Olefin metathesis by reactive distillation

Abstract

A process and reaction system for olefin metathesis by reactive distillation utilizing liquid phase metathesis of reactive olefins in the presence of a homogeneous metathesis catalyst system, where a light metathesis product is produced, leaving a liquid phase as a vapor phase, and a heavy metathesis product is produced in the liquid phase. The light metathesis product can be subjected to a separation, and the heavy metathesis product can be subjected to a different separation.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE This disclosure relates generally to metathesis reactions, and more particularly to the metathesis of olefins by reactive distillation. [Background technology]

[0002] Olefin products can be produced by metathesis. Metathesis generally involves contacting one or more reactive olefins in the presence of a metathesis catalyst to form at least one olefin product different from the one or more reactive olefins. Self-metathesis involves contacting one molecule of a reactive olefin with a second molecule of the same reactive olefin to form one or more olefin products different from the reactive olefin. Cross-metathesis involves contacting a molecule of a first reactive olefin with a molecule of a second reactive olefin to form one or more olefin products different from the reactive olefin.

[0003] In batch metathesis of linear olefins to produce light olefin products (e.g., ethylene and / or propylene), the light olefin products can accumulate in the reactor and form products other than the target olefin products. One solution to removing the light olefin products in batch mode is to operate the reactor under vacuum pressure. However, vacuum pressure can have low separation efficiency and can be too expensive for large-scale operations.

[0004] There is a need for a metathesis process that can be carried out on a large scale and that can remove light olefin products from the reaction to reduce the formation of undesirable by-products that are not the target olefin products. Summary of the Invention

[0005] The process of olefin metathesis by reactive distillation can include reacting a first reactive olefin in the presence of a homogeneous metathesis catalyst system in a reaction zone to form a metathesis product comprising a first product olefin (a light product olefin) and a second product olefin (a heavy product olefin). The metathesis achieved by the process can be carried out on a continuous basis, rather than a batch basis. The first product olefin (e.g., the light product olefin) can be continuously removed from the reaction zone to reduce and / or prevent the formation of by-products that are not the target product olefin.

[0006] The process can be carried out in a distillation column having a reaction zone, a first product separation zone, and a second product separation zone. The reaction zone can include a liquid collection tray and can be positioned above the first product separation zone and below the second product separation zone. The process can further include separating the liquid-phase unreacted reactive olefin and the second product olefin in the first product separation zone into a vapor fraction containing the unreacted reactive olefin and a liquid fraction containing the second product olefin, the vapor fraction being recycled to the reaction zone via a vapor passage in the liquid collection tray. The process can also include separating the vapor-phase unreacted reactive olefin and the first product olefin in the second product separation zone into a vapor fraction containing the first product olefin and a liquid fraction containing the unreacted reactive olefin, the liquid fraction being recycled to the reaction zone.

[0007] The process can also be carried out in a distillation column having a reaction zone and a second product separation zone, and in a stripping column configured as the first product separation zone. The reaction zone contains or consists of a liquid phase and is located below the second product separation zone in the distillation column. The process can include separating the unreacted reactive olefins and the second product olefins received as an overhead reflux in the stripping column of the first product separation zone into a vapor fraction containing the unreacted reactive olefins and a liquid fraction containing the second product olefins, the vapor fraction being recycled to the reaction zone via a stream fluidly connected to the top of the stripping column and the reaction zone of the distillation column. The process can further include separating the unreacted reactive olefins and the first product olefins in the vapor phase in a second product separation zone in the distillation column above the reaction zone into a vapor fraction containing the first product olefins and a liquid fraction containing the unreacted reactive olefins, the liquid fraction being recycled to the reaction zone.

[0008] The olefin metathesis system has a reaction zone, a first product separation zone below the reaction zone, and a second product separation zone above the reaction zone, the reaction zone configured to contact a first reactive olefin in the presence of a homogeneous metathesis catalyst system to form a metathesis product comprising a first product olefin and a second product olefin, the reaction zone having a reaction tray and a liquid collection tray below the reaction tray, the first product separation zone having at least one distillation structure, and a distillation column, the first product separation zone being fluidly connected to the reaction zone via a vapor passageway of the liquid collection tray; and the liquid collection tray of the reaction zone of the distillation column. and a catalyst removal unit fluidly connected to the distillation column and configured to receive a liquid phase containing the second product olefin, unreacted reactive olefin, and the homogeneous metathesis catalyst system from the liquid collection tray and separate the liquid phase into a first stream containing the unreacted reactive olefin and the second product olefin and a second stream containing the homogeneous metathesis catalyst system; the first stream is connected to the catalyst removal unit and to a first product separation zone of the distillation column, the first product separation zone being configured to separate the unreacted reactive olefin and the second product olefin into a vapor fraction containing the unreacted reactive olefin and a liquid fraction containing the second product olefin. The system is capable of continuously performing metathesis.

[0009] The olefin metathesis system includes a reaction zone and a product separation zone above the reaction zone, the reaction zone configured to contact a first reactive olefin in the presence of a homogeneous metathesis catalyst system to form a metathesis product comprising a first product olefin and a second product olefin, the reaction zone having a reaction tray and a liquid collection tray below the reaction tray, the product separation zone having at least one distillation structure, the product separation zone configured to receive a vapor phase containing the unreacted reactive olefin and the first product olefin from the reaction zone; and a distillation column fluidly connected to the reaction zone of the distillation column, the distillation column configured to receive the second product olefin, the unreacted reactive olefin, and the second product olefin from the reaction zone of the distillation column. a catalyst removal unit configured to receive the fins and a liquid phase containing the homogeneous metathesis catalyst system and separate the liquid phase into a first stream containing unreacted reactive olefins and a second stream containing the homogeneous metathesis catalyst system; a stripping column fluidly connected to the first stream and configured to receive the first stream as reflux at an upper portion of the stripping column and separate the first stream into a vapor fraction containing unreacted reactive olefins and a liquid fraction containing the second product olefin, the product separation zone being configured to separate the unreacted reactive olefins and the first product olefin into a vapor fraction containing the first product olefin and a liquid fraction containing unreacted reactive olefin. The system is capable of continuously performing metathesis.

[0010] Other technical features may be readily apparent to those skilled in the art from the following figures, descriptions, and claims.

[0011] For a complete understanding of the present disclosure, reference is made to the following detailed description taken in conjunction with the accompanying drawings. [Brief explanation of the drawings]

[0012] [Figure 1A] 1 shows a schematic diagram of the metathesis reaction process.

[0013] [Figure 1B]1 shows a schematic diagram of another metathesis reaction process.

[0014] [Figure 2] 1 shows a schematic diagram of another apparatus for conducting an olefin metathesis process, wherein the reaction zone, first product separation zone, and second product separation zone are contained within a distillation column.

[0015] [Figure 3] 1 shows a schematic diagram of another apparatus for conducting an olefin metathesis process, in which the reaction zone, the second product separation zone are contained within a distillation column, and the first product separation zone comprises a stripping column. DETAILED DESCRIPTION OF THE INVENTION

[0016] Illustrative aspects of the presently claimed subject matter are disclosed. In the interest of clarity, not all features of an actual implementation are described herein. It will be appreciated that the development of any such actual aspect will require numerous implementation-specific decisions to achieve developer-specific goals, including compliance with system- and business-related constraints that may vary from implementation to implementation. Moreover, it will be appreciated that such a development effort, while complex and time-consuming, would be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure.

[0017] Unless otherwise specified, "contacting," "combining," and their derivatives refer to any additional order, sequence, or concentration when two or more components of the disclosed embodiments are contacted or combined.

[0018] As used herein, the term "flow" refers to the composition of components disclosed herein for each flow. The term "flow" may also refer to and imply associated equipment, such as conduits, lines, and pipes, used to move the composition from one location to another (e.g., flow from one equipment unit to another). Alternatively, the term "flow" may refer only to the composition contained within the equipment (e.g., flow from one zone to another zone, where both zones are contained within the same equipment unit).

[0019] The term "olefin," whenever used in this specification and claims, refers to a hydrocarbon having at least one carbon-carbon double bond that is not part of an aromatic ring or aromatic ring system. The term "olefin," unless otherwise specified, includes aliphatic and aromatic, cyclic and acyclic, and / or straight-chain and branched hydrocarbons having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system. Olefins having only one, two, three, etc. carbon-carbon double bonds can be identified by using terms such as "mono," "di," "tri," etc. in the olefin name. Olefins can be further distinguished by the position of the carbon-carbon double bond(s).

