene fraction can be collected and the first feed can be further partitioned using a second extractive distillation step to produce an n-butene-rich raffinate A stream 304 and an n-butene-lean raffinate B stream 303.
  • the raffinate A stream 304 can be recycled back to the oxidative dehydrogenation step and cycle through the subsequent steps again.
  • the raffinate B stream 303 can be purged to eliminate butanes from the process.
  • FIG. 3 illustrates one example of such a configuration.
  • lean extractive solvent above the n-butene extraction zone.
  • Lean solvent refers to a regenerated solvent containing little absorbed material. In this case, 1 ,3 butadiene is the primary absorbed material, which is “lean” or at a substantially reduced concentration in the regenerated solvent.
  • a lean extractive solvent is prepared, in addition to the solvent injection made for that of the 1 ,3 butadiene extractive distillation column.
  • a lean extractive solvent can include fufurol, acetone, methyl ethyl ketone, dimethyl acetamide, dimethylformamide (DMF), acetonitrile (ACN), n-methyl pyrrolidone (NMP), morpholine, sulfolane, water, and mixtures thereof.
  • This provides an extractive column with a minimum of two extractive solvent injections, one above the new additional n-butene zone, and one above the traditional lean solvent injection from 1 ,3 butadiene recovery.
  • an additional side heater may be placed between the new top extraction zone and above the traditional 1 ,3 butadiene zone to aid stripping of the butenes above or within the 1 ,3 butadiene zone.
  • n-butene raffinate B The upper raffinate (Raffinate B) can be produced substantially solvent free, using a traditional fractionation zone placed above the new n-butene extraction zone.
  • a side rectifier unit may be used for solvent removal. Water washes, typically associated with extractive distillation units, may then be used for both raffinates to provide solvent free product raffinates.
  • a method of manufacturing 1 ,3-butadiene can include dimerizing ethylene via a dimerization step to produce a first product stream including n- butene.
  • n-butene can be converted via an oxidative dehydrogenation step to produce a second product stream including 1 ,3-butadiene.
  • Additional steps can include distilling the 1 ,3-butadiene via a first extractive distillation step to produce a 1 ,3-butadiene fraction and a Raffinate A stream.
  • the Raffinate A stream can include n-butane and butene, where butene can be 1 -butene, cis/trans 2-butene, or mixtures thereof.
  • the Raffinate A stream can be recycled via a recycling step from the first extractive distillation step to the oxidative dehydrogenation step, the feed comprising n-butane and butene.
  • the n-butane in the feed can be present at a first concentration less than or equal to about 2 weight percent before recycling, and the n-butane can be allowed to build-up in the recycled feed to an extent greater than the first concentration and less than about 40 weight percent.
  • the first concentration can be less than or equal to about 3 weight percent, and the n-butane can be allowed to build-up in the recycled feed to an extent greater than the first concentration and less than about 40 weight percent.
  • the first concentration can be less than or equal to about 3 weight percent, and the n-butane can be allowed to build-up in the recycled feed to an extent greater than the first concentration and less than about 20 weight percent. In still another aspect, the first concentration can be less than or equal to about 5 weight percent, and the n-butane can be allowed to build-up in the recycled feed to an extent greater than the first concentration and less than about 15 weight percent.
  • the build-up occurs by cyclic recycling of the feed from the first extractive distillation step to the oxidative dehydrogenation process step.
  • the Raffinate A stream can be purged in an amount of about 0.2% to 20% by mass, or from 0.5% to 5% by mass in another example.
  • the feed can include at least about 80 weight percent of the raffinate A stream. In another aspect, the feed can include at least about 90 weight percent of the raffinate A stream.
  • dimerization of ethylene can produce a first product stream 401 , including n-butene, which can be transferred to an oxidative dehydrogenation step.
  • the oxidative dehydrogenation process can produce a second product stream 402, including 1 ,3-butadiene.
  • the second product stream 402 can be passed to a distillation step utilizing a first extractive distillation step to produce a 1 ,3-butadiene fraction and a raffinate A stream 403.
  • the raffinate A stream 403 can include n-butane and butene, where the butene can include -butene, cis/trans 2-butene, or mixtures thereof.
  • a feed 404 of the composedte A stream 403 can be recycled back to the oxidative dehydrogenation step and residual raffinate product 405 can be purged.
