WO2017093858A1

WO2017093858A1 - Methods for producing olefins

Info

Publication number: WO2017093858A1
Application number: PCT/IB2016/057074
Authority: WO
Inventors: Radu IGNAT; Kuldeep WADHWA; Antonio MATARREDONA; Sekhar MAMILLA; Christoph ROOSEN; Alex LONDONO
Original assignee: Sabic Global Technologies B.V.
Priority date: 2015-11-30
Filing date: 2016-11-23
Publication date: 2017-06-08

Abstract

The presently disclosed subject matter relates to methods and systems for producing olefins. The presently disclosed subject matter is directed to a system for producing high purity olefins which can include one or more reactive distillation columns coupled to an isomerization reactor and/or purification column. A method for producing high purity olefins can include selectively reacting 1-butene and/or 2-butene from a mixed hydrocarbon stream to form 2-butanol, reacting the 2-butanol in the presence of a catalyst to form 2-butene, isomerizing the 2-butene to form 1-butene and purifying the 1-butene to generate a high purity 1-butene product.

Description

METHODS FOR PRODUCING OLEFINS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and the benefit of U.S. Provisional Application No. 62/260,939, filed November 30, 2015. The contents of the referenced application are incorporated into the present application by reference.

FIELD

[0002] The presently disclosed subject matter relates to methods and systems for producing olefins from hydrocarbon streams.

BACKGROUND

[0003] High purity 1-butene can be obtained from C4 hydrocarbon streams by steam cracking or fluid catalytic cracking, followed by separation processes. C4 hydrocarbon streams can include a number of components such as, but not limited to, butadiene, isobutene, 1-butene, 2-butene (cis- and trans-2-butene), iso-butane and n-butane. Because these components have small boiling point differences, form binary and ternary azeotropes, and have low separation factors, simple distillation of 1-butene from other components within the C4 stream is not economically feasible.

[0004] 1-butene can be obtained from other products by a combination of chemical reactions and physical separating operations, such as those known in the art. For example, the process can include removing butadiene from a C4 hydrocarbon stream by extractive distillation and/or selective hydrogenation and selectively removing isobutylene by chemical reactions. The remaining C4 fraction can contain 1-butene, cis-2-butene, trans-2 butene, isobutane and n-butane, and high purity 1-butene can be recovered by distillation. For example, U.S. Patent No. 7,932,428 discloses a process for preparing 1-butene from a mixture of C4 hydrocarbons that includes reacting isobutene to produce products that boil at a temperature higher than 30°C, where isobutene undergoes acid-catalyzed esterification and is separated from 1-butene.

[0005] In certain situations such as the production of copolymers, e.g., ethylene-a-olefin copolymers, product specifications for 1-butene can be strict. For example, if small amounts of butadiene and isobutene are still present in the product, certain 1-butene product specifications cannot be met and the removal of such contaminant compounds requires additional equipment, which can lead to a loss of 1-butene while increasing overall investment costs. Therefore, there remains a need in the art for methods and systems for manufacturing 1-butene.

SUMMARY OF THE DISCLOSED SUBJECT MATTER

[0006] The presently disclosed subject matter provides for systems and methods for manufacturing olefins. For example, and not by way of limitation, the presently disclosed subject matter provides systems and methods for producing alpha-olefins, e.g., 1-butene. In certain embodiments, the presently disclosed subject matter further provides methods for manufacturing esters, alcohols, ethers and amines.

[0007] In certain embodiments, a method for producing olefins, e.g., 1-butene, from a hydrocarbon stream, e.g., a mixed hydrocarbon stream, can include selectively reacting olefins, e.g., 2-butene, from the hydrocarbon stream with a reactant and a first catalyst to form a first stream. In certain embodiments, the first stream includes 2-butanol and light hydrocarbons. In certain embodiments, the first stream is produced in a first reactive distillation column. Alternatively, the first stream is initially produced in a first reactor and then transferred to a first distillation column. Non-limiting examples of the reactant can include water, one or more alcohol(s), one or more carbonic acid(s), one or more halide(s), e.g., hydrogen halides, one or more amine(s) or combinations thereof. In certain embodiments, the method includes removing any light hydrocarbons from the first stream, e.g., in the first distillation column or reactive distillation column, to produce a second stream, which can include, for example, separated 2-butanol, esters, ethers and/or amines.

[0008] In certain embodiments, the method can further include reacting the second stream, e.g., 2-butanol, in the presence of a second catalyst to form a third stream that includes, but is not limited to, 2-butene and/or 1-butene. In certain embodiments, the third stream can be produced in a second reactive distillation column. Alternatively, the third stream can be produced in a second reactor and transferred to a second distillation column. In certain embodiments, the method can further include isomerizing any 2-butene (e.g., cz^'s-2-butene and/or trans-2-butene) present within the third stream to generate a fourth stream that contains 1-butene and/or 2-butene. The method can further include purifying the fourth stream to produce a purified product. In certain embodiments, 1-butene is purified from the fourth stream to produce a purified 1-butene product. In certain embodiments, 2-butene is purified from the fourth stream to produce a purified 2-butene product.

