Process for producing MTBE and 1-butene from a C4 feed stream

Abstract

Systems and methods for producing MTBE and 1-butene are disclosed. A crude C4 hydrocarbon stream is obtained by removing butadiene from a C4 hydrocarbon mixture of a hydrocarbon cracking unit. The crude C4 hydrocarbon stream is then distilled to form (a) a first distillate stream comprising isobutene, isobutane, 1-butene, or a combination thereof and (b) a first bottoms stream comprising 2-butene, n-butane, MTBE synthesis catalyst deactivation compounds. The first distillate stream is then flowed to an MTBE synthesis unit to produce MTBE by reaction with methanol. The raffinate from the MTBE synthesis unit (comprising isobutane and 1-butene) is further separated in a distillation column to produce 1-butene.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority to U.S. Provisional Patent Application Serial No. 62 / 728,593, filed on September 7, 2018, the entire contents of which are incorporated herein by reference in their entirety. Technical Field

[0003] The present invention generally relates to systems and methods for producing methyl tert-butyl ether (MTBE) and 1-butene. More specifically, the present invention relates to an integrated system and method for producing methyl tert-butyl ether (MTBE) and 1-butene that can improve the catalyst life for MTBE synthesis and increase C 2+ from the feedstock compared to conventional MTBE production systems and methods. 4 Utilization of hydrocarbons. Background Art

[0004] MTBE is used as a gasoline blending component. Generally, MTBE can be prepared by reacting isobutylene with methanol. The isobutylene used in the reaction is usually prepared from crude C 4 The raw material stream is obtained, the crude C 4 The stream is typically a by-product stream produced in a cracking process for producing olefins. More particularly, crude C 4 Typically, in the crude C 4 The raw material is fed into the MTBE synthesis unit from the crude C 4 Butadiene is removed from the stream.

[0005] Then make the rest of the crude C 4 The feed stream is reacted with methanol in the presence of a catalyst in an MTBE synthesis unit to produce MTBE and a raffinate. The raffinate from the MTBE synthesis unit is further used to produce purified 1-butene. In this process, the raffinate is subsequently treated in a separation unit consisting of two rectifiers connected in series to produce purified 1-butene. However, in general, in the production process of MTBE and 1-butene, the catalyst life in the MTBE synthesis unit is relatively limited due to the catalyst deactivation compounds mixed in the feedstock during the removal of butadiene. In addition, the hydrocarbons in this process are not fully utilized, resulting in the depletion of 2-butene and other C 4 In addition, the 1-butene separation / purification step is relatively energy intensive, resulting in high production costs for 1-butene.

[0006] In general, while systems and methods exist for producing MTBE and 1-butene, there remains a need for improvement in the art, at least in light of the above-noted shortcomings. Summary of the invention

[0007] A solution to at least some of the above problems associated with systems and methods for producing MTBE and 1-butene has been found. The solution lies in an integrated system for producing MTBE and 1-butene and a method of using the integrated system. In particular, a distillation unit is added to extract C from the C entering the MTBE synthesis unit. 4 The catalyst deactivation compound and 2-butene and n-butane are separated from the mixture. Removal of the catalyst deactivation compound can improve the catalyst life for MTBE synthesis. The separated 2-butene can be further processed by metathesis to produce propylene, or by isomerization to produce additional 1-butene. Overall, the system and method of the present invention can improve the life expectancy of the catalyst and make full use of C 4 The system and method of the present invention thus provides a technical solution to at least some of the problems associated with current methods for producing MTBE and 1-butene.

[0008] Embodiments of the present invention include a method for producing methyl tert-butyl ether (MTBE) and / or 1-butene. The method comprises: distilling crude C 4 The crude C 4 A hydrocarbon stream comprises one or more of n-butane, 1-butene, 2-butene, isobutane, isobutylene, 1,2-butadiene, 1,3-butadiene, and a catalyst deactivation compound comprising dimethylformamide (DMF), acetonitrile (ACN), N-methyl-2-pyrrolidone (NMP), furfural methoxypropionitrile (MOPN), or a combination thereof, to produce: (1) a distillate stream comprising isobutylene, isobutane, and 1-butene, and (2) a bottoms stream comprising 2-butene, n-butane, and the catalyst deactivation compound. The method further comprises: reacting isobutylene (isobutylene) of the distillate stream with methanol in the presence of a catalyst for MTBE synthesis to produce methyl tert-butyl ether and an unreacted portion of the distillate stream. The method further comprises separating the methyl tert-butyl ether from the unreacted portion of the distillate stream, the unreacted portion comprising isobutane and 1-butene.