  • This embodiment can be used as an alternative to the production of 1 ,3 butadiene using the configuration illustrated in FIG. 3.
  • the production of 1 ,3 butadiene, using a dimerization process may utilize a direct recycle.
  • a minor impurity in the feed, n-butane is allowed to build-up allowing high overall conversion. It has been found that building up n-butane in the raffinate recycle to from 1% to 20% can be effective in the methods and systems of the present disclosure, and more typically from 3% to 10% can be desirable.
  • Such a direct recycle configuration is provided in FIG. 4.
  • the n-butane is purged from the process by recycling up to 97% of the produced raffinate from the butadiene extractive distillation column and purging as low as 3% of the raffinate.
  • the method can include dimerizing ethylene via a dimerization step to produce a first product stream including n-butene.
  • the n-butene can be converted via an oxidative dehydrogenation step to produce a second product stream including 1 ,3-butadiene.
  • the second product stream, including 1 ,3-butadiene can be distilled via a first extractive distillation step to produce a 1 ,3-butadiene fraction and a first feed.
  • the first feed from the first extractive distillation step can be
  • n-butene raffinate A stream and an n-butene raffinate B stream The n-butene raffinate A stream from the fractionation step can be recycled to the oxidative dehydrogenation step and the n-butene raffinate B stream can be purged. This embodiment is illustrated in FIG. 5.
  • dimerization of ethylene can produce a first product stream
  • the oxidative dehydrogenation process can produce a second product stream 502 of crude C4s, including 1 ,3-butadiene.
  • the second product stream 502 can be passed to a first extractive distillation step to produce a 1 ,3-butadiene fraction and a first feed 503 that includes the raffinate A from the extractive distillation step.
  • the 1.3-butadiene fraction can be collected and the first feed 503 is split into a recycled raffinate 504, which is recycled back to the oxidative dehydrogenation step, and a raffinate feed 505, which is transferred to the subsequent distillation or fractionation step.
  • the raffinate feed 505 is further partitioned via fractionation into an n-butene-rich raffinate A stream 506 and an n-butene-lean raffinate B stream 507.
  • the raffinate A stream 506 is recycled back to the oxidative distillation step and the raffinate B stream 507 is purged from the process.
  • the method can include dimerizing ethylene via a dimerization step to produce a first product stream including n-butene.
  • the n-butene can be converted via an oxidative dehydrogenation step to produce a second product stream including 1 ,3-butadiene.
  • the second product stream, including 1 ,3-butadiene can be distilled via an extractive distillation step to produce a 1 ,3-butadiene fraction and a first feed.
  • the first feed from the first extractive distillation step can be fractionated to produce an n-butene raffinate A stream and an n-butene raffinate B stream.
  • the n- butene raffinate A stream from the fractionation step can be recycled to the oxidative dehydrogenation step. This embodiment is illustrated in FIG. 6.
  • dimerization of ethylene can produce a first product stream 601 , including n-butene, which can be transferred to an oxidative dehydrogenation step.
  • the oxidative dehydrogenation process can produce a second product stream 602 of crude C4s, including 1 ,3-butadiene.
  • the second product stream 602 can be passed to a first extractive distillation step to produce a 1 ,3-butadiene fraction and a first feed.
  • the 1 ,3-butadiene fraction can be collected and the first feed can be transferred to a fractionation section where the first feed is further partitioned into a 1-butene-rich raffinate A stream 603, which is recycled back to the oxidative dehydrogenation step, and a n-butene-lean raffinate B stream 604, which can be removed from the process.
  • FIGS. 5 and 6 represent other desirable and economic methods for using similarly rich n-butene feed streams, but with even higher utilization. These figures show the use of 1-butene vs. 2-butene, although this feed may include either n-butene isomer or mixtures thereof.
  • "rich 1-butene feed stream” generally refers to a stream or portion thereof containing 1-butene in an amount ranging from 60% to 100% by weight.
  • the rich 1-butene feed stream can contain 1-butene in an amount ranging from 60% to 98% by weight.
  • the rich 1-butene feed stream can contain 1-butene in an amount ranging from 80% to 95% by weight.
  • the rich 1-butene feed stream can contain 1- butene in an amount ranging from 80% to 99% by weight.