[0009] In a further non-limiting embodiment, a method for preparing olefins, e.g., 1-butene, from a hydrocarbon stream, e.g., a C4 olefinic stream, can include selectively reacting olefins, obtained from the hydrocarbon stream, with a reactant and a first catalyst, e.g., within a first reactive distillation column, to form a first stream. In certain embodiments, the first stream can include 2-butanol, esters, ethers, amines and/or light hydrocarbons. The reactant can be water, one or more alcohol(s), one or more carbonic acid(s), one or more halide(s), one or more hydrogen halide(s), one or more amine(s), or combinations thereof. Alternatively, the first stream can initially be produced in a first reactor and then transferred to a first distillation column. In certain embodiments, the method can further include separating any light hydrocarbons from the first stream, e.g., within the first reactive distillation column, to produce a second stream that includes 2-butanol, esters, ethers and/or amines. The method can further include reacting the second stream in the presence of a second catalyst, e.g., in a second reactive distillation column, to form a third stream that includes 1-butene and/or 2- butene. Alternatively, the second stream can initially be produced in a second reactor and then transferred to a second distillation column. In certain embodiments, the method can further include purifying the third stream, e.g., within a purification column, to produce a purified product stream, e.g., a purified 1 -butene product stream. In certain embodiments, purification of the third stream can also result in the generation of a fourth stream, e.g., that includes 2-butene.

[0010] In certain embodiments, the olefins within the hydrocarbon stream are 1 -butene and/or 2-butene. In certain embodiments, the hydrocarbon stream is a C4 stream, e.g., a C4 olefinic stream. In certain embodiments, the purified product stream is a 1 -butene purified product stream. In certain embodiments, the purified product stream is an ester, ether or amine purified product stream. In certain embodiments, the purified product stream is a 2- butene purified product stream.

[0011] In certain embodiments, the method can further include isomerizing the 2-butene present within the fourth stream, e.g., within an isomerization unit, to produce a fifth stream that includes 1 -butene. In certain embodiments, the method can further include purifying 1- butene from the fifth stream to produce an additional purified 1 -butene product stream. Alternatively, the fifth stream and the third stream can be combined, e.g., within a single purification column, and purified to produce a single purified 1 -butene product stream.

[0012] In certain embodiments, the hydrocarbon stream that is used within the disclosed methods can be subjected to a hydrogenation reaction to selectively hydrogenate butadiene within the hydrocarbon stream to form 1 -butene. In certain embodiments, the 1 -butene within such a C4 hydrocarbon stream, e.g., hydrogenated C4 hydrocarbon stream, can be reacted with a reactant and first catalyst to form a stream that includes 2-butanol, esters, ethers or amines, as disclosed above.

[0013] In certain embodiments, the reactant can be water, a halide, a hydrogen halide, hydrogen chloride (HQ), 2-butanol, esters, ethers or amines. In certain embodiments, the ratio of reactant to butenes (e.g., 1-butene and/or 2-butene) can be about 1 :7.5, about 1 :5 or about 1 :2.5 of reactan butene.

[0014] In certain embodiments, the first catalyst is an acid catalyst and the second catalyst is an acid catalyst or a base catalyst. In certain embodiments, the first and/or second catalyst is a homogeneous catalyst. In certain embodiments, the first and second catalysts are the same.

[0015] In certain embodiments, the method can be performed at an operating temperature from about 50 to about 500°C. In certain embodiments, the method can be performed at an operating temperature from about 80 to about 350°C. In certain embodiments, the method can be performed at an operating temperature from about 100 to about 250°C. In certain embodiments, the method can be performed at an operating pressure from about 1 to about 50 bars. In certain embodiments, the method can be performed at an operating pressure from about 2 to about 25 bars. In certain embodiments, the method can be performed at an operating pressure from about 4 to about 16 bars.

[0016] In certain embodiments, a system for producing olefins from a hydrocarbon stream can include a reactive distillation column, configured to react a hydrocarbon stream with one or more reactants in the presence of a first catalyst to produce a first stream. In certain embodiments, the first stream includes 2-butanol, esters, ethers, amines and/or light hydrocarbons. The system can further include a second reactive distillation column, coupled to the first reactive distillation column and configured to produce a second stream. In certain embodiments, the second stream includes 2-butene, e.g., produced from 2-butanol within the first stream. The system can further include an isomerization reactor, coupled to the second distillation column for isomerization of any 2-butene present within the second stream, e.g., into 1-butene. In certain embodiments, the system can further include a purification column, coupled to the isomerization reactor, to produce a purified product. In certain embodiments, the purification column can be coupled to the second distillation column. In certain embodiments, the purified product is a 1-butene purified product. In certain embodiments, the purified product is a 2-butene purified product. In certain embodiments, the purified product is a purified ester, ether and/or amine product.

[0017] In certain embodiments, the first reactive distillation column is replaced with a first reactor coupled to a first distillation column. In certain embodiments, the second reactive distillation column is replaced with a second reactor coupled to a second distillation column.