[0009] Embodiments of the present invention include a method for producing methyl tert-butyl ether (MTBE) and / or 1-butene. The method comprises: distilling crude C 4 The crude C 4A hydrocarbon stream comprises one or more of n-butane, 1-butene, 2-butene, isobutane, isobutylene, 1,2-butadiene, 1,3-butadiene, and a catalyst deactivating compound comprising dimethylformamide (DMF), acetonitrile (ACN), N-methyl-2-pyrrolidone (NMP), furfural methoxypropionitrile (MOPN), or a combination thereof, to produce: (1) a first distillate stream comprising one or more of isobutylene, isobutane, and 1-butene, and (2) a first bottoms stream comprising the catalyst deactivating compound and one or more of 2-butene and n-butane. The method further comprises: reacting the isobutylene of the distillate stream with methanol in the presence of a catalyst for MTBE synthesis to produce methyl tert-butyl ether and an unreacted portion of the distillate stream. The method further comprises separating the methyl tert-butyl ether from the unreacted portion of the distillate stream, the unreacted portion comprising isobutane and 1-butene. The process further comprises distilling the unreacted portion to produce a second distillate stream comprising isobutane and a second bottoms stream comprising primarily 1-butene. The process further comprises reacting the 2-butene of the first bottoms stream with ethylene in an olefin conversion technology unit to produce propylene.

[0010] Included below are definitions of various terms and phrases used throughout this specification.

[0011] The term "about" or "approximately" is defined as close to, as understood by one of ordinary skill in the art. In a non-limiting embodiment, these terms are defined as within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0012] The terms "wt. %, "vol. %" or "mol. %" refer to the weight, volume or mole percentage of a component, respectively, based on the total weight, total volume or total moles of the material including the component. In a non-limiting example, 10 moles of a component in 100 moles of a material is 10 mol.% of the component.

[0013] The term "substantially" and variations thereof are defined to include ranges within 10%, within 5%, within 1% or within 0.5%.

[0014] When used in the claims and / or specification, the terms "inhibit" or "reduce" or "prevent" or "avoid" or any variation of these terms include any measurable amount of reduction or complete inhibition to achieve the desired result.

[0015] The term "effective," as that term is used in the specification and / or claims, means sufficient to achieve a desired, expected, or intended result.

[0016] The use of the terms "a" or "an" when used in conjunction with the terms "comprising," "including," "containing," or "having" in the claims or the specification may mean "one," but it is also consistent with the meaning of "one or more," "at least one," and "one or more than one."

[0017] The terms "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "includes" and "include"), or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended, and do not exclude additional, unrecited elements or method steps.

[0018] The methods of the present invention may "comprise," "consist essentially of," or "consist of" a particular ingredient, component, composition, etc. disclosed throughout the specification.

[0019] The term "mainly", as used in the specification and / or claims, means greater than any one of 50 wt.%, 50 mol.%, and 50 vol.%. For example, "mainly" may include 50.1 wt.% to 100 wt.% and all values ​​and ranges therebetween, 50.1 mol.% to 100 mol.% and all values ​​and ranges therebetween, or 50.1 vol.% to 100 vol.% and all values ​​and ranges therebetween.

[0020] Other objects, features and advantages of the present invention will become apparent from the following drawings, detailed descriptions and examples. However, it should be understood that although the drawings, detailed descriptions and examples show specific embodiments of the present invention, they are only given by way of illustration and are not meant to be limiting. In addition, it is expected that changes and modifications within the spirit and scope of the present invention will become apparent to those skilled in the art through this detailed description. In other embodiments, features from a specific embodiment can be combined with features from other embodiments. For example, features from an embodiment can be combined with features from any other embodiment. In other embodiments, additional features can be added to the specific embodiments described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] For a more comprehensive understanding, reference is now made to the following description in conjunction with the accompanying drawings, in which:

[0022] Figures 1A-1C A schematic diagram of a system for producing MTBE and 1-butene according to an embodiment of the present invention is shown; Figure 1A A schematic diagram of a system for producing MTBE and 1-butene is shown, wherein a first bottom stream from a first distillation column is used as liquefied petroleum gas (LPG); Figure 1B A schematic diagram of a system for producing MTBE and 1-butene is shown, wherein a first bottoms stream from a first distillation column is passed to an isomerization unit; Figure 1C A schematic diagram of a system for producing MTBE and 1-butene is shown, wherein a first bottoms stream from a first distillation column flows to an olefin conversion technology unit; and

[0023] Figure 2 A schematic flow diagram of a method for producing MTBE and 1-butene according to an embodiment of the present invention is shown. DETAILED DESCRIPTION