[0020] The term "α-olefin" as used in the present specification and claims refers to an olefin having a carbon-carbon double bond between the first and second carbon atoms of the longest continuous chain of carbon atoms. The term "α-olefin" includes straight-chain and branched-chain α-olefins unless explicitly stated otherwise. In the case of branched-chain α-olefins, the branch may be at the 2-position (vinylidene) and / or at the 3-position or higher relative to the olefinic double bond. The term "vinylidene," as used in the present specification and claims, always refers to an α-olefin having a branch at the 2-position relative to the olefinic double bond. Unless explicitly stated, the term "α-olefin" itself does not imply the presence or absence of other carbon-carbon double bonds.

[0021] The term "standard α-olefin," as used herein and in the claims, always refers to a straight-chain aliphatic monoolefin having a carbon-carbon double bond between the first and second carbon atoms. Note that "standard α-olefin" is not synonymous with "linear α-olefin," as the term "linear α-olefin" may further include straight-chain olefinic compounds having a double bond between the first and second carbon atoms and additional double bonds.

[0022] Terms referring to states of matter, such as solid, liquid, liquid fraction, gas, vapor, vapor fraction, solid phase, liquid phase, vapor phase, and vapor phase, refer to the states of matter under the operating conditions herein for each step of the disclosed processes. For example, "liquid phase" refers to i) the liquid present in the reaction zone disclosed herein at the temperature and pressure at which the metathesis reaction occurs in the reaction zone, ii) the liquid present in the streams, lines, and conduits present between the reaction zone and the catalyst separation zone at the temperature and pressure at which the streams, lines, and conduits exist, and iii) the liquid present in the catalyst separation zone at the temperature and pressure at which separation occurs. Similarly, "vapor phase" in the context of the reaction zone disclosed herein refers to the gas or vapor present in the reaction zone at the temperature and pressure at which the metathesis reaction occurs.

[0023] Disclosed herein are processes and apparatus for the metathesis of olefins by reactive distillation. The metathesis reaction occurs in the liquid phase using a homogeneous metathesis catalyst system. The reaction occurs under conditions such that the light product olefins (e.g., ethylene, propylene, or both ethylene and propylene) produced by the metathesis reaction are in the vapor phase, separate from the liquid phase as vapors, and do not further react with the homogeneous metathesis catalyst system in the liquid phase, thus reducing the formation of undesirable by-products. The process is generally operated continuously.

[0024] 1A and 1B show schematic diagrams of metathesis reaction processes 100A and 100B. The steps of processes 100A and 100B occur in a reaction zone 110, a catalyst separation zone 120, and a product separation zone 130. Additional steps of process 100B can occur in a second product separation zone 140.

[0025] Processes 100A and 100B generally begin with introducing reactants into reaction zone 110. The reactants include one reactive olefin (reactive olefin) or two reactive olefins (first reactive olefin and second reactive olefin). The use of "reactive olefin(s)" herein is intended to include both of these aspects and embodiments. Thus, in some aspects, processes 100A and 100B can include introducing a first reactive olefin into reaction zone 110; and other aspects can include introducing a first reactive olefin and a second reactive olefin into reaction zone 110. The introduction of the reactants can occur sequentially.

[0026] The reactive olefin(s) may be introduced into reaction zone 110 via feedstream 10. In some embodiments, the reactive olefin(s) comprise one olefin; alternatively, the reactive olefin(s) comprise two olefins; alternatively, the reactive olefin(s) may comprise three or more olefins. When two different reactive olefins are used, the molar ratio of the first reactive olefin to the second reactive olefin may range from about 0.8:1 to about 1.2:1. For example, the molar ratio of the first reactive olefin to the second reactive olefin may be 1:1. When two different reactive olefins are used, the first reactive olefin and the second reactive olefin may be introduced into reaction zone 110 via feedstream 10; alternatively, the first reactive olefin may be introduced into reaction zone 110 via feedstream 10, and the second reactive olefin may be introduced into reaction zone 110 via a separate stream fluidly connected to reaction zone 110.

[0027] One or more of the reactive olefin(s) in feedstream 10 may be selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms; additionally or alternatively, one or more of the reactive olefin(s) in feedstream 10 may be selected from any olefin that is an α-olefin; additionally or alternatively, one or more of the reactive olefin(s) in feedstream 10 may be selected from olefins that are standard α-olefins. Specific non-limiting examples of reactive olefin(s) can include, but are not limited to, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-butene in combination with a higher carbon number olefin, or 1-hexene in combination with a higher carbon number olefin, or combinations thereof.

[0028] In additional embodiments, Processes 100A and 100B can include introducing a homogeneous metathesis catalyst system into reaction zone 110. In some embodiments, the homogeneous metathesis catalyst system can be introduced via Stream 10, while in other embodiments, the homogeneous metathesis catalyst system is introduced in a stream that is separate and distinct from Stream 10. For example, the homogeneous metathesis catalyst system can be contained within a catalyst stream that combines with a reactant stream containing reactive olefin(s) to form feedstream 10, which introduces the reactive olefin(s) and the homogeneous metathesis catalyst system into reaction zone 110. Alternatively, the homogeneous metathesis catalyst system can be contained within a catalyst stream that supplies the homogeneous metathesis catalyst system to reaction zone 110 separately from the reactive olefin(s) in feedstream 10.

[0029] Any suitable homogeneous metathesis catalyst system can be used. Homogeneous metathesis catalyst systems generally include a metathesis catalyst dissolved in an inert solvent such as toluene. Non-limiting examples of homogeneous metathesis catalyst systems include metal oxide-based metathesis catalyst systems, metal halide-based metathesis catalyst systems, metal carbene-based metathesis catalyst systems (also known as Grubbs catalyst-based catalyst systems), or any combination thereof. In one aspect, the metathesis catalyst system can be a metal oxide-based metathesis catalyst system or a metal halide-based metathesis catalyst system; alternatively, it can be a metal oxide-based metathesis catalyst system; alternatively, it can be a metal halide-based metathesis catalyst system; or alternatively, it can be a metal carbene-based metathesis catalyst system.

[0030] The metal oxide-based metathesis catalyst system may comprise (or consist essentially of, or consist of) cobalt oxide, molybdenum oxide, tungsten oxide, rhenium oxide, or any combination thereof. For example, the metal oxide-based catalyst system may comprise (or consist essentially of, or consist of) cobalt oxide; alternatively, molybdenum oxide; alternatively, tungsten oxide; or alternatively, rhenium oxide. Optionally, the metal oxide-based metathesis catalyst system may further comprise a support, or a metal alkyl activator, or both a support and a metal alkyl activator. Exemplary supports can include alumina, silica, silica-alumina, and aluminum phosphate, among other solid oxide materials. Thus, non-limiting examples of supported metal oxide-based metathesis catalyst systems include alumina-supported molybdenum oxide (MoO / AlO), silica-supported tungsten oxide (WO / SiO), alumina-supported rhenium oxide (ReO / AlO), alumina-supported cobalt and molybdenum oxides (CoO / MoO / AlO), or alumina-supported rhenium oxide activated with tetramethyltin (ReO / AlO / SnMe). Other suitable metal oxide-based metathesis catalyst systems are known to those skilled in the art.

[0031] The metal oxide-based metathesis catalyst system can further include a metal alkyl activator. In one embodiment, the metal alkyl can comprise, consist essentially of, or be an alkyllithium, alkylmagnesium, alkylaluminum, alkyltin compound, or any mixture thereof. In one embodiment, the metal alkyl activator can be an alkyllithium compound. In another embodiment, the metal alkyl activator can comprise, consist essentially of, or be an alkylmagnesium compound; alternatively, an alkylaluminum compound; or alternatively, an alkyltin compound. Non-limiting examples of alkylaluminum compounds include trialkylaluminum compounds and / or alkylaluminum halide compounds. The alkyl group on the metal alkyl activator can include any C1-C10 hydrocarbyl group, or alternatively, any C1-C5 hydrocarbyl group. In various embodiments, the alkyl group of the metal alkyl activator can be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl; alternatively, methyl, ethyl, n-butyl, sec-butyl, or tert-butyl; alternatively, methyl; alternatively, ethyl; alternatively, n-butyl; alternatively, sec-butyl; or alternatively, tert-butyl. Representative examples of suitable trialkylaluminum compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, or combinations thereof. The halide of the alkylaluminum halide compound can be chloride, bromide, or iodide; alternatively, chloride; alternatively, bromide; or alternatively, iodide. Examples of suitable alkylaluminum halide compounds include ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, or combinations thereof. Suitable, non-limiting examples of alkyltin compounds include tetramethyltin, tetraethyltin, tetrabutyltin, or combinations thereof.