[0018] Also disclosed in the context of the present invention is embodiments 1-42. Embodiment 1 is a method for producing olefins from a hydrocarbon stream, comprising: (a) selectively reacting olefins, if any, from the hydrocarbon stream with a reactant selected from the group consisting of water, one or more alcohol(s), one or more carbonic acid(s), one or more halide(s), one or more ester(s), or one or more amine(s), and combinations thereof, and a first catalyst to produce a first stream comprising 2-butanol and, if any, light hydrocarbons; (b) removing any light hydrocarbons from the first stream to produce a second stream comprising 2-butanol; (c) reacting the second stream in the presence of a second catalyst to produce a third stream comprising 2-butene and/or 1-butene; (d) isomerizing any 2-butene present within the third stream to produce a fourth stream comprising 2-butene and/or 1- butene; and (e) purifying the fourth stream to produce a purified product. Embodiment 2 is the method of embodiment 1, wherein the olefins within the hydrocarbon stream are 1-butene and/or 2-butene. Embodiment 3 is the method of embodiment 1 or 2, wherein the hydrocarbon stream is a C4 olefinic stream. Embodiment 4 is the method of embodiment 1, wherein the second stream further comprises 1-butanol and/or water. Embodiment 5 is the method of embodiment 4, further comprising separating water from the second stream and recycling the water back to the hydrocarbon stream and/or the reactant. Embodiment 6 is the method of embodiment 1, wherein the second stream further comprises 2-methyl-l-propanol and/or 1,4-butadiol. Embodiment 7 is the method of embodiment 1, wherein the purified product is purified 2-butene. Embodiment 8 is the method of embodiment 1, wherein the purified product is purified 1-butene. [0019] Embodiment 9 is a method for preparing olefins from a hydrocarbon stream, comprising: (a) selectively reacting olefins, present within the hydrocarbon stream, with a reactant selected from the group consisting of water, one or more alcohol(s), one or more carbonic acid(s), one or more halide(s), one or more hydrogen halide(s), one or more amine(s), or combinations thereof, and a first catalyst to produce a first stream comprising 2- butanol and light hydrocarbons; (b) removing any light hydrocarbons from the first stream to produce a second stream comprising 2-butanol; (c) reacting the second stream in the presence of a second catalyst to produce a third stream comprising 2-butene and/or 1-butene; and (d) purifying the third stream to produce a purified product stream. Embodiment 10 is the method of embodiment 9, wherein the olefins within the hydrocarbon stream are 1-butene and/or 2-butene. Embodiment 11 is the method of embodiment 9, wherein the hydrocarbon stream is a C4 olefinic stream. Embodiment 12 is the method of embodiment 9, wherein the second stream further comprises 1 -butanol and/or water. Embodiment 13 is the method of embodiment 9, wherein the second stream further comprises 2-methyl-l-propanol and/or 1,4- butadiol. Embodiment 14 is the method of embodiment 9, wherein the purified product is purified 1-butene. Embodiment 15 is the method of embodiment 9, wherein the purified product is purified 2-butene. Embodiment 16 is the method of embodiment 9, further comprising isomerizing the 2-butene from the third stream to 1-butene. Embodiment 17 is the method of any one of embodiments 1-16, wherein the reactant comprises water. Embodiment 18 is the method of any one of embodiments 1-17, wherein the reactant comprises a hydrogen halide. Embodiment 19 is the method of embodiment 18, wherein the hydrogen halide is hydrogen chloride (HC1). Embodiment 20 is the method of any one of embodiments 1-19, wherein the ratio of reactants to the olefins is about 1 :7.5 reactants:olefins. Embodiment 21 is the method of any one of embodiments 1-19, wherein the ratio of reactants to the olefins is about 1 :5 reactants:olefins. Embodiment 22 is the method of any one of embodiments 1-19, wherein the ratio of reactants to the olefins is about 1 :2.5 reactants:olefins. Embodiment 23 is the method of any one of embodiments 1-22, further comprising hydrogenating the hydrocarbon stream to selectively hydrogenate butadiene to generate 1- butene. Embodiment 24 is the method of any one of embodiments 1-23, wherein the first catalyst comprises an acid catalyst. Embodiment 25 is the method of any one of embodiments 1-23, wherein the second catalyst comprises an acid or a base catalyst. Embodiment 26 is the method of any one of embodiments 1-23, wherein the first catalyst and the second catalyst are the same. Embodiment 27 is the method of any one of embodiments 1-23, wherein the first and/or second catalyst comprises a homogeneous or heterogeneous catalyst. Embodiment 28 is the method of any one of embodiments 1-27, wherein the method further comprises an operating temperature of from about 50 to about 500°C. Embodiment 29 is the method of any one of embodiments 1-27, wherein the method is performed at an operating temperature of from about 80 to about 350°C. Embodiment 30 is the method of any one of embodiments 1-27, wherein the method is performed at an operating temperature of from about 100 to about 250°C. Embodiment 31 is the method of any one of embodiments 1-30, wherein the method is performed at an operating pressure from about 1 to about 50 bars. Embodiment 32 is the method of any one of embodiments 1-30, wherein the method is performed at an operating pressure from about 2 to about 25 bars. Embodiment 33 is the method of any one of embodiments 1-30, wherein the method is performed at an operating pressure from about 4 to about 16 bars. [0020] Embodiment 34 is a system for producing olefins from a hydrocarbon stream, comprising: (a) a first reactive distillation column configured to react a hydrocarbon stream with one or more reactants in the presence of a first catalyst to produce a first stream; (b) a second reactive distillation column, coupled to the first reactive distillation column, configured to produce a second stream from the first stream; (c) an isomerization reactor, coupled to the second reactive distillation column, for producing a third stream; and (d) a purification column, coupled to the isomerization reactor and/or the reactive second distillation column, to produce a purified product from the third stream. Embodiment 35 is the system of embodiment 34, wherein the first stream comprises 2-butanol, esters, ethers, amines and/or light hydrocarbons. Embodiment 36 is the system of embodiment 34, wherein the second stream comprises 2-butene. Embodiment 37 is the system of embodiment 34, wherein the third stream comprises 1-butene and/or 2-butene. Embodiment 38 is the system of embodiment 34, wherein the purified product is purified 1-butene. Embodiment 39 is the system of embodiment 34, wherein the purified product is purified 2-butene. Embodiment 40 is the system of embodiment 34, wherein the purified product is purified esters, ethers and/or amines. Embodiment 41 is the system of embodiment 34, wherein the first reactive distillation column is replaced with a first reactor coupled to a first distillation column. Embodiment 42 is the system of embodiment 34, wherein the second reactive distillation column is replaced with a second reactor coupled to a second distillation column.

BRIEF DESCRIPTION OF THE DRAWINGS

[0021] FIG. 1 is a schematic diagram depicting an exemplary state of the art process for obtaining high purity 1-butene from hydrocarbon streams.