[0024] Currently, C from steam crackers is used 4 Hydrocarbon mixture is used as raw material to produce MTBE. First, C 4 hydrocarbon mixture to remove butadiene and make C 4 The isobutene in the remainder of the hydrocarbon mixture reacts with methanol to form MTBE and raffinate. The raffinate from the MTBE synthesis unit is further distilled in two series-connected rectifiers to produce purified 1-butene. 4 The catalyst deactivating compounds that flow into the MTBE synthesis unit together with the remainder of the hydrocarbon mixture can significantly reduce the life expectancy of the catalyst in the MTBE synthesis unit. 4 The present invention provides a solution to one or more of these problems. The solution is based on a system and method, which includes: using a distillation column to distill C into the MTBE synthesis unit. 4 The remainder of the hydrocarbon mixture is separated into a distillate stream comprising 1-butene, isobutane and isobutylene and a bottoms stream comprising 2-butene, n-butane and catalyst deactivation compounds. Thus, the catalyst deactivation compounds are removed from the MTBE synthesis unit to avoid poisoning the catalyst used in the MTBE synthesis. In addition, 1-butene can be separated from the raffinate from the MTBE synthesis unit in a single distillation step, rather than using two distillation steps in conventional processes, thereby reducing the energy consumption for purifying 1-butene. Moreover, the separated 2-butene can be used to produce propylene by metathesis or isomerized to produce additional 1-butene, thereby increasing C 4The utilization of hydrocarbon mixtures and reducing the production costs of MTBE and / or 1-butene. These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.

[0025] A. System for producing MTBE and 1-butene

[0026] In an embodiment of the present invention, the system for producing MTBE and / or 1-butene may include a first distillation column, an MTBE synthesis unit, and a second distillation column. Figures 1A-1C , a schematic diagram of a system 100 for producing MTBE and / or 1-butene having improved catalyst life expectancy and reduced production costs is shown.

[0027] According to an embodiment of the present invention, the system 100 may include a first distillation column 101, which is configured to receive and distill the crude C 4 The hydrocarbon stream 11 is used to form: (1) a first distillate stream 12 comprising isobutylene, isobutane and 1-butene, and (2) a first bottoms stream 13 comprising 2-butene and n-butane. 4 The hydrocarbon stream 11 may contain 1-butene, 2-butene, isobutane, isobutylene and n-butane. According to an embodiment of the present invention, the C from the stream cracker may be 4 The hydrocarbon stream flows and from C 4 Butadiene is removed from hydrocarbon streams to form C 4 The crude C 4 Hydrocarbon stream 11. According to an embodiment of the present invention, the hydrocarbon stream 11 can be extracted and / or selectively hydrogenated from C 4 Butadiene is removed from hydrocarbon streams.

[0028] In an embodiment of the present invention, the top outlet of the first distillation column 101 may be fluidly connected to the MTBE synthesis unit 102 so that the first distillation stream 11 flows from the first distillation column 101 to the MTBE synthesis unit 102. According to an embodiment of the present invention, the MTBE synthesis unit 102 may include one or more MTBE synthesis reactors and one or more separation units. In an embodiment of the present invention, the one or more MTBE synthesis reactors may be configured to react isobutylene (isobutylene) of the first distillate stream 12 with methanol to produce MTBE. The one or more separation units may be configured to separate the effluent from the one or more MTBE synthesis reactors to form (a) an MTBE stream 14 mainly comprising MTBE and (b) a raffinate stream 15 mainly comprising isobutane and 1-butene. In an embodiment of the present invention, the MTBE synthesis reactor may contain a molten metal selected from an acidic resin, a zeolite, a fluorine-promoted SiO2 -Al 2 O 3 and sulfur-promoted ZrO 2 or a catalyst of the group consisting of a combination thereof.

[0029] According to an embodiment of the present invention, the outlet of the MTBE synthesis unit 102 can be in fluid communication with the second distillation column 103, so that the raffinate stream 15 flows from the MTBE synthesis unit 102 to the second distillation column 103. In an embodiment of the present invention, the second distillation column 103 can be configured to separate the raffinate stream 15 to form a second distillate stream 16 comprising 50 to 99 wt.% isobutane and a 1-butene stream 17 comprising 95 to 99.9 wt.% 1-butene.