  • FIG. 6 provides the use of a lean feed from a vapor side draw.
  • lean feed generally refers to a stream or portion thereof containing n-butene in an amount ranging from 20% to 95% by weight.
  • the n-butene can be present in an amount ranging from 50% to 95% by weight.
  • an additional fractionation unit FIG. 5
  • zone FIG. 6
  • the n-butane can be present in a bottom stream from the fractionator in an amount ranging from 15% to 99% by weight.
  • heat integration refers to the use of a hot process stream to handle some energy duty, required by the distillation column reboiler. This stream could be obtained from a pump around, vapor side draw or a process condenser load.
  • heat integration schemes with this new column can be constructed by those skilled in the art.
  • FIGS. 5 and 6 wherein the 1 ,3 butadiene extractive distillation section and 1-butene fractionation zone are integrated using a single column with divided walls or separate rectifying and/or stripping sections.
  • the method can include dimerizing ethylene via a dimerization step to produce a first product stream including n-butene.
  • the n-butene can be converted via an oxidative dehydrogenation step to produce a second product stream including 1 ,3-butadiene.
  • the second product stream, including 1 ,3-butadiene can be distilled via a first extractive distillation step to produce a 1 ,3-butadiene fraction and a first feed.
  • the first feed from the first extractive distillation step can be distilled via a second extractive distillation step to produce a second feed and an n-butene raffinate A stream.
  • the second feed from the second extractive distillation step can be
  • n-butene raffinate B stream fractionated to produce an n-butene raffinate B stream.
  • the n-butene raffinate A stream and the n-butene raffinate B stream from the second extractive distillation step and the fractionation step can be recycled to the oxidative dehydrogenation step.
  • dimerization of ethylene can produce a first product stream 701 , including n-butene, which can be transferred to an oxidative dehydrogenation step.
  • the oxidative dehydrogenation process can produce a second product stream 702 of crude C4s, including 1 ,3-butadiene.
  • the second product stream 702 can be passed to a first extractive distillation step to produce a 1 ,3-butadiene fraction and a first feed.
  • 1 ,3- butadiene can be collected and the first feed can be passed to a second extractive distillation step to produce a second feed 703 and an n-butene raffinate A stream 704.
  • the second feed 703 is further partitioned via fractionation to produce bottoms 705 rich in butanes, which are removed from the process, and overhead 706 rich in 1-butene, to produce a 1-butene-rich raffinate B stream 707 being recycled back to the oxidative dehydrogenation step.
  • a system for manufacturing 1 ,3-butadiene can include a dimerization unit configured to dimerize ethylene into a first product stream including n-butene.
  • the system can also include an oxidative
  • dehydrogenation unit configured to receive the first product stream including n-butene and to convert the n-butene into a second product stream including 1 ,3-butadiene.
  • the system can include a first extractive distillation unit configured to receive the second product stream including 1 ,3-butadiene and to produce a 1 ,3-butadiene fraction and a first feed.
  • a partition module can be included, which is configured to receive the first feed and to produce an n-butene raffinate A stream and an n-butene raffinate B stream.
  • a recycle line can also be included that is configured to recycle at least a portion of the raffinate A stream from the partition module to the oxidative dehydrogenation unit.
  • a variety of dimerization units are known in the art and any suitable dimerization unit can be used with the present technology.
  • a suitable dimerization unit can be designed to house a variety of catalysts, such as supported catalysts including a metal or combinations of metals from Group VIII of the Periodic Table and an oxide of a metal or combination of metals from group VI IB of the Periodic Table.
  • catalysts can include palladium and molybdenum oxide.
  • the catalysts can be adapted to have varying surface areas and particle sizes based on preference of the user.
  • dimerization unit can be adapted to accommodate a variety of
  • Dimerization units using a variety of such parameters to optimize desired outcomes are contemplated as useful in the present technology.
  • Oxidative dehydrogenation units are known in the art and can be adapted to house a variety of catalysts known in the art, such as metal oxides, including ferrites and bismuth-molybdate. Oxidative dehydrogenation units can be adapted to
  • Oxidative dehydrogenation units using a variety of such parameters to optimize desired outcomes are contemplated as useful in the present technology.
  • a first extractive distillation unit can include any suitable extractive distillation unit. Such units are known in the art and are contemplated as useful in the present technology.