[0032] The metal halide-based metathesis catalyst system may comprise (or consist essentially of, or consist of) a tungsten halide, a molybdenum halide, or a combination thereof. For example, the metal halide-based metathesis catalyst system may comprise (or consist essentially of, or consist of) a tungsten halide; or alternatively, a molybdenum halide. The halide of the metal halide-based metathesis catalyst system may be chloride, bromide, or iodide. In one embodiment, the halide may comprise, essentially consist of, or be chloride; alternatively, bromide; or alternatively, iodide. Thus, the metal halide-based metathesis catalyst system may comprise (or consist essentially of, or consist of) tungsten chloride, molybdenum chloride, or a mixture thereof; alternatively, tungsten chloride; or alternatively, molybdenum chloride.

[0033] Optionally, the metal halide-based metathesis catalyst system may further comprise a metal alkyl activator (as described herein), oxygen, an alcohol, or any combination thereof; alternatively, a metal alkyl activator; alternatively, oxygen; or alternatively, an alcohol. Non-limiting examples of metal halide-based metathesis catalyst systems include tungsten chloride / tetrabutyltin (WCl / SnMe), tungsten chloride / ethylaluminum dichloride (WCl / EtAlCl), tungsten chloride / ethylaluminum dichloride / ethyl alcohol (WCl / EtAlCl / EtOH), molybdenum chloride / triethylaluminum (MoCl / AlEt), or molybdenum chloride / triethylaluminum / O (MoCl / AlEt / O). Other suitable metal halide-based metathesis catalyst systems are known to those skilled in the art.

[0034] The metal of the metal carbene-based metathesis catalyst system can comprise (or consist essentially of, or consist of) tungsten, tantalum, osmium, molybdenum, ruthenium, or any combination thereof. For example, the metal of the metal carbene-based metathesis catalyst system can comprise (or consist essentially of, or consist of) tungsten; alternatively, tantalum; alternatively, osmium; alternatively, molybdenum; or alternatively, ruthenium. These metal carbene-based metathesis catalyst systems can contain compounds that have a stable metal-carbon double bond or that can form a metal-carbon double bond in situ from a metal precursor that has a stable metal-carbon single bond.

[0035] Processes 100A and 100B can include reacting a first reactive olefin in the presence of a homogeneous metathesis catalyst system in reaction zone 110 to form a metathesis product containing a first product olefin and a second product olefin.

[0036] Reaction zone 110, as disclosed herein, is defined as a region within a metathesis reactor having any configuration of equipment (e.g., vessel(s), piping, valve(s), combinations thereof) suitable for a metathesis reaction to occur as disclosed herein, where all necessary reaction components (e.g., reactive olefin(s) and homogeneous metathesis catalyst system) and reaction conditions (e.g., temperature, pressure, flow rate, reactive olefin concentration) are present such that the metathesis reaction can occur at a desired rate. In some embodiments, the boundaries of reaction zone 110 can be defined by the necessary reaction components and reaction conditions, which can exist to maintain the metathesis reaction within 25 percent of the average reaction rate (e.g., based on a volume average of the reaction rate in reaction zone 110). In certain embodiments, reaction zone 110 can be embodied as at least a portion of a distillation column or other vessel configured to retain a liquid phase in which a reaction phase occurs and a vapor phase leaks into the space within the distillation column or vessel above the liquid phase.

[0037] In some aspects, reaction zone 110 does not include a heterogeneous metathesis catalyst or heterogeneous metathesis catalyst system, i.e., embodiments contemplate that the metathesis catalyst remains dissolved in the liquid while in reaction zone 110.

[0038] By contacting the reactive olefin(s) in the presence of the homogeneous metathesis catalyst system in reaction zone 110 (in the liquid phase), at least a portion of the total amount of reactive olefin(s) in reaction zone 110 is converted to metathesis products. The metathesis products may include a first product olefin (e.g., a light metathesis product, such as ethylene or propylene) and a second olefin (e.g., a heavy metathesis product). Other olefin products may also be produced in amounts less than those produced for the first and second product olefins.

[0039] The operating conditions of reaction zone 110 are configured so that the first product olefin exists in a vapor phase that separates from the liquid phase in which the metathesis reaction occurs. In certain aspects, a first concentration of the first product olefin in the liquid phase is lower than a second concentration of the first product olefin in the vapor phase. In certain aspects, the concentration of the first product olefin (e.g., ethylene) in the liquid phase can be less than about 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.02 wt.%, based on the total amount of first product olefin in the liquid phase. In embodiments, the concentration of the first product olefin (e.g., ethylene) in the vapor phase can range from about 1 mol.% to about 9 mol.%; alternatively, it can be from about 2 mol.% to about 8 mol.%, based on the total moles of the vapor phase. For example, in an aspect involving the self-metathesis of 1-hexene, the concentration of ethylene in the vapor phase can be about 3.5 mol.%. In another example embodiment involving the self-metathesis of 1-butene, the concentration of ethylene in the vapor phase can be about 7.0 mol %.

[0040] Any conditions capable of forming a metathesis product having a first product olefin in the vapor phase and one or more reactive olefins in the liquid phase may be utilized, such as the process conditions taught in U.S. Patent Application Publication No. 2003 / 0135080 and U.S. Patent No. 8,765,984. Metathesis conditions capable of forming a metathesis product may include, but are not limited to, pressure, temperature, time, and concentration (relating to solution-phase formation of the metathesis product), and are described independently herein. These independently described conditions may be utilized in any combination, without limitation, to further describe the processes disclosed herein.

[0041] In certain embodiments, Processes 100A and 100B can utilize any pressure capable of forming a metathesis product having a first product olefin in the vapor phase and one or more reactive olefins in the liquid phase. In one embodiment, the minimum pressure that can be utilized to form a metathesis product (or liquid metathesis product) can be 5 psia (34.5 kPa), 10 psia (68.9 kPa), 14 psia (96.5 kPa), 14.7 psia (101.4 kPa), 20 psia (138.9 kPa), or 50 psia (344.7 kPa); alternatively or additionally, the maximum pressure can be 450 psia (3.1 MPa), 350 psia (2.4 MPa), 250 psia (1.7 MPa), or 150 psia (1.0 MPa). The range of pressures that can be utilized to form a metathesis product can range from any minimum pressure to any maximum pressure described herein for the metathesis conditions. In some embodiments, suitable ranges of pressure that may be utilized to form the metathesis product (or liquid metathesis product) may include, but are not limited to, 5 psia (34.5 kPa) to 450 psia (3.10 MPa); alternatively, 10 psia (68.9 kPa) to 350 psia (2.4 MPa); alternatively, 14 psia (96.5 kPa) to 250 psi (1.7 MPa); alternatively, 14 psia (96.5 kPa) to 150 psia (1.0 MPa); alternatively, 14.7 psia (101.4 kPa) to 150 psia (1.0 MPa); or alternatively, 20 psia (138.9 kPa) to 150 psia (1.0 MPa). Other pressure ranges that may be utilized to form the metathesis product will be readily apparent to one of ordinary skill in the art using this disclosure.

