阅读说明：本技术 通过高效的下游分离由正丁烷脱氢制备1-丁烯的方法 (Method for producing 1-butene from n-butane dehydrogenation by efficient downstream separation ) 是由 谢赫扎达·胡拉姆 穆罕默德·H·海德 瓦利德·阿尔达赫劳斯 于 2019-08-27 设计创作，主要内容包括：公开了制备1-丁烯的系统和方法。方法包括将丁烷脱氢以形成包含丁烯异构体的混合物。使用包括膜的系统将1-丁烯从混合物中分离。系统还包括异构化装置,其用于将顺-2-丁烯和反-2-丁烯异构化以形成额外的1-丁烯。(Systems and methods for producing 1-butene are disclosed. The process includes dehydrogenating butane to form a mixture comprising butene isomers. 1-butene is separated from the mixture using a system comprising a membrane. The system also includes an isomerization unit for isomerizing cis-2-butene and trans-2-butene to form additional 1-butene.)

1. A process for the preparation of 1-butene, said process comprising:

dehydrogenating n-butane to produce a first stream comprising 1-butene, isobutene, trans-2-butene, cis-2-butene and n-butane;

distilling the first stream in a distillation column to produce a second stream comprising predominantly 1-butene and isobutylene and a third stream comprising predominantly trans-2-butene and cis-2-butene; and

the second stream is separated to produce a fourth stream comprising predominantly 1-butene and a fifth stream comprising predominantly isobutylene.

2. The method of claim 1, wherein the separating of the second stream is performed using a membrane.

3. The method of any one of claims 1 and 2, wherein the membrane comprises a Zeolitic Imidazolate Framework (ZIF).

4. The method of any one of claims 1 to 3, further comprising:

a sixth stream is extracted from the distillation column, wherein the sixth stream comprises predominantly n-butane.

5. The process of any of claims 1-4, wherein the fourth stream comprises 90 to 95 wt.% 1-butene and 5 to 10 wt.% isobutylene.

6. The process of any of claims 1-5, wherein the fifth stream comprises 98 wt.% to 99 wt.% isobutylene.

7. The method of any one of claims 1 to 6The process wherein the dehydrogenation is carried out under conditions comprising a temperature of from 500 ℃ to 650 ℃, a pressure of from 0 bar to 10 bar and 1000h^-1To 5000h^-1GHSV of (1).

8. The process according to any one of claims 1 to 7, wherein dehydrogenation is catalyzed by a catalyst comprising platinum and/or tin.

9. The process of any of claims 1-8, wherein the first stream comprises 20 to 30 wt% 1-butene, 2 to 5 wt% isobutene, 25 to 35 wt% trans-2-butene, 20 to 30 wt% cis-2-butene, and 30 to 50 wt% n-butane.

10. The process of any one of claims 1 to 9, wherein the conditions under which the distillation is carried out include an overhead boiling range of-7 ℃ to 0 ℃, a reboiler boiling range of 1 ℃ to 5 ℃, and a pressure of 0.01MPa to 1 MPa.

11. The process of any of claims 1 to 10, wherein the sixth stream is extracted from trays numbered from 98% to 99% of the total number of distillation column trays, wherein the trays are numbered from the bottom of the distillation column upwards.

12. The process according to any one of claims 1 to 11, wherein the sixth stream is recycled to the dehydrogenation reactor where the dehydrogenation is carried out.

13. The process of any of claims 1-12, wherein sixth stream comprises 98 wt.% to 99 wt.% n-butane.

14. The process of any of claims 1-13, wherein the third stream comprises 50 to 60 weight percent trans-2-butene and 40 to 50 weight percent cis-2-butene.

15. The method of any one of claims 1 to 14, further comprising:

isomerizing at least some of the trans-2-butene and at least some of the cis-2-butene in the third stream in the isomerization unit to form 1-butene, the 1-butene being contained in a seventh stream flowing from the isomerization unit.

16. The process of claim 15, wherein the conditions under which isomerization is carried out comprise a temperature of from 50 ℃ to 60 ℃, a pressure of from 0MPa to 5MPa and 1000h^-1To 2000h^-1Space velocity of (a).

17. The process of any of claims 15-16, wherein the seventh stream comprises from 99 wt% to 99.8 wt% 1-butene.

18. The method of any one of claims 15 to 17, wherein the fourth stream and the seventh stream are combined to form an eighth stream.