[0030] In an embodiment of the present invention, Figure 1B As shown, the bottom outlet of the first distillation tower 101 can be connected to the isomerization unit 104 fluid, so that at least some of the first bottom stream 13 flows from the first distillation tower 101 to the isomerization unit 104. In an embodiment of the present invention, the isomerization unit 104 can be configured to isomerize at least some of the 2-butene of the first bottom stream 13 to 1-butene. The isomerization unit 104 may contain a catalyst, the catalyst including an iridium pincer complex catalyst or a supported catalyst containing at least one Group VIII noble metal, the at least one Group VIII noble metal selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum or nickel. The catalyst can be treated with a sulfur-containing compound before use and then treated with hydrogen. According to an embodiment of the present invention, the outlet of the isomerization unit 104 can be connected to the inlet fluid of the distillation tower 101, so that the isomerized recycle stream 20 from the isomerization unit 104 flows from the isomerization unit 104 to the first distillation tower 101. In an embodiment of the present invention, the isomerization recycle stream 20 may be mixed with the crude C 4 The hydrocarbon streams 11 are combined. The isomerization recycle stream 20 may comprise one or more of 1-butene, 2-butene, and n-butane.

[0031] Alternatively or additionally, such as Figure 1CAs shown, the bottom outlet of the first distillation tower 101 can be fluidly connected to the olefin conversion technology unit 105, so that the first bottom stream 13 flows from the first distillation tower 101 to the olefin conversion technology unit 105. In an embodiment of the present invention, the olefin conversion technology unit 105 can be configured to react at least some of the 2-butene of the first bottom stream 13 with ethylene to produce propylene (propylene) (propylene (propene)) by a metathesis reaction. The olefin conversion technology unit may contain a catalyst, the catalyst comprising Schrock catalyst, tungsten oxide on a silica or alumina carrier, molybdenum oxide on a silica or alumina carrier, rhenium oxide on a silica or alumina carrier, cobalt molybdate on alumina, and mixtures or combinations thereof. In an embodiment of the present invention, the olefin conversion technology unit 105 may include one or more metathesis reactors and one or more separation units, so that the reaction stream from the one or more metathesis reactors is separated in one or more separation units to form a propylene stream 21 mainly comprising propylene (propylene) (i.e., propylene (propene)) and an LPG stream comprising n-butane and / or unreacted 2-butene.

[0032] B. Process for producing MTBE and / or 1-butene

[0033] A process for producing MTBE and / or 1-butene has been discovered to improve the life expectancy of catalysts used in MTBE synthesis, increase C 4 The utilization rate of hydrocarbon raw materials can be improved, and the production cost of MTBE and 1-butene can be reduced. Figure 2 As shown, embodiments of the present invention include using crude C 4 Method 200 for producing MTBE and / or 1-butene using a hydrocarbon mixture as a feedstock. Figure 1A and 1C As shown, the method 200 can be implemented by the system 100. According to an embodiment of the present invention, the method 200 may include distilling the crude C in the first distillation column 101. 4 The hydrocarbon stream 11 is processed to produce a first distillate stream 12 and a first bottoms stream 13 as shown in block 201 .

[0034] In an embodiment of the present invention, the C 4 Butadiene is removed from the hydrocarbon mixture to obtain crude C 4 Hydrocarbon stream 11. According to an embodiment of the present invention, C from a steam cracker 4 The hydrocarbon mixture may contain 1-butene, 2-butene, isobutene, n-butane, butadiene and isobutane. Solvent extraction can be used to achieve the extraction of C from a steam cracker. 4 Butadiene is removed from a hydrocarbon mixture. 4The hydrocarbon stream 11 may comprise n-butane, 1-butene, 2-butene, isobutane, isobutylene, 1,2-butadiene, 1,3-butadiene, and a catalyst deactivating compound comprising dimethylformamide (DMF), acetonitrile (ACN), N-methyl-2-pyrrolidone (NMP), furfural methoxypropionitrile (MOPN), or a combination thereof. According to an embodiment of the present invention, the crude C 4 The hydrocarbon stream 11 may contain 0 to 1 wt.% catalyst deactivating compound and all ranges and values ​​therebetween, including 0 to 0.1 wt.%, 0.1 to 0.2 wt.%, 0.2 to 0.3 wt.%, 0.3 to 0.4 wt.%, 0.4 to 0.5 wt.%, 0.5 to 0.6 wt.%, 0.6 to 0.7 wt.%, 0.7 to 0.8 wt.%, 0.8 to 0.9 wt.%, and 0.9 to 1.0 wt.%. In an embodiment of the present invention, the catalyst deactivating compound may be capable of deactivating the catalyst used in the MTBE synthesis. The catalyst deactivating compound may be obtained by reacting the catalyst with the C 4 A solvent extraction process for removing butadiene from hydrocarbon mixtures was introduced.