[0042] In certain embodiments, Processes 100A and 100B may utilize any temperature capable of forming a metathesis product having a first product olefin in the vapor phase and one or more reactive olefins in the liquid phase. In one embodiment, the minimum temperature that may be utilized to form the metathesis product may be 30°C, 35°C, 40°C, 45°C, or 50°C; alternatively or additionally, the maximum temperature that may be utilized to form the metathesis product may be 150°C, 140°C, 130°C, 120°C, 110°C, 90°C, 80°C, 70°C, or 60°C. The range of temperatures that may be utilized to form the metathesis product may range from any minimum temperature described herein to any maximum temperature described herein. In some embodiments, suitable ranges of temperatures that may be utilized to form the metathesis product may include, but are not limited to, 30° C. to 150° C.; alternatively, 35° C. to 100° C.; alternatively, 40° C. to 90° C.; alternatively, 45° C. to 80° C.; alternatively, 50° C. to 70° C.; alternatively, 50° C. to 65° C.; or alternatively, 50° C. to 60° C. Other temperature ranges that may be utilized to form the metathesis product (or liquid metathesis product) will be readily apparent to one of ordinary skill in the art using this disclosure.

[0043] In certain embodiments, processes 100A and 100B can utilize any residence time (duration or average duration) within reaction zone 110 necessary to form the desired amount of metathesis product; alternatively, the desired homogeneous metathesis catalyst system productivity; alternatively, provide the desired conversion (e.g., at least 50%, 60%, 70%, or 80% by weight). In one embodiment, the minimum time (or minimum average time) that can be utilized to form metathesis product can be 1 second, 1 minute, 2 minutes, 4 minutes, 6 minutes, 8 minutes, or 10 minutes; alternatively or additionally, the maximum time (or average maximum time) can be 1 hour, 1.5 hours, 2 hours, 4 hours, 6 hours, 8 hours, or 10 hours. The range of times (or average times) that can be utilized to form metathesis product can range from any minimum time to any maximum time described herein for the metathesis conditions. In some embodiments, suitable ranges of times (or average times) that may be utilized to form a metathesis product may include, but are not limited to, 1 second to 10 hours; alternatively, 1 minute to 8 hours; alternatively, 2 minutes to 6 hours; alternatively, 4 minutes to 4 hours; alternatively, 6 minutes to 2 hours; alternatively, 8 minutes to 90 minutes; or alternatively, 10 minutes to 1 hour. Other ranges of times (or average times) that may be utilized to form a metathesis product (or liquid metathesis product) will be readily apparent to one of ordinary skill in the art using this disclosure.

[0044] In certain embodiments, Processes 100A and 100B are capable of forming metathesis products using any concentration of homogeneous metathesis catalyst system that can produce the desired amount of metathesis product, desired metathesis catalyst system productivity, and / or desired conversion of reactive olefin(s) disclosed herein within a desired residence time (or average time). In one embodiment, the minimum concentration of the homogeneous metathesis catalyst system can be 100, 200, 300, 400, or 500 ppm by weight; alternatively or additionally, the maximum concentration of the homogeneous metathesis catalyst system can be 1,000, 900, 800, 700, or 600 ppm by weight. The range of homogeneous metathesis catalyst system concentrations that can be utilized can range from any minimum catalyst system concentration disclosed herein to any maximum catalyst system concentration disclosed herein. In some embodiments, suitable ranges of homogeneous metathesis catalyst system concentrations that may be utilized to form metathesis products may include, but are not limited to, 100 to 1,000 ppm by weight, 110 to 900 ppm by weight, 120 to 800 ppm by weight, 130 to 700 ppm by weight, or 130 ppm by weight. Other catalyst system concentration ranges that may be utilized to produce metathesis products will be readily apparent to one of ordinary skill in the art using this disclosure. Generally, ppm-based catalyst system concentrations may be based on the mass of the reactive olefin(s).

[0045] In certain aspects, processes 100A and 100B may include removing the metathesis product from reaction zone 110. In embodiments, removing the metathesis product from reaction zone 110 may include removing a liquid phase containing second product olefins (e.g., heavy product olefins), the homogeneous metathesis catalyst system, and optionally unreacted reactive olefins from reaction zone 110, and removing a vapor phase containing first product olefins (e.g., light product olefins) from reaction zone 110. In aspects of these embodiments, the liquid and vapor phases from reaction zone 110 occur continuously. In embodiments, metathesis product olefin(s) may be removed from reaction zone 110 via first effluent stream 112 and second effluent stream 114. The vapor-phase first product olefins and optionally unreacted reactive olefins may flow from reaction zone 110 in stream 112. The liquid-phase second product olefins may flow from reaction zone 110 in reaction zone effluent stream 114. The reaction zone effluent stream 114 may also contain the homogeneous metathesis catalyst system and any unreacted reactive olefins in the liquid phase.

[0046] The carbon number of the product olefin(s) produced in reaction zone 110 depends on the reactive olefin(s) introduced into reaction zone 110 and generally includes the reaction product of a metathesis reaction resulting from contact of the reactive olefin(s) in the presence of a homogeneous metathesis catalyst system in reaction zone 110. In certain embodiments, a first product olefin can have a carbon number less than the carbon number of the first reactive olefin, and a second product olefin can have a carbon number greater than the carbon number of the first reactive olefin. For example, the self-metathesis of 1-butene as the reactive olefin in the presence of a homogeneous metathesis catalyst system can produce ethylene (first product olefin) and 1-hexene (second product olefin). In another example, the self-metathesis of 1-hexane as the reactive olefin in the presence of a homogeneous metathesis catalyst system can produce ethylene (first product olefin) and 1-decene (second product olefin). In additional aspects of embodiments including a second reactive olefin fed to reaction zone 110, the first product olefin can have a carbon number less than the carbon number of both the first reactive olefin and the second reactive olefin, and the second product olefin can have a carbon number greater than the carbon number of both the first reactive olefin and the second reactive olefin. For example, the cross-metathesis of 1-butene and 1-tetradecene in the presence of a homogeneous metathesis catalyst system can produce ethylene (the first product olefin) and C16-olefins and / or C26-olefins (either of which can be the second product olefin).

[0047] Processes 100A and 100B may include introducing a liquid phase of the metathesis product in stream 114 into a catalyst separation zone 120 and separating the liquid phase into a first stream 122 containing the second product olefins and optionally unreacted reactive olefins and a second stream 124 containing the homogeneous metathesis catalyst system. The homogeneous metathesis catalyst system in second stream 124 may be in the form of spent catalyst or may contain both spent and fresh catalyst.

[0048] The catalyst separation zone 120 disclosed herein generally comprises any equipment configured to separate a mixture containing product olefin(s) and a homogeneous metathesis catalyst system (e.g., in the form of spent catalyst or including both spent and unused catalyst) from a stream containing the homogeneous metathesis catalyst system and a stream containing the product olefin(s). The homogeneous metathesis catalyst system can be separated from the mixture by distillation (SPD), membrane separation, conversion of the homogeneous catalyst to a heterogeneous catalyst, phase separation, or solvent extraction. Examples of membrane separation for separating a homogeneous metathesis catalyst from a metathesis reaction mixture can be found in U.S. Patent Application Publication No. 2008 / 0103346.

[0049] In processes 100 A and 100 B, the mixture from which the homogeneous metathesis catalyst system is separated is received from stream 114 containing the reaction effluent from reaction zone 110 .

[0050] Processes 100A and 100B may further include introducing first effluent stream 112 into product separation zone 130 and separating the second product olefins and unreacted reactive olefins in product separation zone 130 into a vapor fraction containing unreacted reactive olefins and a liquid fraction containing the second olefin product. The vapor fraction may be recovered in stream 132 and the liquid fraction may be recovered in stream 134. In some embodiments, the unreacted reactive olefins in the vapor fraction in stream 132 may be recycled to reaction zone 110. In some embodiments, the unreacted reactive olefins may be condensed (e.g., via a condenser in stream 132) and recycled in the liquid phase to reaction zone 110.

[0051] Process 100B of FIG. 1B further utilizes a second product separation zone 140. As described above, first product olefins in a vapor phase can flow from reaction zone 110 in stream 112. Stream 112 can further include unreacted reactive olefins in a vapor phase. Thus, second product separation zone 140 can be utilized in process 100B, where first effluent stream 112 contains first product olefins and unreacted reactive olefins. Process 100B can further include introducing the vapor phase into second product separation zone 140 and separating the vapor phase in second product separation zone 140 into a vapor portion containing the first product olefin and a liquid portion containing unreacted reactive olefins. In these embodiments, a portion of the unreacted reactive olefins can be present in the vapor phase, and another portion of the unreacted reactive olefins can be present in the liquid phase. In one embodiment, the vapor portion can flow in stream 142 from the second product separation zone 140 and the liquid portion can flow in stream 144 from the product separation zone 140 to the reaction zone 110 .