  • an extractive distillation unit can be adapted to use a variety of separation solvents such as acetonitrile, methyl ethyl ketone, dimethylformamide, furfural, N-methyl-2-pyrrolidone, acetone, sulfalone, dimethylacetamide, water, other suitable solvents, and combinations thereof.
  • the extractive distillation unit can be adapted to accommodate a variety of flow rates, temperatures, pressures, columns, column configurations, and other suitable parameters based on desired separation outcomes.
  • a partition module can include a second extractive distillation unit.
  • a partition module can include a fractionation unit. Such a fractionation unit can be positioned relative to the first extractive distillation unit such that a solvent can cascade from the fractionation unit to the first extractive distillation unit.
  • Fractionation units are generally known in the art. Any suitable fractionation unit can be used in the current technology and can employ any suitable optimization parameters such as temperatures, pressures, flow rates, columns, separation solvents, and other suitable parameters.
  • a recycle line can be configured to recycle at least a portion of the raffinate A stream from the partition module to the oxidative dehydrogenation unit.
  • the partition module can include both a second extractive distillation unit and a fractionation unit.
  • the second extractive distillation unit can be configured to receive the first feed and to produce a second feed and the n-butene raffinate A stream.
  • the fractionation unit can be configured to receive the second feed and to produce the n-butene raffinate B stream.
  • the recycle line can be configured to recycle at least a portion of both the raffinate A stream and raffinate B stream to the oxidative dehydrogenation unit.
  • a system for manufacturing 1 ,3-butadiene can include a dimerization unit configured to dimerize ethylene into a first product stream including n-butene. Additionally, the system can include an oxidative dehydrogenation unit configured to receive the first product stream including n-butene and to convert the n-butene into a second product stream including 1 ,3-butadiene. The system can also include a first extractive distillation unit configured to receive the second product stream including 1 ,3-butadiene and to produce a 1,3- butadiene fraction and a first feed.
  • the system can include a second extractive distillation unit configured to receive the first feed and to produce an n-butene raffinate A stream.
  • the system can include a fractionation unit configured to receive the second feed and to produce an n-butene raffinate B stream.
  • the system can also include a recycle line configured to recycle at least a portion of the raffinate A stream and at least a portion of the raffinate B stream from the second extractive distillation unit and the fractionation unit to the oxidative dehydrogenation unit.
  • a system for manufacturing 1 ,3-butadiene can include a dimerization unit configured to dimerize ethylene into a first product stream including n-butene.
  • the system can include an oxidative dehydrogenation unit configured to receive the first product stream including n-butene and to convert the n-butene into a second product stream including 1 ,3-butadiene.
  • the system can also include a first extractive distillation unit configured to receive the second product stream including 1 ,3-butadiene and to produce a 1 ,3-butadiene fraction and a first feed.
  • the system can include a fractionation unit configured to receive the first feed and to produce an n-butene raffinate A stream and an n-butene raffinate B stream.
  • the system can also inlcude a recycle line configured to recycle at least a portion of the raffinate A stream from the fractionation unit to the oxidative dehydrogenation unit.
  • a system for manufacturing 1 ,3-butadiene can include a dimerization unit configured to dimerize ethylene into a first product stream including n-butene.
  • the system can include an oxidative dehydrogenation unit configured to receive the first product stream including n-butene and to convert the n-butene into a second product stream including 1 ,3-butadiene.
  • the system can also include a first extractive distillation unit configured to receive the second product stream including 1 ,3-butadiene and to produce a 1 ,3-butadiene fraction and a first feed.
  • the system can include a second extractive distillation unit configured to receive the first feed and to produce an n-butene raffinate A stream and an n-butene raffinate B stream.
  • the system can also include a recycle line configured to recycle at least a portion of the raffinate A stream from the second extractive distillation unit to the oxidative dehydrogenation unit.
  • a system for manufacturing 1 ,3-butadiene can include a dimenzation unit configured to dimerize ethylene into a first product stream including n-butene.
  • the system can include an oxidative dehydrogenation unit configured to receive the first product stream including n-butene and to convert the n-butene into a second product stream including 1 ,3-butadiene.
  • the system can also include a first extractive distillation unit configured to receive the second product stream including 1 ,3-butadiene and to produce a 1 ,3-butadiene fraction and a first feed.