[0035] In an embodiment of the present invention, the first distillate stream 12 may collectively mainly comprise isobutylene, isobutane and 1-butene. According to an embodiment of the present invention, the first distillate stream 12 may further comprise 0 to 10 ppm of catalyst deactivation compounds and all ranges and values ​​therebetween, including 0 to 1 ppm, 1 to 2 ppm, 2 to 3 ppm, 3 to 4 ppm, 4 to 5 ppm, 5 to 6 ppm, 6 to 7 ppm, 7 to 8 ppm, 8 to 9 ppm and 9 to 10 ppm. The first bottom stream 13 may mainly comprise 2-butene, n-butane and catalyst deactivation compounds. According to an embodiment of the present invention, the first bottom stream 13 may include 0 to 10 wt.% catalyst deactivation compounds and all ranges and values ​​therebetween, including 0 to 1 wt.%, 1 to 2 wt.%, 2 to 3 wt.%, 3 to 4 wt.%, 4 to 5 wt.%, 5 to 6 wt.%, 6 to 7 wt.%, 7 to 8 wt.%, 8 to 9 wt.% and 9 to 10 wt.% ranges. In an embodiment of the present invention, the catalyst deactivation compound may flow into the first bottom stream 13, as shown in FIG. 1, and then flow into the liquefied petroleum gas stream. In an embodiment of the present invention, the crude C in the first distillation column 101 of block 201 is distilled to obtain the crude C 4The hydrocarbon stream 11 may be operated under operating conditions including a bottom boiling temperature range of 50 to 100° C. and all ranges and values ​​therebetween, including ranges of 50 to 55° C., 55 to 60° C., 60 to 65° C., 65 to 70° C., 70 to 75° C., 75 to 80° C., 80 to 85° C., 85 to 90° C., 90 to 95° C., and 95 to 100° C. The operating conditions of the first distillation column 101 of block 201 may further include an overhead boiling temperature range of 30 to 60° C. and all ranges and values ​​therebetween, including ranges of 30 to 33° C., 33 to 36° C., 36 to 39° C., 39 to 42° C., 42 to 45° C., 45 to 48° C., 48 to 51° C., 51 to 54° C., 54 to 57° C., and 57 to 60° C. The operating conditions of the first distillation column 101 of block 201 may further include a molar reflux ratio in the range of 0.5 to 100, and all ranges and values ​​therebetween, including the ranges of 0.5 to 1, 1 to 2, 2 to 3, 3 to 4, 4 to 5, 5 to 6, 6 to 7, 7 to 8, 8 to 9, 9 to 10, 10 to 20, 20 to 30, 30 to 40, 40 to 50, 50 to 60, 60 to 70, 70 to 80, 80 to 90, and 90 to 100. The operating conditions of the first distillation column 101 of block 201 may further include an operating pressure in the range of 3 to 10 bar, and all ranges and values ​​therebetween, including 4 bar, 5 bar, 6 bar, 7 bar, 8 bar, and 9 bar. In an embodiment of the present invention, the number of theoretical plates of the first distillation column 101 may be in the range of 25 to 120, and all ranges and values ​​therebetween, including ranges of 25 to 30, 30 to 35, 35 to 40, 40 to 45, 45 to 50, 50 to 55, 55 to 60, 60 to 65, 65 to 70, 70 to 75, 75 to 80, 80 to 85, 85 to 90, 90 to 95, 95 to 100, 100 to 105, 105 to 110, 110 to 115, and 115 to 120.

[0036] According to an embodiment of the present invention, the method 200 may further include: in the MTBE synthesis unit 102, in the presence of a catalyst for MTBE synthesis, reacting the isobutylene of the first distillate stream 12 with methanol to produce methyl tert-butyl ether and an unreacted portion of the first distillate stream 12, as shown in box 202. In an embodiment of the present invention, the reaction in the MTBE synthesis unit of box 202 may be carried out at a reaction temperature of 30 to 120°C and all ranges and values ​​therebetween, including the ranges of 30 to 36°C, 36 to 42°C, 42 to 48°C, 48 to 54°C, 54 to 60°C, 60 to 66°C, 66 to 72°C, 72 to 78°C, 78 to 84°C, 84 to 90°C, 90 to 96°C, 96 to 102°C, 102 to 108°C, 108 to 114°C, and 114 to 120°C. The reaction of box 202 in the MTBE synthesis unit 102 can be carried out at the following reaction pressure: 5 to 20 bar and all ranges and values ​​therebetween, including ranges of 5 to 6 bar, 6 to 7 bar, 7 to 8 bar, 8 to 9 bar, 9 to 10 bar, 10 to 11 bar, 11 to 12 bar, 12 to 13 bar, 13 to 14 bar, 14 to 15 bar, 15 to 16 bar, 16 to 17 bar, 17 to 18 bar, 18 to 19 bar and 19 to 20 bar. The volume ratio of methanol fed to the MTBE synthesis unit 102 to the first distillate stream 12 can be in the range of 0 to 1, and all ranges and values ​​therebetween, including the ranges of 0 to 0.1, 0.1 to 0.2, 0.2 to 0.3, 0.3 to 0.4, 0.4 to 0.5, 0.5 to 0.6, 0.6 to 0.7, 0.7 to 0.8, 0.8 to 0.9, and 0.9 to 1.0.