[0052] 2 and 3 illustrate apparatuses 200 and 300 that utilize process 100B shown in FIG. 1B. Apparatus 200 and 300 perform reactive distillation in reaction zone 110 of distillation column 201 / 301, followed by spent catalyst removal and then product olefin recovery. In both apparatuses 200 and 300, the liquid phase described above is contained within reaction zone 110, and distillation column 201 and 301 of each apparatus 200 and 300 are configured such that one or more reactive olefin(s) are introduced into distillation column 201 and 301, separated, and reacted in reaction zone 110 in the presence of a liquid-phase homogeneous metathesis catalyst system to form a meta-cracked product comprising at least two product olefins (a first product olefin in the vapor phase and a second product olefin in the liquid phase).

[0053] 2 shows a schematic diagram of an apparatus 200 for conducting an olefin metathesis process, in which reaction zone 110, first product separation zone 130, and second product separation zone 140 are contained within a distillation column 201. First product separation zone 130 is below reaction zone 110, and second product separation zone 140 is above reaction zone 110. Second product separation zone 140 is sometimes referred to as the rectification section of distillation column 201.

[0054] The reaction zone 110 in the apparatus 200 has a liquid collection tray 203 disposed below the reactive tray 202 in the distillation column 201. The reactive olefin(s) and the homogeneous metathesis catalyst system are introduced into the distillation column 201 via the feed stream 10 at a location above the reactive tray 202. The reaction tray 202 may be embodied, for example, as a sieve tray with a downcomer. The liquid collection tray 203 may be embodied as a chimney tray, a vane collector tray, a trap-out pan, a flange-type collector tray, or a combination thereof. The liquid collection tray 203 is sometimes referred to as a bubble cap tray. The liquid collection tray 203 is generally configured with a vapor passage 204 through which the vapor portion of the product separation zone 130 can flow, but the liquid phase in the reaction zone 110 does not. Vapor passage 204 may be formed by one or more distillation tray chimneys, vane configurations, or other structure or arrangement of structures configured to allow vapor passage therethrough. Reaction components (e.g., reactive olefin(s) and homogeneous metathesis catalyst system) are introduced into distillation column 201 above reaction tray 202 and fall onto reaction tray 202, forming a liquid phase layer on reaction tray 202 within reaction zone 110. Liquid exits in the direction of arrow A (e.g., through a downcomer or holes formed in reaction tray 202) to liquid collection tray 203, forming another liquid phase layer in reaction zone 110 above liquid collection tray 203.

[0055] 2, the liquid phase of reaction zone 110 in distillation column 201 is embodied as a first portion 205 of the liquid phase retained on reaction tray 202 and a second portion 207 of the liquid phase retained on liquid collection tray 203. First portion 205 and second portion 207 of the liquid phase are separated by vapor space 206, which is located between the top of second portion 207 of the liquid phase and the bottom of reaction tray 202. It is believed that no significant metathesis reaction occurs in vapor space 206 of reaction zone 110 of distillation column 201, and that the metathesis reaction occurs primarily in first portion 205 and second portion 207 of the liquid phase within reaction zone 110.

[0056] The reaction effluent, also referred to herein as the liquid phase, from reaction zone 110 of apparatus 200 can be passed as side draw stream 214 (stream 214 corresponds to stream 114 in FIGS. 1A and 1B ) to catalyst separation zone 120. Side draw stream 214 is fluidly connected to liquid collection tray 203 and a catalyst separation unit in catalyst separation zone 120. The catalyst separation unit in catalyst separation zone 120 is configured, according to the technology disclosed herein, to separate the liquid phase received via stream 214 into a first stream 122 containing the second product olefin and any unreacted reactive olefins and a second stream 124 containing the homogeneous metathesis catalyst system. First stream 122 is fluidly connected to the catalyst separation unit in catalyst separation zone 120 and to a product separation zone 130 in distillation column 201.

[0057] The second product olefin and any unreacted reactive olefins are received in the liquid phase into product separation zone 130 via first stream 122. Product separation zone 130 may contain trays, baffles, packing, or other structure(s) configured to effect distillation of the second product olefin and any unreacted reactive olefins, whereby the second product olefins condense to form a liquid portion as described herein and unreacted reactive olefins that remain in the vapor phase to form a vapor portion as described herein. In an embodiment, the second product olefin and any unreacted reactive olefins are introduced into an upper distillation tray of product separation zone 130 of distillation column 201, which is below liquid collection tray 203. The vapor portion travels in the direction of arrow 232 into reaction zone 110 of distillation column 201 via vapor passageway 204 formed in liquid collection tray 203. The movement of the vapor portion in the direction of arrow 232 into reaction zone 110 may be referred to as recycling the vapor portion from product separation zone 130 to reaction zone 110. Upon entering reaction zone 110, at least a portion of the vapor fraction may condense to a liquid phase and react in the presence of the homogeneous metathesis catalyst system that is also contained in the liquid phase of reaction zone 110 within distillation column 201. The liquid fraction travels in the direction of arrow 233, traveling down distillation column 201 and exiting distillation column 201 via stream 234. Stream 234 may contain a reboiler that may be configured to heat at least a portion of the liquid fraction for recycle to product separation zone 130 within distillation column 201 to provide heat to distillation column 201 and improve the separation efficiency of product separation zone 130 of distillation column 201.

[0058] In one embodiment, the temperature and pressure at any point in product separation zone 130 within distillation column 201 are sufficient to recover second product olefins in the liquid portion and unreacted reactive olefins from product separation zone 130 in the vapor portion.

[0059] The vapor phase containing the first product olefin and any unreacted reactive olefin may travel in the direction of arrow 212 into second product separation zone 140. Product separation zone 140 may contain trays, baffles, packing, or other structure(s) configured to carry out distillation of the first product olefin and any unreacted reactive olefin, such that the first product olefin remains in the vapor phase to form a vapor portion as described herein, and the unreacted reactive olefin condenses to form a liquid portion that travels in the direction of arrow 244 to reaction zone 110. In an embodiment, the first product olefin and any unreacted reactive olefin traveling in the direction of arrow 212 may be introduced to a bottom distillation tray in product separation zone 140 of distillation column 201, the bottom distillation tray being above liquid collection tray 203 and reaction tray 202. The movement of the liquid portion from product separation zone 140 to reaction zone 110 in the direction of arrow 244 may be referred to as recycling the liquid portion from product separation zone 140 to reaction zone 110. Upon entering reaction zone 110, at least a portion of the vapor fraction condenses to a liquid phase and can react in the presence of the homogeneous metathesis catalyst system, which is also contained in the liquid phase of reaction zone 110, within distillation column 201. The vapor fraction within product separation zone 140 travels up distillation column 201 in the direction of arrow 212 and exits distillation column 201 via stream 242. Stream 242 may contain a condenser configured to condense and recycle at least a portion of the vapor fraction in stream 242 to product separation zone 140 of distillation column 201 to improve the separation efficiency of product separation zone 140 of distillation column 201.

[0060] In one embodiment, the temperature and pressure at any point within product separation zone 140 of distillation column 201 are sufficient to recover unreacted reactive olefins in the liquid portion and to recover first product olefins from product separation zone 140 of distillation column 201 in the vapor portion.

[0061] In one embodiment, the pressures in reaction zone 110, product separation zone 130, and product separation zone 140 within distillation column 201 are approximately equal to one another.

[0062] 3 shows a schematic diagram of another apparatus 300 for conducting an olefin metathesis process, in which reaction zone 110 and second product separation zone 140 are in a distillation column 301, and first product separation zone 130 is embodied in a stripping column 331. Second product separation zone 140 is located above reaction zone 110 within distillation column 301. Second product separation zone 140 is sometimes referred to as the rectification section of distillation column 301.

[0063] The reaction zone 110 within the distillation column 301 of the apparatus 300 is a space filled with a liquid phase, with or without the above-mentioned reaction tray(s). The reactive olefin(s) and the homogeneous metathesis catalyst system are introduced into the distillation column 301 via the feed stream 10 at a location above the liquid phase or the top surface of the upper reaction tray. The reaction components (e.g., the reactive olefin(s) and the homogeneous metathesis catalyst system) are introduced into the distillation column 301 and fall into the liquid phase within the reaction zone 110 of the distillation column 301.