  • the system can include a fractionation unit configured to receive the first feed and to produce an n-butene raffinate A stream and an n-butene raffinate B stream.
  • the system can also include a recycle line configured to recycle at least a portion of the raffinate A stream from the fractionation unit to the oxidative dehydrogenation unit.
  • the fractionation unit can be positioned above or otherwise relative to the extractive distillation unit such that a solvent can cascade from the fractionation unit down to the extractive distillation unit.
  • a system for manufacturing 1 ,3-butadiene can include a dimerization unit configured to dimerize ethylene into a first product stream including n- butene. Further, the system can include an oxidative dehydrogenation unit configured to convert the n-butene into a second product stream including 1 ,3-butadiene. The system can also include a first extractive distillation unit configured to produce a 1 ,3-butadiene fraction and a Raffinate A stream comprising n-butane and butene, the butene comprising 1 -butene, cis/trans 2-butene, or mixtures thereof.
  • a feed line can also be present and configured to recycle a feed from the Raffinate A stream from the first extractive distillation unit to the oxidative dehydrogenation unit.
  • the feed can comprise n-butane and butene.
  • the system can be adapted such that the n- butane in the feed before recycling can be present at a first concentration less than or equal to about 2 weight percent and n-butane can be allowed to build-up in the recycled feed to an extent greater than the first concentration and less than about 40 weight percent.
  • the build-up occurs by cyclic recycling of the feed from the first extractive distillation unit to the oxidative dehydrogenation unit.
  • a simulation representative of the configuration illustrated in FIG. 5 is provided below.
  • a mixed 1 -butene recycle stream is recycled back to the oxidative dehydrogenation section, n-butane is purged from the overall system as bottoms from a fractionator, and the mixed recycle is produced through both the direct recycle of a produced raffinate (after BD extraction) and recycle of a butene rich fraction produced (as overheads via fractionation).
  • the oxidative dehydrogenation effluent, going into extraction, was carried out using techniques generally known to those in the art.
  • the feed used for oxidative dehydrogenation was chosen as 1 -butene. No isomerization of 1 -butene to 2-butenes was considered in the oxidative dehydrogenation section.
  • Tables 2 and 3 provide two additional cases, whereby the price of 1-butene to
  • Tables 1-3 The main variable changes between the 3 cases (Tables 1-3) in Example 1 occur through adjustments in (1) the quantity of Raffinate sent to fractionation and (2) the distillation overhead design specification.
  • Table 2 is based on 20% of the Raffinate sent to distillation, using 60 trays at a 5 reflux ratio.
  • Table 3 is based on 30% of the Raffinate sent to distillation, using 60 tray and a 3 reflux ratio.
  • Example 1 shows how an oxidative dehydrogenation unit, using a rich 1-butene feedstock, can be integrated into an existing ethylene complex, containing a Raffinate II superfractionator, for separation of 1-butene and 2-butenes. Given the small quantity of purge required, it can be seen that this design would require minimal modification and/or change to a fractionator's hydraulic capacity, while increasing the overall 1- butene utilization and corresponding butadiene yield.
  • Table 1 represents a valuation between 1 ,3 butadiene to 1-butene where the added utilities cost associated with recycling the feed is justified. For smaller price spreads, the specification on the fractionation can be reduced and/or the total quantity of feed sent to fractionation can be modified, as provided in Tables 2 & 3.
  • Table 4 provides the compositional and flowrate information for the feed, recycle, and purge streams.
  • Example 1 A trade off from Example 1 to Example 2 is the increased hydraulic sizing of the all the equipment used in the oxidative dehydrogenation section as well as the use of heat recovery equipment. A good comparison of cases to illustrate this comes from Table 2 vs. Table 4, whereby the feed utilization is higher (99.99% vs. 99.7%) and the quantity of n-butane in the recycle raffinate is approximately 3 times lower. As such, addition of fractionation is often justified when high feed utilization of butenes is needed.
  • an extractive distillation tower as depicted in FIG. 8 can be used with this and other system configurations.
  • Stream 802 is introduced along the vertical tower between the two raffinate products.
  • a first solvent injection (Traditional), Stream 801 is used to impart the butadiene recovery from the extractive distillation unit.