19. The process of claim 18, where the eighth stream comprises from 99 wt% to 99.8 wt% 1-butene.

Technical Field

The present invention relates generally to the production of 1-butene. More particularly, the invention relates to the dehydrogenation of n-butane to form a mixture comprising butene isomers and recovering 1-butene from the mixture.

Background

1-butene is commonly used as a comonomer in the production of polyethylene. One way of preparing 1-butene is to separate it from C₄Separation in refinery streams. C₄Refinery streams are formed during the steam cracking or fluid catalytic cracking of hydrocarbon feeds to produce ethylene. 1-butene is also produced by the dehydrogenation of n-butane to form isomers of butene, including 1-butene, and one or more of isobutene, trans-2-butene, and cis-2-butene. After dehydrogenation, the 1-butene is separated from the other isomers. In the production of butenes by dehydrogenation of n-butane, the separation of 1-butene from the other butene isomers is a major obstacle to overcome if a high quality 1-butene product is to be obtained.

The separation of 1-butene from other butene isomers is very challenging because the boiling points of these materials are all close. Thus, conventional separation techniques (e.g., distillation) are relatively inefficient. In addition, the conversion of n-butane to 1-butene in these processes is relatively low, and thus it is difficult to achieve a suitable 1-butene production capacity in existing refineries.

Disclosure of Invention

In view of the above-mentioned problems associated with the production of 1-butene, processes have been developed that are capable of achieving the desired 1-butene production capacity in the desired purity. In this process, n-butane is dehydrogenated to form a mixture comprising butene isomers and unreacted n-butane. The mixture is separated and the unreacted n-butane from the separation process is returned as recycle to the dehydrogenation. The isobutylene and 1-butene recycled in the separation process are sent to a membrane to separate isobutylene and 1-butene. The trans-2-butene and cis-2-butene mixture obtained from the separation process can be used as a feed to an isomerization unit. In the isomerization unit, both trans-2-butene and cis-2-butene are converted to 1-butene.

Embodiments of the invention include a process for making 1-butene. The process includes dehydrogenating n-butane to produce a first stream comprising 1-butene, isobutylene, trans-2-butene, cis-2-butene, and n-butane. The process further includes distilling the first stream in a distillation column to produce a second stream comprising primarily 1-butene and isobutylene, and a third stream comprising primarily trans-2-butene and cis-2-butene. Still further, the process includes separating the second stream to produce a fourth stream comprising primarily 1-butene and a fifth stream comprising primarily isobutene.

Embodiments of the invention include a process for making 1-butene. The process includes dehydrogenating n-butane to produce a first stream comprising 1-butene, isobutylene, trans-2-butene, cis-2-butene, and n-butane. The process further includes distilling the first stream in a distillation column to produce a second stream comprising primarily 1-butene and isobutylene, and a third stream comprising primarily trans-2-butene and cis-2-butene. Still further, the process includes separating the second stream into a fourth stream comprising primarily 1-butene and a fifth stream comprising primarily isobutene. The separation of the second stream is performed using a membrane. The process also includes extracting a sixth stream from the distillation column, wherein the sixth stream comprises primarily n-butane.

The following includes definitions of various terms and phrases used throughout this specification.

The term "about" or "approximately" is defined as being approximately as understood by one of ordinary skill in the art. In one non-limiting embodiment, the term is defined as within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

The terms "weight%", "volume%" or "mole%" refer to the percentage of the weight, volume or mole of a component, respectively, based on the total weight, volume or moles of the material comprising the component. In a non-limiting example, 10 mole composition in 100 moles of material is 10 mole% composition.

The term "substantially" and variations thereof are defined as being within 10%, within 5%, within 1%, or within 0.5%.

The terms "inhibit" or "reduce" or "prevent" or "avoid" or any variation of these terms, when used in the claims and/or specification, includes any measurable reduction or complete inhibition to achieve the intended result.

The term "effective" when used in the claims and/or specification means sufficient to achieve a desired, expected, or expected result.

When used in the claims or the specification with the term "comprising", "including", "containing" or "having", elements may be preceded by a quantity that does not denote "a", but which also conform to the meaning of "one or more", "at least one", and "one or more than one".