[0022] FIG. 2 is a schematic diagram depicting an exemplary system for obtaining high purity 1-butene from C4 hydrocarbon streams in accordance with one non-limiting embodiment of the disclosed subject matter.

[0023] FIG. 3 is a schematic diagram depicting an exemplary system for obtaining high purity 1-butene from C4 hydrocarbon streams in accordance with one non-limiting embodiment of the disclosed subject matter.

[0024] FIG. 4 is a schematic diagram depicting an exemplary system for obtaining high purity 1-butene from C4 hydrocarbon streams in accordance with one non-limiting embodiment of the disclosed subject matter.

[0025] FIG. 5 is a schematic diagram depicting an exemplary system for obtaining high purity 1-butene from C4 hydrocarbon streams in accordance with one non-limiting embodiment of the disclosed subject matter.

[0026] FIG. 6 depicts a method for the production of high purity 1-butene according to one exemplary non-limiting embodiment of the disclosed subject matter.

[0027] FIG. 7 depicts a method for the production of high purity 1-butene according to one exemplary non-limiting embodiment of the disclosed subject matter.

[0028] FIG. 8 depicts a method for the production of high purity 1-butene according to one exemplary non-limiting embodiment of the disclosed subject matter.

DETAILED DESCRIPTION

[0029] The presently disclosed subject matter provides for systems and methods for producing olefins. For example, and not by way of limitation, the presently disclosed subject matter provides systems and methods for producing 1-butene and/or 2-butene. The presently disclosed subject matter further provides methods and systems for producing esters, alcohols, ethers and/or amines.

[0030] In certain embodiments, the presently disclosed subject matter is directed to a system that includes at least one or more reactors, distillation columns, purification columns and/or reactive distillation columns for the production of olefins, e.g., 1-butene, from hydrocarbon streams, e.g., C4 hydrocarbon streams. For example, and not by way of limitation, the system can include one or more reactors and one or more distillation columns. In certain embodiments, the system can include two distillation columns, e.g., reactive distillation columns. In certain embodiments, the presently disclosed subject matter is directed to a system that includes at least two reactive distillation columns coupled to an isomerization reactor and/or a purification column for the production of high purity 1-butene and/or 2-butene.

[0031] For the purpose of illustration and not limitation, FIG. 2 is a schematic representation of an exemplary system according to the disclosed subject matter. In certain embodiments, the system 200 includes two or more distillation columns 201 and 202. The distillation columns used in the disclosed subject matter can be any distillation column known in the art. In certain embodiments, the distillation columns are reactive distillation columns.

[0032] In certain embodiments, the system 200 includes a feed line 203 to introduce a reactant into the first reactive distillation column 201. Non-limiting examples of the reactant include water, one or more alcohol(s), one or more carbonic acid(s), hydrogen chloride (HCl), one or more halide(s), e.g., hydrogen halide(s), one or more amine(s), or combinations thereof. In certain embodiments, the system 200 includes a feed line 204 to introduce a hydrocarbon stream, e.g., a C4 hydrocarbon stream, into the first reactive distillation column 201. The C4 hydrocarbon stream can include, but is not limited to, 1-butene, czs-2-butene, tram--2-butene, isobutane and/or n-butane. In certain embodiments, the C4 hydrocarbon stream can further include 1,3-butadiene (also referred to herein as butadiene) and isobutene.

[0033] In certain embodiments, the system 200 can include one or more transfer lines. In certain embodiments, the transfer lines can transport intermediate streams, e.g., the second stream and/or third streams, between reactive distillation columns 201 and 202, the isomerization reactor 206 and/or the purification column 207 (see FIG. 2). In certain embodiments, the first reactive distillation column 201 is coupled to the second reactive distillation column 202, e.g., via transfer line 211. In certain embodiments, a second stream, e.g., that includes 2-butanol (see below for further discussion), is separated at the bottom of the first reactive distillation column 201 to generate a third stream, which can be transferred via a transfer line 211 to the second reactive distillation column 202. In certain embodiments, light hydrocarbons are removed as an overhead stream via transfer line 210 from the first reactive distillation column 201.

[0034] In certain embodiments, the bottom of the second reactive distillation column 202 is coupled to the reactant feed line 203 via transfer line 205. In certain embodiments, transfer line 205 can be used to transfer components, e.g., water, from the second reactive distillation column 202 to the reactant feed line 203 which can then be fed into the first reactive distillation column 201.

[0035] In certain embodiments, the second reactive distillation column 202 is coupled to the isomerization reactor 206 via transfer line 212. In certain embodiments, components, e.g., 2-butene, from the second reactive distillation column 202 can be transferred to the isomerization reactor 206 via transfer line 212 and isomerized within the isomerization reactor 206. In certain embodiments, the isomerization reactor 206 is coupled to the purification column 207 via transfer line 213. In certain embodiments, components from the isomerization reactor 206, e.g., 1-butene produced by the isomerization of 2-butene, can be transferred to the purification column 207 via transfer line 213 and purified within the purification column 207. In certain embodiments, a transfer line 208 connects the purification column 207 and the isomerization reactor 206. In certain embodiments, the purification column 207 can be coupled to the isomerization unit 206 and/or transfer line 212 via transfer line 214 to transfer components that are separated from the 1-butene within the purification column 207, such as 2-butene, from the purification column 207 and to the isomerization reactor 206. In certain embodiments, the second reactive distillation column 202 can be coupled to the purification column 207 to transfer components from the second reactive distillation column 202, e.g., 2-butene, and purified within the purification column 207, e.g., to produce a 2-butene purified product.