[0037] According to an embodiment of the present invention, as shown in box 203, method 200 may further include separating MTBE from the unreacted portion of the first distillate stream 12 to form an MTBE stream 14 mainly comprising MTBE and a raffinate stream 15 mainly comprising isobutane and 1-butene. In an embodiment of the present invention, in box 203, about 95% to 100% of the MTBE produced in box 202 can be recovered. In an embodiment of the present invention, the MTBE stream 14 can contain 97 to 100 wt.% MTBE. The raffinate stream 15 can contain about 5 to 95 wt.% 1-butene and about 5 to 95 wt.% isobutane. In an embodiment of the present invention, the separation of box 203 can be performed in a separation unit of an MTBE synthesis unit comprising one or more distillation columns, reactive distillation columns, or a combination thereof.

[0038] According to an embodiment of the present invention, as shown in box 204, the method 200 may further include distilling the raffinate stream 15 in the second distillation column 103 to produce a second distillate stream 16 comprising 50 to 99 wt.% isobutane and a second bottoms stream 17 comprising 95 to 99.9 wt.% 1-butene. In an embodiment of the present invention, the distillation in the second distillation column 103 of box 204 can be carried out under operating conditions comprising the following overhead boiling temperature range: 30 to 60°C and all ranges and values ​​therebetween, including 30 to 33°C, 33 to 36°C, 36 to 39°C, 39 to 42°C, 42 to 45°C, 45 to 48°C, 48 to 51°C, 51 to 54°C, 54 to 57°C, and 57 to 60°C. The bottom boiling temperature of the distillation of block 204 may be in the range of 40 to 70° C. and all ranges and values ​​therebetween, including the ranges of 40 to 43° C., 43 to 46° C., 46 to 49° C., 49 to 52° C., 52 to 55° C., 55 to 58° C., 58 to 61° C., 61 to 64° C., 64 to 67° C., and 67 to 70° C. The operating conditions of the second distillation column 103 may further include a molar reflux ratio in the range of 1 to 100, and all ranges and values ​​therebetween, including the ranges of 1 to 2, 2 to 3, 3 to 4, 4 to 5, 5 to 6, 6 to 7, 7 to 8, 8 to 9, 9 to 10, 10 to 20, 20 to 30, 30 to 40, 40 to 50, 50 to 60, 60 to 70, 70 to 80, 80 to 90, and 90 to 100. The second distillation column 103 can have a number of theoretical plates in the range of 20 to 120, and all ranges and values ​​therebetween, including ranges of 20 to 30, 30 to 40, 40 to 50, 50 to 60, 60 to 70, 70 to 80, 80 to 90, 90 to 100, 100 to 110, and 110 to 120.

[0039] According to an embodiment of the present invention, the method 200 may further include isomerizing at least some of the 2-butene in the first bottoms stream 13 in the isomerization unit 104 to form 1-butene in the isomerization recycle stream 20, as shown in box 205. In an embodiment of the present invention, the isomerization recycle stream 20 may contain 1-butene, 2-butene, n-butane, or a combination thereof. The isomerization recycle stream 20 may further include a catalyst deactivation compound. As an alternative or in addition to flowing the deactivation compound into the recycle stream 20, before the first bottoms stream 13 enters the isomerization unit 104, it can be passed through a guard bed ( Figure 1B100) is not shown in the figure to remove the catalyst deactivation compound in the first bottom stream 13. As an alternative or in addition to being removed, the catalyst deactivation compound can be passed through the isomerization unit 104. According to an embodiment of the present invention, the isomerization in the isomerization unit 104 at box 205 can be carried out at a reaction temperature of 100 to 700°C and a reaction pressure of 3 to 40 bar. In an embodiment of the present invention, at box 205, 2-butene can be converted at the following conversion rate: 0 to 30% and all ranges and values ​​therebetween, including 0 to 3%, 3 to 6%, 6 to 9%, 9 to 12%, 12 to 15%, 15 to 18%, 18 to 21%, 21 to 24%, 24 to 27% and 27 to 30%. In an embodiment of the present invention, the method 200 may further include isomerizing the recycle stream 20 with the crude C 4 The hydrocarbon streams 11 are combined, as shown in block 206. The combined streams may flow into the first distillation column 101.