  • Only trace quantities of butenes will reside in the bottoms solvent stream sent to recovery [807, so essentially 100% of the butenes are recovered as draws, either as raff i nates A 805 and B 804 or as minor impurities within the butadiene stream 806.
  • Example 3 provides an additional option for reducing the recycle described in
  • Example 2 With the addition of a second raffinate purge (Raffinate B) and a solvent injection to a conventional butadiene extractive distillation unit, some additional separation of the butenes from the n-butane can be set up, without substantial equipment modification.
  • Raffinate A & Raffinate B both with relatively high butene concentrations, but disproportionate n-butane contents, high utilization of the butene feed can be accomplished while allowing for an n-butane purge.
  • FIG. 9 provides a simplified view of such an extractive distillation tower section and FIG. 3 provides the overall oxidative dehydrogenation process flow utilized for this example.
  • Raffinate A represents a side draw of approximately 89% of the total Raffinate produced through the use of the extractive distillation process provided in Figure 9.
  • Raffinate B represents 11% of this material, which is taken as an n-butane purge for the system.
  • Stream 902. is introduced between the two raffinate products.
  • a first solvent injection (Traditional), Stream 901 , is used to impart the butadiene recovery from the extractive distillation unit.
  • the relative solvent mass flow rates, Streams 901 and 902, to the crude C4 feed Stream 903 were set as follows:
  • the 1 ,3 Butadiene purity was set to be 99 wt%, and a solvent of NMP and water was utilized.
  • Table 5 illustrates the second injection benefit, showing a 50% increase in the relative n-butane content in the Raffinate B draw.
  • Raffinate B was approximately 11 % of the total raffinate produced.
  • the relative quantity of n-butane found in Raffinate B is
  • both solvent injections could represent the same solvent composition and varying flow rates.
  • Information provided in Table 5 utilized varying water contents for the two injections, whereby more relative water to solvent ratio was utilized for the top injection.
  • solvent injections with varying aqueous concentrations and/or varying solvent compositions may be utilized to further aid the relative volatility between the desired recycle component (butenes) and the purge component (n-butane).
  • varying flow rates and added equipment for reducing solvent carryover or recovering heat may be used, as would be appreciated by one skilled in the art.
  • Table 6 represents a process with 98.7% Feed Utilization
  • Table 7 represents a slightly higher Feed Utilization of 99.7%.
  • the n-butene Raffinate A stream can be a vapor side draw comprising n-butene in an amount ranging from 60% to 99% by weight.
  • the n-butene raffinate B stream can be an overhead comprising n-butene in an amount ranging from 40% to 96% by weight

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Abstract

La présente invention porte sur des procédés et systèmes pour la préparation de 1,3-butadiène. De tels procédés et systèmes peuvent comprendre la dimérisation d'éthylène pour produire un premier courant de produits, comprenant du n-butène. Le premier courant de produits peut être converti en un second courant de produits, comprenant du 1,3-butadiène, par déshydrogénation oxydative. Le second courant de produits peut être distillé par au moins une première étape de distillation extractive pour produire une fraction de 1,3-butadiène et un produit raffinat. Au moins une partie du produit raffinat peut être recyclée et/ou introduite dans des étapes de séparation supplémentaires.
PCT/US2014/058678 2013-10-02 2014-10-01 Procédés et systèmes pour la préparation de 1,3-butadiène WO2015051028A1 (fr)

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WO2018124580A1 (fr) * 2016-12-29 2018-07-05 (주) 엘지화학 Procédé de production de butadiène
WO2018124579A1 (fr) * 2016-12-29 2018-07-05 (주) 엘지화학 Procédé de préparation de butadiène
KR20180077768A (ko) * 2016-12-29 2018-07-09 주식회사 엘지화학 부타디엔 제조방법
KR20180077703A (ko) * 2016-12-29 2018-07-09 주식회사 엘지화학 부타디엔 제조방법
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KR102246184B1 (ko) 2016-12-29 2021-04-29 주식회사 엘지화학 부타디엔 제조방법
KR102246175B1 (ko) 2016-12-29 2021-04-29 주식회사 엘지화학 부타디엔 제조방법
CN109311782B (zh) * 2016-12-29 2021-08-17 株式会社Lg化学 制备丁二烯的方法

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