[0064] The reaction effluent, also referred to herein as the liquid phase, from reaction zone 110 of apparatus 300 can be passed as bottoms stream 314 (stream 314 corresponds to stream 114 in FIGS. 1A and 1B ) to catalyst separation zone 120. Bottoms stream 314 is fluidly connected to the bottom of distillation column 301 and the catalyst separation unit in catalyst separation zone 120. The catalyst separation unit in catalyst separation zone 120 is configured, according to the techniques disclosed herein, to separate the liquid phase received via stream 314 into a first stream 122 containing the second product olefin and any unreacted reactive olefins, and a second stream 124 containing the homogeneous metathesis catalyst system. First stream 122 is fluidly connected to the catalyst separation unit in catalyst separation zone 120 and stripping column 331.

[0065] The second product olefins and any unreacted reactive olefins are received in the liquid phase via first stream 122 into stripping column 331. In one embodiment, first stream 122 is connected to the top of stripping column 331 and configured to introduce the second product olefins and any unreacted reactive olefins into the top of stripping column 331 as liquid reflux. Stripping column 331 in product separation zone 130 is configured to separate the second product olefins and any unreacted reactive olefins received via stream 122 into a vapor fraction containing the unreacted reactive olefins and a liquid fraction containing the second product olefins. The vapor and liquid fractions move countercurrently within stripping column 331. The vapor fraction moves within stripping column 331 in the direction of arrow 337, and the liquid fraction moves within stripping column 331 in the direction of arrow 338. Due to mass transfer conditions within stripping column 331, unreacted reactive olefins received via Stream 122 move from the liquid phase to a vapor fraction, and second product olefins received via Stream 122 remain in the liquid phase to form a liquid fraction. In certain aspects, stripping column 331 has a reboiler 335. In some aspects, stripping column 331 can include a condenser, while in other aspects, stripping column 331 does not include a condenser. That is, in some embodiments, product separation zone 130 of apparatus 300 can include a condenser for Stream 332 of stripping column 331, while in other aspects, it may not include a condenser for Stream 332 of stripping column 331. In certain aspects, stripping column 331 can contain trays, baffles, packing, or other structure(s) configured to effect the movement of unreacted reactive olefins to the vapor fraction, such that second product olefins remain in the liquid phase to form a liquid fraction.

[0066] In one embodiment, the temperature and pressure at any point within stripping column 331 are sufficient to allow second product olefins to be recovered in the liquid portion and unreacted reactive olefins to be recovered from stripping column 331 in the vapor portion.

[0067] 3, processes 100A and 100B described herein may include receiving a vapor portion from stripping column 331 into reaction zone 110 of distillation column 301 (e.g., via stream 332). FIG. 3 shows stream 332 being connected to the bottom of distillation column 301; however, alternative embodiments contemplate that stream 332 may be connected to a side of distillation column 301 that is fluidly connected to reaction zone 110 within distillation column 301 or to product separation zone 140 within distillation column 301.

[0068] 3, processes 100A and 100B described herein may also include removing a liquid portion from a bottom section of stripping column 331. The liquid portion may be removed via stream 333 fluidly connected to stripping column 331. The bottom section may be the bottom of stripping column 331 (as illustrated in FIG. 3) or a side of stripping column 331 near the bottom.

[0069] In connection with apparatus 300 of FIG. 3 , processes 100A and 100B described herein may also include reboiling at least a portion of the liquid fraction after removing it from the bottom section of stripping column 331. Stream 333 containing the liquid fraction may be fluidly connected to reboiler 335. Within the reboiler, the liquid fraction is heated and at least a portion of the liquid fraction may convert to a vapor phase and flow back to stripping column 331 in stream 336. Stream 336 may be connected to the side (as shown in FIG. 3 ) or bottom of stripping column 331. The portion of the liquid fraction that remains in a liquid state may flow from reboiler 335 via stream 334.

[0070] The flow of the vapor portion in stream 332 to reaction zone 110 of distillation column 301 may be referred to as a recycle of the vapor portion from product separation zone 130 to reaction zone 110. Upon entering reaction zone 110, at least a portion of the vapor portion may condense to become a liquid phase and react in the presence of the homogeneous metathesis catalyst system that is also contained in the liquid phase of reaction zone 110 in distillation column 301.

[0071] The liquid phase in distillation column 301 containing the first product olefin and any unreacted reactive olefins can travel in the direction of arrow 312 into a second product separation zone 140 in distillation column 301. Product separation zone 140 can contain trays, baffles, packing, or other structure(s) configured to carry out distillation of the first product olefin and any unreacted reactive olefins, such that the first product olefin remains in the vapor phase to form a vapor portion as described herein, and the unreacted reactive olefins condense to form a liquid portion that travels in the direction of arrow 344 to the reaction zone 110 of distillation column 301. In one embodiment, the first product olefin and any unreacted reactive olefins traveling in the direction of arrow 312 can be introduced into a bottom distillation tray in product separation zone 140 of distillation column 301, the bottom distillation tray being above the liquid surface of the liquid phase in the reaction zone 110 of distillation column 301. The movement of the liquid fraction from product separation zone 140 to reaction zone 110 in the direction of arrow 344 can be referred to as a recycle of the liquid fraction from product separation zone 140 to reaction zone 110. Upon entering reaction zone 110, at least a portion of the liquid fraction can react in the presence of a homogeneous metathesis catalyst system that is also contained in the liquid phase of reaction zone 110 within distillation column 301. The vapor fraction within product separation zone 140 travels up distillation column 301 in the direction of arrow 312 and exits distillation column 301 via stream 342.

[0072] In one embodiment, the temperature and pressure at any point within product separation zone 140 of distillation column 301 are sufficient to recover unreacted reactive olefins in the liquid portion and to recover first product olefins from product separation zone 140 of distillation column 301 in the vapor portion.

[0073] In one embodiment, the pressures in reaction zone 110 and product separation zone 140 within distillation column 301 are approximately equal to one another.

[0074] Stream 342 may contain a condenser configured to condense and recycle at least a portion of the vapor portion in stream 342 to product separation zone 140 of distillation column 301 to improve the separation efficiency of product separation zone 140 of distillation column 301.

[0075] Stream 334 may contain a reboiler that may be heated and configured to recycle at least a portion of the liquid phase to reaction zone 110 within distillation column 301 or to product separation zone 140 of distillation column 301. [Example]

[0076] The following examples are illustrative of metathesis reactions with reactive olefin(s) in the liquid phase and in the presence of a homogeneous metathesis catalyst system.

[0077] Example 1 is a simulation of an olefin metathesis reaction using a homogeneous metathesis catalyst in a reaction zone 110 as disclosed herein. The reactive olefin was 1-butene, and the feedstream contained 100 wt. % 1-butene. Double bond isomerization was set at a rate 0.11 times that of metathesis. The simulation represented that ethylene and propylene were flashed out of the reaction medium by distillation and did not react again. By selecting a 1-butene conversion of 13.4% at steady state, the metathesis product contained 3.26 wt. % ethylene, 0.14 wt. % propylene, 86.59 wt. % butenes, 0.24 wt. % pentenes, and 9.77 wt. % 1-hexene.

[0078] Example 2 is a simulation of an olefin metathesis reaction using a homogeneous metathesis catalyst in the reaction zone 110 as disclosed herein. The reactive olefin was 1-hexene, and the feedstream contained 100 wt. % 1-hexene. Double bond isomerization was set at a rate 0.11 times that of metathesis. The simulation represented that ethylene and propylene were flashed out of the reaction medium by distillation and did not react again. By selecting a 6.9% 1-hexene conversion at steady state, the metathesis product contained 1.11 wt. % ethylene, 0.03 wt. % propylene, 0.04 wt. % pentenes, 93.11 wt. % 1-hexene, 0.05 wt. % heptane, 0.08 wt. % nonene, and 5.58 wt. % decene.