The words "comprising," "having," "including," or "containing" are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

The methods of the present invention can "comprise," "comprise," or "consist essentially of" or "consist of" the particular materials, ingredients, compositions, etc. disclosed throughout this specification.

The term "predominantly" when used in the claims and/or specification refers to any of greater than 50 weight percent, greater than 50 mole percent, and greater than 50 volume percent. For example, "predominantly" may include 50.1% to 100% by weight and all values and ranges therebetween, 50.1% to 100% by mole and all values and ranges therebetween, or 50.1% to 100% by volume and all values and ranges therebetween.

Other objects, features and advantages of the present invention will become apparent from the drawings, detailed description and examples which follow. It should be understood, however, that the drawings, detailed description and examples, while indicating specific embodiments of the present invention, are given by way of illustration only and not by way of limitation. It is further contemplated that variations and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In other embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In other embodiments, additional features may be added to the specific embodiments described herein.

Drawings

For a more complete understanding, reference is now made to the following descriptions taken in conjunction with the accompanying drawing, in which:

FIG. 1 is a system for producing 1-butene according to an embodiment of the present invention; and

FIG. 2 is a process for producing 1-butene according to an embodiment of the present invention.

Detailed Description

A process for the preparation of 1-butene was found which has improved preparation capacity and purity over conventional processes. In the process of this discovery, n-butane is dehydrogenated to form a mixture comprising butene isomers and unreacted n-butane. Unreacted n-butane is separated from the mixture. Unreacted n-butane from the separation process is returned as recycle to the dehydrogenation. The isobutylene and 1-butene recovered in the separation process are sent to a membrane to separate isobutylene and 1-butene. The mixture of trans-2-butene and cis-2-butene obtained from the separation process can be used as a feed to an isomerization unit. In the isomerization unit, both trans-2-butene and cis-2-butene are converted to 1-butene.

FIG. 1 shows a system 10 for producing 1-butene in accordance with an embodiment of the present invention. FIG. 2 shows a process 20 for the preparation of 1-butene according to an embodiment of the present invention. Method 20 may be implemented using system 10. In embodiments of the invention, where the mass numbers of the streams shown in FIG. 1 may vary, the mass number of each stream may include mass numbers in the range of less than 10% to greater than 10% of the mass number shown, including all ranges and values therein.

A method 20 implemented using the system 10 may include, at block 200, flowing a feed stream 100 comprising primarily n-butane to a dehydrogenation reactor 110. In an embodiment of the invention, the feed stream 100 may be combined with the recycled n-butane stream 106 to form a combined stream 109, which flows to the dehydrogenation reactor 110. Alternatively or additionally, the feed stream 100 and the recycled n-butane stream 106 can be provided separately to the dehydrogenation reactor 110. According to embodiments of the present invention, feed stream 100 may be from different types of feedstocks and may comprise from 99 wt% to 99.5 wt% n-butane.

At block 201, the process 20 may further include dehydrogenating n-butane in the feed stream 100 in the dehydrogenation reactor 110 to produce the reactor effluent stream 101. According to an embodiment of the invention, the reactor effluent stream 101 is a mixture comprising one or more than one of 1-butene, isobutylene, trans-2-butene, cis-2-butene, and n-butane. In an embodiment of the present invention, the dehydrogenation reactor 110 is operated to provide reaction conditions for the feed stream 100 including a temperature of 500 ℃ to 650 ℃, a pressure of 0 bar to 10 bar, 1000h^-1To 5000h^-1GHSV of (1). According to an embodiment of the invention, the reactor effluent stream 101 comprises 20 to 30 wt% 1-butene, 2 to 5 wt% isobutene, 25 to 35 wt% trans-2-butene, 20 to 30 wt% cis-2-butene, and 30 to 50 wt% n-butane. Further, in embodiments of the present invention, the dehydrogenation reaction occurring in the dehydrogenation reactor 110 may be catalyzed by a catalyst comprising platinum and/or tin.

In accordance with an embodiment of the present invention, at block 202, method 20 includes flowing reactor effluent stream 101 to distillation column 111. Then, in accordance with an embodiment of the invention, reactor effluent stream 101 is distilled in distillation column 111 at block 203 to produce overhead stream 102, bottom stream 103, and recycled normal butane stream 106. According to an embodiment of the invention, the conditions under which the distillation is carried out comprise: -an overhead boiling range of 7 ℃ to 0 ℃, a reboiler boiling range of 1 ℃ to 5 ℃, a pressure of 0.01MPa to 1 MPa. In an embodiment of the invention, the overhead stream 102 comprises primarily 1-butene and isobutylene and the bottoms stream 103 comprises primarily trans-2-butene and cis-2-butene.