[0040] Alternatively or additionally, according to embodiments of the present invention, at least some of the first bottoms stream 13 may be passed to an olefin conversion technology unit 105 and reacted with ethylene under reaction conditions sufficient to produce propylene by metathesis, as shown in block 207. In embodiments of the present invention, an unreacted portion of the first bottoms stream 13 may be separated from propylene to form an LPG stream 22 comprising primarily n-butane and / or unreacted 2-butene. In an embodiment of the invention, at box 207, the reaction conditions may include a reaction temperature in the range of 100 to 500°C and all ranges and values ​​therebetween, including ranges of 100 to 120°C, 120 to 140°C, 140 to 160°C, 160 to 180°C, 180 to 200°C, 200 to 220°C, 220 to 240°C, 240 to 260°C, 260 to 280°C, 280 to 300°C, 300 to 320°C, 320 to 340°C, 340 to 360°C, 360 to 380°C, 380 to 400°C, 400 to 420°C, 420 to 440°C, 440 to 460°C, 460 to 480°C, and 480 to 500°C. The reaction conditions of box 207 can further include a reaction pressure of 10 to 100 bar and all ranges and values ​​therebetween, including 10 to 20 bar, 20 to 30 bar, 30 to 40 bar, 40 to 50 bar, 50 to 60 bar, 60 to 70 bar, 70 to 80 bar, 80 to 90 bar and 90 to 100 bar. In an embodiment of the present invention, at box 207, unreacted ethylene and unreacted 2-butene from the olefin conversion technology unit 105 can be recycled to the inlet of the olefin conversion technology unit 105, and 2-butene can be converted at the following conversion rate: 20% to 80% per pass and all ranges and values ​​therebetween, including 20 to 24%, 24 to 28%, 28 to 32%, 32 to 36%, 36 to 40%, 40 to 44%, 44 to 48%, 48 to 52%, 52 to 56%, 56 to 60%, 60 to 64%, 64 to 68%, 68 to 72%, 72 to 76% and 76 to 80%. According to embodiments of the present invention, the total conversion of 2-butene in block 207 may be in the range of 70 to 99% and all ranges and values ​​therebetween, including 70 to 73%, 73 to 76%, 76 to 79%, 79 to 82%, 82 to 85%, 85 to 88%, 88 to 91%, 91 to 94%, 94 to 97%, and 97 to 99%. In embodiments of the present invention, the deactivated compound may be passed through the olefin conversion technology unit 105. As an alternative or in addition to passing the deactivated compound through the olefin conversion technology unit 105, the first bottoms stream 13 may be passed through a guard bed ( Figure 1CIn an embodiment of the present invention, the catalyst deactivation compound passed through the olefin conversion technology unit 105 can be flowed into the LPG stream 22.

[0041] Although referenced Figure 2 The blocks of the present invention describe the embodiments of the present invention, but it should be understood that the operation of the present invention is not limited to Figure 2 Therefore, embodiments of the present invention may use the same Figure 2 Various blocks in different orders are used to provide the functions described in this document.

[0042] As part of the disclosure of the present invention, specific examples are included below. The examples are for illustrative purposes only and are not intended to limit the present invention. Those skilled in the art will readily recognize that parameters that may be changed or modified to produce substantially the same results.

[0043] Example

[0044] (System simulation for the production of MTBE and / or 1-butene)

[0045] For the system shown in Figure 1, AspenPlus v10.0 was used to simulate the first distillate stream (corresponding to Figure 1A The composition of the first distillate stream 12) (Table 2) and the second distillate stream 16 (corresponding to Figure 1A The simulation involved the use of about 28 t / h of C 4 Hydrocarbon stream (corresponding to Figure 1A C 4 The hydrocarbon stream 11) flows to the first distillation column (corresponding to Figure 1A The first distillation column 101 in the crude C 4 The composition of the hydrocarbon stream is shown in Table 1. The first distillate stream is passed to the MTBE synthesis unit (corresponding to Figure 1A MTBE synthesis unit 102 in the embodiment of the present invention, in which the isobutylene in the first distillate stream is reacted with 8.1 tons / hour of methanol in two reactors in the MTBE synthesis unit. In the simulation, the second distillate stream rich in isobutane, 7 tons / hour, is recycled and mixed with the first distillate stream before entering the MTBE synthesis unit.

[0046] In the simulation, a MTBE stream of about 20.8 t / h was formed (corresponding to Figure 1A The MTBE stream 14 in the MTBE synthesis unit is further recovered by two distillation columns. The raffinate from the MTBE synthesis unit, which mainly comprises 1-butene and isobutane, is passed to the second distillation column (corresponding to Figure 1AThe second distillation column 103 in the MTBE synthesis unit is used to produce a second bottoms stream containing greater than 98 wt.% 1-butene. The purity of 1-butene can be improved by increasing the load of the second distillation column or increasing the ratio of methanol to isobutylene in the MTBE synthesis unit.