[0036] For the purpose of illustration and not limitation, FIGS. 3 and 4 are schematic representations of exemplary systems 300 and 400 according to the disclosed subject matter. In certain embodiments, the system can include, but is not limited to, two distillation columns, e.g., reactive distillation columns, coupled to a purification column.

[0037] In certain embodiments, the system 300 can include a feed line 301 coupled to a first distillation column 303, e.g., a reactive distillation column. In certain embodiments, the feed line 301 can transport a reactant, e.g., water, one or more alcohol(s), one or more carbonic acid(s), HC1, one or more halide(s), e.g., hydrogen halides, one or more amine(s), one or more ester(s), or combinations thereof, into the first reactive distillation column 303. In certain embodiments, the system 300 can include a second feed line 302, e.g., to introduce a C4 hydrocarbon stream into the first reactive distillation column 303.

[0038] In certain embodiments, the first reactive distillation column 303 is coupled to a second distillation column 305, e.g., a reactive distillation column, via a transfer line 310. For example and not by way of limitation, light hydrocarbons can be removed as an overhead stream via transfer line 304 from the first reactive distillation column 303 to produce a second stream containing a reaction product, e.g., 2-butanol, which can be transferred to the second reactive distillation column 305 via transfer line 310. In certain embodiments, the second reactive distillation column 305 is coupled to feed line 301, e.g., for transferring components from the second reactive distillation column 305 to the feed line 301. For example, and not by way of limitation, a water stream can be transferred from the second reactive distillation column 305 to the first reactive distillation column 303 via transfer line [0039] In certain embodiments, the second reactive distillation column 305 is coupled to a purification column 306, e.g., via a transfer line 311. In certain embodiments, a third stream, e.g., containing 1-butene, can be transported from the second reactive distillation column 305 to the purification column 306 to purify 1-butene from the other components within the third stream.

[0040] In certain embodiments, the purification column 306 is coupled to an isomerization reactor 308, e.g., via a transfer line 307. In certain embodiments, components within the third stream, e.g., 2-butene, can be transported from the purification column 306 to the isomerization reactor 308. For example, and not by way of limitation, 2-butene can be isomerized in the isomerization reactor 308 to generate 1-butene. In certain embodiments, the isomerization reactor 308 is also coupled to the purification column 306, e.g., via a transfer line 312. In certain embodiments, a fourth stream, e.g., that includes 1-butene, is transferred from the isomerization unit 308 to the purification column 306 to generate a purified 1-butene product.

[0041] Alternatively or additionally, in certain embodiments and as shown in FIG. 4, the system does not include an isomerization unit and the purification column 406 can be coupled to a second distillation column 405, e.g., reactive distillation column, via a transfer line 408. In certain embodiments, a hydrocarbon stream can be transferred to the first reactive distillation column 403 via transfer line 401. The olefins, e.g., 2-butene, within the hydrocarbon stream can, in turn, be reacted with a reactant in the presence of a catalyst in the first distillation column 403, e.g., reactive distillation column, to generate 2-butanol. In certain embodiments, the 2-butanol can be transferred to the second reactive distillation column as described above. In certain embodiments, where the system does not include an isomerization unit, 2-butene separated from the purified 1-butene product, e.g., within the purification column 406, can be further purified to generate a purified 2-butene product. [0042] For the purpose of illustration and not limitation, FIG. 5 is a schematic representation of an exemplary system 500 according to the disclosed subject matter. In certain embodiments, the system can include two or more distillation columns 504 and 506, e.g., reactive distillation columns, coupled to a hydrogenation reactor 502 and a purification column 507 to obtain olefins, e.g., 1-butene, from a C4 hydrocarbon stream, e.g., a C4 olefinic stream. In certain embodiments, the system 500 can include a feed line 501 to introduce a C4 hydrocarbon stream into a selective hydrogenation reactor 502. For example, and not by way of limitation, butadiene within the C4 hydrocarbon stream can be selectively hydrogenated in the hydrogenation reactor 502 to generate 1-butene.

[0043] In certain embodiments, the selective hydrogenation reactor 502 is coupled to a first reactive distillation column 504, e.g., via a transfer line 512. For example, and not by way of limitation, a first stream, e.g., a hydrogenated C4 stream that includes hydrogenation product 1-butene, is transferred to the first reactive distillation column 504 via transfer line 512.

[0044] In certain embodiments, the system 500 can further include a feed line 511 to introduce a reactant, as described above, into the first reactive distillation column 504. In certain embodiments, the first reactive distillation column 504 is coupled to a second reactive distillation column, e.g., via a transfer line 514. In certain embodiments, the light hydrocarbons are removed via a transfer line 505 as overhead stream from the first stream present within the first reactive distillation column 504. In certain embodiments, a second stream that includes, for example, 2-butanol is transferred to a second reactive distillation column 506 and reacted within the second reactive distillation column 506 to generate a third stream, e.g., that includes 1-butene. In certain embodiments, the second reactive distillation column 506 is coupled to the feed line 511 via transfer line 510. In certain embodiments, transfer line 510 can be used to transfer components present within the second reactive distillation column 506, e.g., water, to the feed line 511, which is then fed into the first reactive distillation column 504.

[0045] In certain embodiments, the second reactive distillation column 506 is coupled to a purification column 507, e.g., via a transfer line 514. In certain embodiments, the 1-butene present within the third stream can be separated at the top of the second reactive distillation column 506 and transferred to and purified within the purification column 507. In certain embodiments, a transfer line 509 transports the other components present within the third stream, e.g., as a bottom stream (e.g., a fourth stream), away from the purification column 507. In certain embodiments, the bottom stream can include 2-butene.