In an embodiment of the invention, at block 204, the overhead stream 102 is sent to a membrane separation device 112. According to an embodiment of the present invention, the membrane separation device 112 comprises a membrane suitable for separating hydrocarbon mixtures based on molecular size. In an embodiment of the invention, at block 205, the membrane separation device 112 separates the overhead stream 102 into a stream 104 comprising primarily 1-butene and a stream 105 comprising primarily isobutene.

According to an embodiment of the present invention, the membrane of the membrane separation device 112 comprises a crystalline microporous material, such as one or more Zeolitic Imidazolate Frameworks (ZIFs). ZIFs correspond in structure to zeolites and/or other crystalline materials, but have different building blocks. ZIFs typically have a pore size of less than 2 nm. Their regular pore structure enables them to distinguish gas molecules according to their molecular size. ZIFs in this technology were developed and functionalized as efficient and stable gas separation membranes, whether in powder form or continuous membrane form. See U.S. patent application No. 13/709155. Preferably, the overhead stream 102 is fed to the membrane separation unit 112 in a substantially vapor phase. In an embodiment of the invention, the separation process performed at the membrane separation device 112 at block 205 may include separating from C₃₊Separation of C from hydrocarbons (e.g. propane, propene, butane, butenes, isobutene)_2-Hydrocarbons (e.g., hydrogen, methane, ethane, and ethylene).

In an embodiment of the invention, stream 104 comprises from 90 wt% to 95 wt% 1-butene and from 5 wt% to 10 wt% isobutene. In an embodiment of the invention, stream 105 comprises from 98 wt% to 99 wt% isobutylene.

At block 206, the method 20 may include flowing the bottoms stream 103 to the isomerization unit 113. According to an embodiment of the invention, the bottom of the columnStream 103 comprises 50 to 60 weight percent trans-2-butene and 40 to 50 weight percent cis-2-butene. Isomerization unit 113 is adapted to isomerize cis-2-butene and isobutene to form 1-butene. Thus, according to an embodiment of the invention, block 207 comprises isomerizing at least some of the trans-2-butene and at least some of the cis-2-butene in the bottoms stream to form 1-butene. As shown in fig. 1, according to an embodiment of the invention, at block 208, these 1-butenes are contained in an isomerization unit effluent stream 107, which isomerization unit effluent stream 107 exits from the isomerization unit 113. According to an embodiment of the present invention, at block 207, the isomerization unit 113 is operated to provide reaction conditions for the isomerization, including a temperature of 50 ℃ to 60 ℃, a pressure of 0MPa to 5MPa, 1000h, by using sulfonic acid cation exchange^-1To 2000h^-1Space velocity of (a). In an embodiment of the invention, isomerization unit effluent stream 107 comprises 99 wt.% to 99.5 wt.% 1-butene.

According to an embodiment of the invention, recycled n-butane stream 106 extracted from distillation column 111 comprises predominantly n-butane. In an embodiment of the invention, the recycled n-butane stream 106 can be extracted from trays numbered from 98% to 99% of the total number of distillation column trays, wherein the trays are numbered from the bottom of the distillation column upwards. For example, if distillation column 111 has 100 trays, recycled n-butane stream 106 can be extracted from either tray 98 or tray 99, counting from the bottom up. As described above, the recycled n-butane stream 106 can be recycled to the dehydrogenation reactor 110 (either combined with the feed stream 100, separate from the feed stream 100, or both), the recycled n-butane stream 106 can be subjected to dehydrogenation conditions, and at least a portion of the recycled n-butane stream can be dehydrogenated to form butenes. In an embodiment of the invention, the recycled n-butane stream 106 comprises from 98 wt% to 99 wt% n-butane.

In embodiments of the invention, at block 208, method 20 includes combining stream 104 with isomerization unit effluent stream 107 to form combined product stream 108. According to an embodiment of the invention, the combined product stream 108 comprises from 99 wt% to 99.8 wt% 1-butene.