[0079] Additional explanation A process and apparatus for olefin metathesis by reactive distillation is described. This application is also directed to the subject matter described in the following numbered paragraphs (referred to as "para" or "paras"):

[0080] Para 1: A process for olefin metathesis by reactive distillation, comprising reacting a first reactive olefin in the presence of a homogeneous metathesis catalyst system in a reaction zone of a distillation column to produce a metathesis product comprising a first product olefin and a second product olefin.

[0081] Paragraph 2: The process of paragraph 1, wherein the first product olefin has a carbon number less than the carbon number of the first reactive olefin, and the second product olefin has a carbon number greater than the carbon number of the first reactive olefin.

[0082] Paragraph 3: The process of paragraph 1 or 2, further comprising (continuously) removing from the reaction zone of the distillation column a liquid phase comprising the second product olefin and the homogeneous metathesis catalyst system; and (continuously) removing from the distillation column a vapor phase comprising the first product olefin.

[0083] Paragraph 4: The process of paragraph 3, further comprising, after removing the liquid phase, (sequentially) separating the liquid phase into a first stream comprising the second product olefin and a second stream comprising the homogeneous metathesis catalyst system.

[0084] Paragraph 5: The process of paragraphs 3 or 4, wherein the liquid phase further comprises unreacted reactive olefins, including the first reactive olefin, and wherein the first stream further comprises unreacted reactive olefins, and the process further comprises (continuously) introducing the first stream into a product separation zone; and (continuously) separating in the first product separation zone the second product olefin and the unreacted reactive olefin from a first vapor fraction comprising the unreacted reactive olefin and a first liquid fraction comprising the second product olefin.

[0085] Paragraph 6: The process of paragraph 5, further comprising recycling the first vapor portion to the reaction zone.

[0086] Paragraph 7: The process of paragraphs 3-6, wherein the vapor phase further comprises unreacted reactive olefins, and the process comprises, after removing the vapor phase, (continuously) introducing the vapor phase into a second product separation zone; and (continuously) separating the vapor phase in the second product separation zone into a second vapor fraction comprising the first product olefin and a second liquid fraction comprising the unreacted reactive olefins, the second liquid fraction flowing from the second product separation zone to the reaction zone.

[0087] Paragraph 8: The process of paragraph 7, wherein the reaction zone, the first product separation zone, and the second product separation zone are contained within a distillation column, the first product separation zone being below the reaction zone and the second product separation zone being above the reaction zone.

[0088] Paragraph 9: The process of any of paragraphs 1 to 8, wherein the reaction zone has a liquid collection tray disposed below the reaction tray within the distillation column, and wherein the first reactive olefin and the homogeneous metathesis catalyst system are introduced into the distillation column above the reaction tray.

[0089] Paragraph 10: The process of paragraph 9, wherein the liquid phase is removed from the reaction zone of the distillation column via a side draw stream fluidly connected to a liquid collection tray.

[0090] Paragraph 11: The process of paragraph 9 or 10, wherein the first vapor portion is (continuously) recycled to the reaction zone via vapor passages formed in the liquid collection tray.

[0091] Paragraph 12: The process of paragraph 7, wherein the reaction zone and second product separation zone are contained within a distillation column, the second product separation zone being above the reaction zone within the distillation column, and the first product separation zone being within a stripping column.

[0092] Paragraph 13: The process of paragraph 12, wherein the first stream is introduced (continuously) as reflux into the top of the stripping column.

[0093] Paragraph 14: The process of paragraph 12 or 13, further comprising: (continuously) receiving a first vapor portion from the stripping column into a reaction zone of the distillation column; (continuously) removing a first liquid portion from a bottom section of the stripping column; (continuously) reboiling at least a portion of the first liquid portion after removing the first liquid portion; and introducing at least a portion of the reboiled first liquid portion into the stripping column.

[0094] Paragraph 15: The process of any of paragraphs 1 to 14, wherein the reaction zone does not contain a heterogeneous metathesis catalyst.

[0095] Para. 16: The process of any of Paras. 1-15, wherein: 1) one or more of the reactive olefin(s) is / are: i) an α-olefin, ii) a linear α-olefin, iii) a standard α-olefin, iv) or a combination thereof; 2) one or more of the product olefin(s) is / are: i) an α-olefin, ii) a linear α-olefin, iii) a standard α-olefin, iv) or a combination thereof; 3) the first product olefin is ethylene, propylene, or both ethylene and propylene; 4) the first product olefin has a carbon number less than the carbon number of the one or more reactive olefin(s); 5) the second product olefin has a carbon number greater than the carbon number of the one or more reactive olefin(s); 6) the reactive olefin(s) is / are 1-butene or 1-butene in combination with a higher carbon number olefin; 7) the reactive olefin(s) is / are 1-hexene or 1-hexene in combination with a higher carbon number olefin; 8) or a combination thereof.

[0096] Paragraph 17: The process of any of paragraphs 1 to 16, wherein the homogeneous metathesis catalyst system comprises a metathesis catalyst dissolved in an inert solvent (e.g., toluene).

[0097] Paragraph 18: The process of any of paragraphs 1 to 18, wherein the homogeneous metathesis catalyst system comprises a metal oxide-based metathesis catalyst system, a metal halide-based metathesis catalyst system, a metal carbene-based metathesis catalyst system, or any combination thereof.

[0098] Paragraph 19: The process of any of paragraphs 1 to 18, further comprising (continuously) introducing a second reactive olefin into a reaction zone of the distillation column; and (continuously) reacting the second reactive olefin in the reaction zone in the presence of a homogeneous metathesis catalyst system to form a metathesis product.

[0099] Paragraph 21: The process of Paragraph 19, wherein the first product olefin has a carbon number less than the carbon number of the second reactive olefin, and the second product olefin has a carbon number greater than the carbon number of the second reactive olefin.

[0100] Paragraph 21: The process of paragraph 19, wherein the first product olefin has a carbon number that is less than the carbon number of the second reactive olefin and the carbon number of the first reactive olefin, and the second product olefin has a carbon number that is greater than the carbon number of the second reactive olefin and the carbon number of the first reactive olefin.

[0101] Paragraph 22: The process of any of paragraphs 1 to 21, further comprising (continuously) introducing the first reactive olefin and the homogeneous metathesis catalyst system into a reaction zone of the distillation column.

[0102] Paragraph 23: The process of any of paragraphs 1 to 22, wherein the first reactive olefin is introduced into the reaction zone of the distillation column separately from the homogeneous metathesis catalyst system.

[0103] Paragraph 24: The process of any of paragraphs 1 to 23, wherein the first reactive olefin and the homogeneous metathesis catalyst system are both introduced into a reaction zone of a distillation column.

[0104] Paragraph 25: The process of any of paragraphs 19 to 24, wherein the first reactive olefin is introduced into the reaction zone of the distillation column separately from the second reactive olefin.

[0105] Paragraph 26: The process of any of paragraphs 19 to 25, wherein the first reactive olefin and the second reactive olefin are both introduced into the reaction zone of the distillation column.

[0106] Paragraph 27: An olefin metathesis system, a distillation column having a reaction zone, a first product separation zone below the reaction zone, and a second product separation zone above the reaction zone, the reaction zone configured to contact a first reactive olefin in the presence of a homogeneous metathesis catalyst system to form a metathesis product comprising a first product olefin and a second product olefin, the reaction zone having a reaction tray and a liquid collection tray below the reaction tray, the first product separation zone having at least one distillation structure, the first product separation zone fluidly connected to the reaction zone via a vapor passageway in the liquid collection tray; a catalyst removal unit fluidly connected to the liquid collection tray of the reaction zone of the distillation column and configured to receive a liquid phase containing the second product olefins, unreacted reactive olefins, and the homogeneous metathesis catalyst system from the liquid collection tray and separate the liquid phase into a first stream comprising the unreacted reactive olefins and the second product olefins and a second stream comprising the homogeneous metathesis catalyst system; the first stream is connected to a catalyst removal unit and a first product separation zone of the distillation column; The system wherein the first product separation zone is configured to separate the unreacted reactive olefin and the second product olefin into a vapor portion containing the unreacted reactive olefin and a liquid portion containing the second product olefin.

[0107] Paragraph 28: The system of paragraph 27 having any function, any aspect, feature, additional component having a corresponding function, aspect, or feature, or combination thereof, as described herein.