[0046] In certain embodiments, the distillation columns, e.g., reactive distillation columns, and/or reactors of the presently disclosed systems contain one or more catalysts. In certain embodiments, the first reactive distillation column contains an acid catalyst. In certain embodiments, the second reactive distillation column contains a selective catalyst. In certain embodiments, the second reactive distillation column contains a catalyst selective for Hofmann products. In certain embodiments, the first reactive distillation column and/or the second reactive distillation column contain a heterogeneous catalyst. In certain embodiments, the first reactive distillation column and/or the second reactive distillation column contain a homogeneous catalyst. In certain embodiments, the reactive distillation columns contain one or more catalysts. In certain embodiments, the first reactive distillation column and the second reactive distillation column contain the same catalyst. Alternatively, the first reactive distillation column and the second reactive distillation column contain different catalysts.

[0047] In certain embodiments, the first reactive distillation column is replaced with a first reactor coupled to a first distillation column, where the reaction takes placed in the reactor and the product stream is transferred to the first distillation column for separation of the components within the product stream. Alternatively and/or additionally, the second reactive distillation column can be replaced with a second reactor coupled to a second distillation column, where the reaction takes placed in the reactor and the product stream is transferred to the second distillation column for separation of the components within the product stream.

[0048] The presently disclosed subject matter further provides for methods of obtaining olefins, e.g., 1-butene and/or 2-butene, from hydrocarbon streams. In certain embodiments, the presently disclosed subject matter further provides methods for producing esters, alcohols, ethers and/or amines from a hydrocarbon stream. In certain embodiments, the hydrocarbon stream is a C4 hydrocarbon stream, e.g., a C4 olefinic stream. In certain embodiments, the hydrocarbon stream, e.g., C4 hydrocarbon stream, that includes butadiene, isobutene, 1- butene, 2-butene (cz^'s-2-butene and/or trans-2-butene), isobutane and/or n-butane.

[0049] For the purpose of illustration and not limitation, FIGS. 6, 7 and 8 are schematic representations of methods according to non-limiting embodiments of the disclosed subject matter. In certain embodiments, and as shown in FIG. 6, the method 600 can include reacting a hydrocarbon stream with one or more reactants in the presence of a first catalyst to produce a first stream 601, e.g., within the first reactive distillation column. In certain embodiments, the first stream can be produced in a first reactor. For example, and not by way of limitation, the reactant can include water, one or more alcohol(s), one or more carbonic acid(s), halide(s), e.g., HC1 and other hydrogen halides, one or more amine(s) or combinations thereof. In certain embodiments, the reactant is water. In certain embodiments, the first catalyst selectively catalyzes the reaction between the reactant and one or more olefins, e.g., 1-butene and/or 2-butene, from the hydrocarbon stream to produce a first stream that includes 2- butanol. In certain embodiments, the first stream can further include 1-butanol and light hydrocarbons, e.g., unreacted light hydrocarbons. Non-limiting examples of light hydrocarbons include isobutane, n-butane, isobutylene and butadiene. In certain embodiments, isobutene and butadiene within the C4 hydrocarbon steam can react with the reactant, e.g., water, in the presence of the first catalyst to form 2-methyl-l-propanol and 1,4- butadiol, respectively, and the 2-methyl-l-propanol and 1,4-butadiol can be present within the first stream. For example, and not by way of limitation, isobutene within the hydrocarbon stream can react with water to produce 2-methyl-l-propanol, e.g., within the first stream. In certain embodiments, butadiene within the hydrocarbon stream can react with water to produce 1,4-butadiol, e.g., within the first stream.

[0050] In certain embodiments, the method can further include separating the unreacted light hydrocarbons from the 2-butanol present in the first stream, e.g., within the first reactive distillation column, to produce a second stream that includes 2-butanol 602. In certain embodiments, 2-butanol can be separated at the bottom of the first reactive distillation unit to produce the second stream. In certain embodiments, if the system includes a first reactor and a first distillation column, the first stream produced within the first reactor can be transferred to the first distillation column for the separation of 2-butanol from the first stream. In certain embodiments, the second stream can also include 2-methyl-l-propanol and 1,4-butadiol. Alternatively or additionally, in certain embodiments, the 2-methyl-l-propanol and/or 1,4- butadiol can be separated from the first stream to produce a separate stream that includes 2- methyl-l-propanol and/or 1,4-butadiol.

[0051] In certain embodiments, the method can further include reacting the second stream that includes 2-butanol in the presence of a second catalyst, e.g., within a second reactive distillation column, to form a third stream containing 2-butene 603. In certain embodiments, the third stream can further include water. In certain embodiments, the third stream can also include 2-methyl-l-propanol and 1,4-butadiol. In certain embodiments, the second catalyst can have the same or different composition as the first catalyst that is used to generate the first stream that contains 2-butanol.

[0052] In certain embodiments, the water present in the third stream can be recycled, e.g., from the second reactive distillation column to the first reactive distillation column, for further reaction with 1-butene and/or 2-butene in the hydrocarbon stream. In certain embodiments, the 2-methyl-l-propanol and 1,4-butadiol present within the third stream can be separated from the system, e.g., from the third stream, before the water is recycled. In certain embodiments, if the system includes a second reactor and a second distillation column, the third stream produced within the second reactor can be transferred to the second distillation column for the separation of 2-butene from the third stream.