Although embodiments of the present invention have been described with reference to the blocks in fig. 2, it should be understood that the operations of the present invention are not limited to the specific blocks and/or the specific order of the blocks illustrated in fig. 2. Thus, embodiments of the invention may use different blocks in a different order than that of FIG. 2 to provide the functionality described herein.

In the context of the present invention, at least the following 19 embodiments are described. Embodiment 1 is a process for the preparation of 1-butene. The process includes dehydrogenating n-butane to produce a first stream containing 1-butene, isobutylene, trans-2-butene, cis-2-butene, and n-butane. The process further includes distilling the first stream in a distillation column to produce a second stream comprising primarily 1-butene and isobutylene, and a third stream comprising primarily trans-2-butene and cis-2-butene. The process also includes separating the second stream to produce a fourth stream comprising predominantly 1-butene and a fifth stream comprising predominantly isobutylene. Embodiment 2 is the method of embodiment 1, wherein the separating of the second stream is performed using a membrane. Embodiment 3 is the method of embodiment 1 or 2, wherein the membrane comprises a Zeolitic Imidazolate Framework (ZIF). Embodiment 4 is the method of any one of embodiments 1 to 3, further comprising extracting a sixth stream from the distillation column, wherein the sixth stream comprises predominantly n-butane. Embodiment 5 is the process of any one of embodiments 1 to 4, wherein the fourth stream comprises 90 to 95 weight percent 1-butene and 5 to 10 weight percent isobutene. Embodiment 6 is the method of any one of embodiments 1 to 5, wherein the fifth stream comprises 98 wt% to 99 wt% isobutylene. Embodiment 7 is the method of any one of embodiments 1 to 6, wherein the conditions under which the dehydrogenation is carried out include a temperature of 500 ℃ to 650 ℃, a pressure of 0 bar to 10 bar, and 1000h^-1To 5000h^-1GHSV of (1). Embodiment 8 is the method of any one of embodiments 1 to 7, wherein the dehydrogenation reaction is catalyzed by a catalyst comprising platinum and/or tin. Embodiment 9 is the method of any one of embodiments 1 to 8, wherein the first stream comprises 20 to 30 weight percent 1-butene, 2 to 5 weight percent isobutylene, 25 to 35 weight percent trans-2-butene, 20 to 30 weight percent cis-2-butene, and 30 to 50 weight percent n-butane. Embodiment 10 is the method of any one of embodiments 1 to 9A process wherein the conditions under which the distillation is carried out comprise an overhead boiling range of-7 ℃ to 0 ℃, a reboiler boiling range of 1 ℃ to 5 ℃, and a pressure of 0.01MPa to 1 MPa. Embodiment 11 is the method of any one of embodiments 1 to 10, wherein the sixth stream can be extracted from trays numbered from 98% to 99% of the total number of distillation column trays, wherein the trays are numbered from the bottom of the distillation column upward. Embodiment 12 is the method of any one of embodiments 1 to 11, wherein the sixth stream is recycled to the dehydrogenation reactor for dehydrogenation. Embodiment 13 is the method of any one of embodiments 1 to 12, wherein the sixth stream comprises 98 wt% to 99 wt% n-butane. Embodiment 14 is the method of any one of embodiments 1 to 13, wherein the third stream comprises 50 to 60 weight percent trans-2-butene and 40 to 50 weight percent cis-2-butene. Embodiment 15 is the process of any one of embodiments 1 to 14, further comprising isomerizing at least some of the trans-2-butene and at least some of the cis-2-butene in the third stream in the isomerization unit to form 1-butene, the 1-butene being contained in a seventh stream flowing from the isomerization unit. Embodiment 16 is the process of embodiment 15, wherein the conditions under which the isomerization is carried out include a temperature of 50 ℃ to 60 ℃, a pressure of 0MPa to 5MPa, and 1000h^-1To 2000h^-1Space velocity of (a). Embodiment 17 is the process of any one of embodiments 15 to 16, wherein the seventh stream comprises 99 to 99.8 weight percent 1-butene. Embodiment 18 is the method of any one of embodiments 15 to 17, wherein the fourth stream and the seventh stream are combined to form an eighth stream. Embodiment 19 is the process of embodiment 18, wherein the eighth stream comprises 99 to 99.8 weight percent 1-butene.

Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the embodiments 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 process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.