[0108] Paragraph 29: An olefin metathesis system, a distillation column having a reaction zone, a first product separation zone above the reaction zone, the reaction zone configured to contact a first reactive olefin in the presence of a homogeneous metathesis catalyst system to form a metathesis product comprising a first product olefin and a second product olefin, the reaction zone having a reaction tray and a liquid collection tray below the reaction tray, the product separation zone having at least one distillation structure, the product separation zone configured to receive a vapor phase containing unreacted reactive olefin and the first product olefin from the reaction zone; a catalyst removal unit fluidly connected to the reaction zone of the distillation column and configured to receive a liquid phase containing the second product olefins, unreacted reactive olefins, and the homogeneous metathesis catalyst system from the reaction zone of the distillation column and separate the liquid phase into a first stream comprising the unreacted reactive olefins and the second product olefins and a second stream comprising the homogeneous metathesis catalyst system; a stripping column fluidly connected to the first stream and configured to receive the first stream as reflux at an upper portion of the stripping column and separate the first stream into a vapor portion comprising unreacted reactive olefins and a liquid portion comprising second product olefins; The system, wherein the product separation zone is configured to separate the unreacted reactive olefins and the first product olefins into a vapor fraction containing the first product olefins and a liquid fraction containing the unreacted reactive olefins.

[0109] Paragraph 30: The system of paragraph 29 having any function, any aspect, feature, additional component having a corresponding function, aspect, or feature, or combination thereof, as described herein.

[0110] Although the present disclosure and its advantages have been described in detail, it should be understood that various changes, substitutions, and alterations can be made therein without departing from the spirit and scope of the present disclosure, as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the processes, machines, manufacture, compositions of matter, means, processes, and steps described in the specification. As those skilled in the art will readily appreciate from this disclosure, any now-existing or later-developed processes, machines, manufacture, compositions of matter, means, processes, or steps that perform substantially the same function or achieve substantially the same function will result in the corresponding embodiments described herein being utilized in accordance with the present disclosure. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, processes, or steps.

Claims

1. 1. A process for olefin metathesis by reactive distillation comprising: reacting a first reactive olefin in the presence of a homogeneous metathesis catalyst system in a reaction zone of a distillation column to form a metathesis product comprising a first product olefin and a second product olefin.

2. 2. The process of claim 1, wherein the first product olefin has a carbon number less than the carbon number of the first reactive olefin and the second product olefin comprises a carbon number greater than the carbon number of the first reactive olefin.

3. removing a liquid phase comprising the second product olefin and the homogeneous metathesis catalyst system from the reaction zone of the distillation column; 10. The process of claim 1 further comprising removing a vapor phase comprising said first product olefin from said distillation column.

4. 4. The process of claim 3, further comprising, after removing the liquid phase, separating the liquid phase into a first stream comprising the second product olefin and a second stream comprising the homogeneous metathesis catalyst system.

5. the liquid phase further comprises unreacted reactive olefins comprising the first reactive olefin, the first stream further comprises the unreacted reactive olefin, and the process comprises: introducing said first stream into a first product separation zone; 5. The process of claim 4, comprising separating said second product olefins and said unreacted reactive olefins in said first product separation zone into a first vapor fraction comprising said unreacted reactive olefins and a first liquid fraction comprising said second product olefins.

6. 6. The process of claim 5, further comprising recycling the first vapor portion to the reaction zone.

7. the vapor phase further comprising the unreacted reactive olefin, and the process comprises: removing said vapor phase and then introducing said vapor phase into a second product separation zone; further comprising separating the vapor phase in the second product separation zone into a second vapor portion comprising the first product olefin and a second liquid portion comprising the unreacted reactive olefin; 6. The process of claim 5, wherein the second liquid portion flows from the second product separation zone to the reaction zone.

8. 8. The process of claim 7, wherein the reaction zone, the first product separation zone, and the second product separation zone are contained within the distillation column, the first product separation zone being below the reaction zone and the second product separation zone being above the reaction zone.

9. 9. The process of claim 8, wherein the reaction zone has a liquid collection tray disposed below the reaction tray within the distillation column, and the first reactive olefin and the homogeneous metathesis catalyst system are introduced into the distillation column above the reaction tray.

10. 10. The process of claim 9, wherein the liquid phase is removed from the reaction zone of the distillation column via a side draw stream fluidly connected to the liquid collection tray.

11. 10. The process of claim 9, wherein the first vapor portion is recycled to the reaction zone via vapor passages formed in the liquid collection tray.

12. 8. The process of claim 7, wherein the reaction zone and the second product separation zone are contained within the distillation column, the second product separation zone being above the reaction zone within the distillation column, and the first product separation zone being within a stripping column.

13. 13. The process of claim 12, wherein the first stream is introduced as reflux into the top of the stripping column.

14. receiving the first vapor portion from the stripping column into the reaction zone of the distillation column; removing the first liquid portion from a bottom section of the stripping column; reboiling at least a portion of the first liquid portion after removing the first liquid portion; 13. The method of claim 12, further comprising introducing said at least a portion of said reboiled first liquid portion into said stripping column.

15. 10. The process of claim 1, wherein the reaction zone does not contain a heterogeneous metathesis catalyst.

16. 10. The process of claim 1, wherein the first product olefin is ethylene or propylene.

17. 10. The process of claim 1, wherein the homogeneous metathesis catalyst system comprises a metathesis catalyst dissolved in an inert solvent.

18. 20. The process of claim 17, wherein the homogeneous metathesis catalyst system comprises a metal carbene-based metathesis catalyst system.

19. introducing a second reactive olefin into the reaction zone of the distillation column; 10. The process of claim 1, further comprising reacting said second reactive olefin in the presence of said homogeneous metathesis catalyst system in said reaction zone to form said metathesis product.

20. 20. The process of claim 19, wherein the first product olefin has a carbon number less than the carbon number of the second reactive olefin and the second product olefin has a carbon number greater than the carbon number of the second reactive olefin.

21. 1. An olefin metathesis system comprising: a distillation column having a reaction zone, a first product separation zone below the reaction zone, and a second product separation zone above the reaction zone, the reaction zone configured to contact a first reactive olefin in the presence of a homogeneous metathesis catalyst system to form a metathesis product comprising a first product olefin and a second product olefin, the reaction zone having a reaction tray and a liquid collection tray below the reaction tray, the first product separation zone having at least one distillation structure, the first product separation zone fluidly connected to the reaction zone via a vapor path in the liquid collection tray; a catalyst removal unit fluidly connected to the liquid collection tray of the reaction zone of the distillation column and configured to receive a liquid phase containing the second product olefins, unreacted reactive olefins, and the homogeneous metathesis catalyst system from the liquid collection tray and separate the liquid phase into a first stream comprising the unreacted reactive olefins and the second product olefins and a second stream comprising the homogeneous metathesis catalyst system; the first stream is connected to the catalyst removal unit and the first product separation zone of the distillation column; the first product separation zone is configured to separate the unreacted reactive olefins and the second product olefins into a vapor fraction containing the unreacted reactive olefins and a liquid fraction containing the second product olefins.

22. 1. An olefin metathesis system comprising: a distillation column having a reaction zone and a product separation zone above the reaction zone, the reaction zone configured to contact a first reactive olefin in the presence of a homogeneous metathesis catalyst system to form a metathesis product comprising a first product olefin and a second product olefin, the reaction zone having a reaction tray and a liquid collection tray below the reaction tray, the product separation zone having at least one distillation structure, the product separation zone configured to receive a vapor phase comprising unreacted reactive olefin and the first product olefin from the reaction zone; a catalyst removal unit fluidly connected to the reaction zone of the distillation column and configured to receive a liquid phase containing the second product olefins, unreacted reactive olefins, and the homogeneous metathesis catalyst system from the reaction zone of the distillation column and separate the liquid phase into a first stream comprising the unreacted reactive olefins and the second product olefins and a second stream comprising the homogeneous metathesis catalyst system; a stripping column fluidly connected to said first stream and configured to receive said first stream as reflux at an upper portion of said stripping column and to separate said first stream into a vapor portion comprising said unreacted reactive olefins and a liquid portion comprising said second product olefins; the product separation zone is configured to separate the unreacted reactive olefins and the first product olefins into a vapor fraction containing the first product olefins and a liquid fraction containing the unreacted reactive olefins.

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