[0053] In certain embodiments, the method can further include isomerizing the 2-butene present within the third stream to generate a fourth stream that includes 1-butene 604. For example, and not by way of limitation, the 2-butene can be isomerized to 1-butene within an isomerization unit to generate the fourth stream. In certain embodiments, the method can further include purifying 1-butene from the fourth stream, e.g., from any remaining 2-butene within the fourth stream, to produce a purified 1-butene product stream 605. For example, and not by way of limitation, the purified 1-butene product stream can include greater than about 90%, greater than about 91%, greater than about 92%, greater than about 93%, greater than about 94%, greater than about 95%, greater than about 96%, greater than about 97%, greater than about 98%, greater than about 99%, greater than about 99.1%, greater than about 99.2%, greater than about 99.3%, greater than about 99.4%, greater than about 99.5%, greater than about 99.6%, greater than about 99.7%, greater than about 99.8% or greater than about 99.9%) 1-butene. In certain embodiments, 1-butene can be purified from the fourth stream within a purification column.

[0054] In certain embodiments, the remaining 2-butene from the fourth stream after purification can be isomerized to generate 1-butene, e.g., by returning the 2-butene to the isomerization unit from the purification unit as a fifth stream (see FIG. 2). Alternatively and/or additionally, the 2-butene within the fourth stream can be purified, e.g., within the purification column, to generate a purified 2-butene product stream, e.g., in the absence of further isomerization. For example, and not by way of limitation, the purified 2-butene product stream can include greater than about 90%, greater than about 91%, greater than about 92%), greater than about 93%, greater than about 94%, greater than about 95%, greater than about 96%, greater than about 97%, greater than about 98%, greater than about 99%, greater than about 99.1%, greater than about 99.2%, greater than about 99.3%, greater than about 99.4%), greater than about 99.5%, greater than about 99.6%, greater than about 99.7%, greater than about 99.8% or greater than about 99.9% 2-butene.

[0055] Alternatively, in certain embodiments and as shown in FIG. 7, a method of the present disclosure 700 can include reacting the second stream containing 2-butanol in the presence of a second catalyst to form a third stream containing 1-butene 703, within the second reactive distillation column, without requiring the use of isomerization unit (see FIGS. 3 and 4). In certain embodiments, the third stream can further include 2-butene. In certain embodiments, the second catalyst is selective for Hofmann products, e.g., 1-butene. In certain embodiments, the second catalyst is heterogeneous. In certain embodiments, the second catalyst is homogeneous. In certain embodiments, the method 700 can further include purifying the third stream, e.g., from any remaining 2-butene, to produce a purified 1-butene product stream 704. In certain embodiments, 1-butene can be purified from the third stream in a purification column. In certain embodiments, the remaining 2-butene from the third stream can be isomerized to generate 1-butene and returned to the purification unit, e.g., as a fourth stream (see FIG. 3). In certain embodiments, the remaining 2-butene from the third stream can be returned to the hydrocarbon stream and/or first stream, e.g., within the first reactive distillation column, to react with the reactant in the presence of the first catalyst. Alternatively and/or additionally, the 2-butene within the third stream can be purified, e.g., within the purification column, to generate a purified 2-butene product stream, e.g., in the absence of further isomerization (see FIGS. 4 and 5). [0056] Alternatively, in certain embodiments and as shown in FIG. 8, a method of the present disclosure 800 can include selectively hydrogenating butadiene in the hydrocarbon stream to form a first stream 801, e.g., a C4 olefin stream including the hydrogenation product 1-butene (see, also, FIG. 5). In certain embodiments, the method 800 can include reacting the first stream in the presence of first catalyst and reactant to form a second stream that includes 2-butanol 802, e.g., within the first reactive distillation column. In certain embodiments, the second stream can further include 1-butanol. In certain embodiments, the reactant can be water, one or more alcohol(s), one or more carbonic acid(s), one or more halide(s), HC1 and other hydrogen halides, or one or more amine(s), or combinations thereof. In certain embodiments, isobutene and butadiene within the hydrocarbon stream can react with the reactant in the presence of the first catalyst to form 2-methyl-l-propanol and 1,4- butadiol, respectively, and the 2-methyl-l-propanol and 1,4-butadiol can be present within the second stream.

[0057] In certain embodiments, the method 800 can further include separating the unreacted light hydrocarbons from the 2-butanol present in the second stream and reacting the 2-butanol in the presence of a second catalyst to form a third stream containing 1-butene 804, e.g., within the second reactive distillation column. In certain embodiments, the method can further include purifying 1-butene from the third stream, e.g., from any remaining 2- butenes within the third stream, to produce a purified 1-butene product stream 804.

[0058] In certain embodiments, an ether, e.g., within the first or second stream described herein, can be formed as an intermediate instead of an alcohol, e.g., 2-butanol, during the production of 1-butene. In certain embodiments, the ether intermediate can be purified to produce purified product steams that include the ether as purified product streams. In certain embodiments, for producing an ether intermediate, the reactants can include, but are not limited to, hydrofluoric acid, hydrochloric acid, hydrobromic acidic and/or hydroiodic acid. [0059] In certain embodiments, the ratio of reactant to olefins (e.g., 1-butene and/or 2- butene) within the hydrocarbon stream is about 1 :2.5 to about 1 :7.5 reactants:olefins. In certain embodiments, the ratio of reactant to olefin is about 1 :7.5 reactants:olefins. In certain embodiments, the ratio of reactant to olefin is about 1 :5 reactants:olefins. In certain embodiments, the ratio of reactant to olefin is about 1 :2.5 reactants:olefins.

[0060] The term "about" or "substantially" means within an acceptable error range for the particular value as determined by one of ordinary skill in the art, which will depend in part on how the value is measure or determine, i.e., the limitations of the measurement system. For example, "about" can mean a range of up to 20%, up to 10%, up to 5% or up to 1% of a given value.

[0061] In certain embodiments, the operating pressure range of the disclosed methods can be from about 1 to about 50 bars. In certain embodiments, the operating pressure range of the disclosed methods can be from about 2 to about 25 bars. In certain embodiments, the operating pressure range of the disclosed methods can be from about 4 to about 16 bars. In certain embodiments, the operating pressure range of the disclosed methods can be from about 6 to about 10 bars. In certain embodiments, the operating temperature of the disclosed methods can be from about 50°C to about 500°C. In certain embodiments, the operating temperature of the disclosed methods can be from about 80 to about 350°C. In certain embodiments, the operating temperature of the disclosed methods can be from about 100°C to about 250°C. In certain embodiments, the operating temperature of the disclosed methods can be from about 110°C to about 150°C.

[0062] In addition to the various embodiments depicted and claimed, the disclosed subject matter is also directed to other embodiments having other combinations of the features disclosed and claimed herein. As such, the particular features presented herein can be combined with each other in other manners within the scope of the disclosed subject matter such that the disclosed subject matter includes any suitable combination of the features disclosed herein. The foregoing description of specific embodiments of the disclosed subject matter has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosed subject matter to those embodiments disclosed.

[0063] It will be apparent to those skilled in the art that various modifications and variations can be made in the compositions and methods of the disclosed subject matter without departing from the spirit or scope of the disclosed subject matter. Thus, it is intended that the disclosed subject matter include modifications and variations that are within the scope of the appended claims and their equivalents. Various patents and patent applications are cited herein, the contents of which are hereby incorporated by reference herein in their entireties.

Claims

1. A method for producing olefins from a hydrocarbon stream, comprising:

a) selectively reacting olefins, if any, from the hydrocarbon stream with a reactant selected from the group consisting of water, one or more alcohol(s), one or more carbonic acid(s), one or more halide(s), one or more ester(s), or one or more amine(s), and combinations thereof, and a first catalyst to produce a first stream comprising 2-butanol and, if any, light hydrocarbons; b) removing any light hydrocarbons from the first stream to produce a second stream comprising 2-butanol;

c) reacting the second stream in the presence of a second catalyst to produce a third stream comprising 2-butene and/or 1-butene;

d) isomerizing any 2-butene present within the third stream to produce a fourth stream comprising 2-butene and/or 1-butene; and

e) purifying the fourth stream to produce a purified product.

2. The method of claim 1, wherein the olefins within the hydrocarbon stream are 1- butene and/or 2-butene.

3. The method of claim 1 or 2, wherein the hydrocarbon stream is a C4 olefinic stream.

4. The method of claim 1, wherein the second stream further comprises 1-butanol and/or water.

5. The method of claim 4, further comprising separating water from the second stream and recycling the water back to the hydrocarbon stream and/or the reactant.

6. The method of claim 1, wherein the second stream further comprises 2-methyl-l- propanol and/or 1,4-butadiol.

7. The method of claim 1, wherein the purified product is purified 2-butene or purified 1-butene.

8. A method for preparing olefins from a hydrocarbon stream, comprising:

a) selectively reacting olefins, present within the hydrocarbon stream, with a reactant selected from the group consisting of water, one or more alcohol(s), one or more carbonic acid(s), one or more halide(s), one or more hydrogen halide(s), one or more amine(s), or combinations thereof, and a first catalyst to produce a first stream comprising 2-butanol and light hydrocarbons; b) removing any light hydrocarbons from the first stream to produce a second stream comprising 2-butanol;

c) reacting the second stream in the presence of a second catalyst to produce a third stream comprising 2-butene and/or 1-butene; and

d) purifying the third stream to produce a purified product stream.

9. The method of claim 8, wherein the olefins within the hydrocarbon stream are 1- butene and/or 2-butene.

10. The method of claim 8, wherein the hydrocarbon stream is a C4 olefinic stream.

11. The method of claim 8, wherein the second stream further comprises 1-butanol and/or water.

12. The method of claim 8, wherein the second stream further comprises 2-methyl-l- propanol and/or 1,4-butadiol.

13. The method of claim 8, wherein the purified product is purified 1-butene or purified 2-butene.

14. The method of claim 8, further comprising isomerizing the 2-butene from the third stream to 1-butene.

15. The method of any one of claims 1-14, wherein the reactant comprises water and/or a hydrogen halide, preferably hydrogen chloride (HC1).

16. The method of any one of claims 1-15, wherein the ratio of reactants to the olefins is about 1 :7.5 reactants: olefins, about 1 :5 reactants:olefins, or about 1 :2.5 reactants:olefins.

17. The method of any one of claims 1-16, further comprising hydrogenating the hydrocarbon stream to selectively hydrogenate butadiene to generate 1-butene.

18. The method of any one of claims 1-17, wherein the first catalyst comprises an acid catalyst or the second catalyst comprises an acid or base catalyst.

19. The method of any one of claims 1-18, wherein the method further comprises:

an operating temperature of from about 50 to about 500°C, about 80 to about 350°C, or about 80 to about 350°C; and/or

an operating pressure from about 1 to about 50 bars, 2 to about 25 bars, or 4 to about 16 bars.

20. A system for producing olefins from a hydrocarbon stream, comprising:

a) a first reactive distillation column configured to react a hydrocarbon stream with one or more reactants in the presence of a first catalyst to produce a first stream;

b) a second reactive distillation column, coupled to the first reactive distillation column, configured to produce a second stream from the first stream; c) an isomerization reactor, coupled to the second reactive distillation column, for producing a third stream; and

d) a purification column, coupled to the isomerization reactor and/or the reactive second distillation column, to produce a purified product from the third stream.