[0047] Table 1 Crude C flowing into the first distillation column 4 Composition of hydrocarbon streams

[0048]

[0049]

[0050] Table 2 Composition of the first distillate stream from the first distillation column

[0051] Components Composition (weight fraction) n-Butane 0.004 Isobutane 0.027 1-Butene 0.343 trans-2-butene <1000ppm Cis-2-Butene <1000ppm Isobutylene 0.627 Dimethylformamide (deactivated component) <1ppm

[0052] Table 3 Composition of the second distillate stream from the second distillation column

[0053] Components Composition (weight fraction) n-Butane 0.005 Isobutane 0.284 1-Butene 0.704 trans-2-butene <1000ppm Cis-2-Butene <1000ppm Isobutylene 0.006

[0054] In the context of the present invention, at least the following 19 embodiments are described. Embodiment 1 is a method for producing methyl tert-butyl ether (MTBE) and / or 1-butene. The method comprises: distilling crude C 4 The crude C 4 A hydrocarbon stream contains n-butane, 1-butene, 2-butene, isobutane, isobutylene, 1,2-butadiene, 1,3-butadiene, and a catalyst deactivating compound comprising dimethylformamide (DMF), acetonitrile (ACN), N-methyl-2-pyrrolidone (NMP), furfural methoxypropionitrile (MOPN), or a combination thereof, to produce: (1) a distillate stream containing isobutylene, isobutane, and 1-butene, and (2) a bottoms stream containing 2-butene, n-butane, and the catalyst deactivating compound. The method further comprises: reacting the isobutylene of the distillate stream with methanol in the presence of a catalyst for MTBE synthesis to produce methyl tert-butyl ether and an unreacted portion of the distillate stream, and separating the methyl tert-butyl ether from the unreacted portion of the distillate stream, the unreacted portion containing isobutane and 1-butene. Embodiment 2 is a method as described in embodiment 1, further comprising isomerizing at least some of the 2-butene in the bottoms stream in an isomerization unit to form an isomerization recycle stream comprising 1-butene, non-isomerized 2-butene, and n-butane, and mixing the isomerization recycle stream with the crude C 4The hydrocarbon streams are combined for the distillation step. Embodiment 3 is a method as described in Embodiment 2, wherein the isomerization unit includes a catalyst selected from the group consisting of: an iridium pincer complex catalyst, or a supported catalyst containing at least one Group VIII noble metal, wherein the at least one Group VIII noble metal is selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum or nickel. The catalyst is treated with a sulfur-containing compound before use and then treated with hydrogen. Embodiment 4 is a method as described in any one of Embodiments 2 or 3, wherein the isomerization is carried out at a temperature of 100 to 700°C. Embodiment 5 is a method as described in any one of Embodiments 2 to 4, wherein the isomerization is carried out at a pressure of 3 to 40 bar. Embodiment 6 is a method as described in Embodiment 1, further comprising flowing the bottom stream to an olefin conversion technology unit, and reacting at least some of the 2-butene of the bottom stream with ethylene in the olefin conversion technology unit to form an effluent containing propylene and liquefied petroleum gas. Embodiment 7 is a method as described in Embodiment 6, wherein the olefin conversion technology unit contains a catalyst selected from the group consisting of: Schrock catalyst, tungsten oxide on a silica or alumina support, molybdenum oxide on a silica or alumina support, rhenium oxide on a silica or alumina support, cobalt molybdate on alumina, and mixtures or combinations thereof. Embodiment 8 is a method as described in any one of Embodiments 6 or 7, wherein the olefin conversion technology unit is operated at a temperature of 100 to 500°C. Embodiment 9 is a method as described in any one of Embodiments 6 to 8, wherein the olefin conversion technology unit is operated at a pressure of 10 to 100 bar. Embodiment 10 is a method as described in any one of Embodiments 1 to 9, wherein the crude C 4 The distillation of the hydrocarbon stream is carried out under the following operating conditions: a bottom boiling temperature range of 50 to 100° C., a top boiling range of 30 to 60° C., a molar reflux ratio in the range of 0.5 to 100, and a theoretical plate number in the range of 25 to 120. Embodiment 11 is a method as described in any one of Embodiments 1 to 10, wherein the crude C 4The distillation of the hydrocarbon stream is carried out at a pressure of 3 to 10 bar. Embodiment 12 is a method as described in any one of embodiments 1 to 11, wherein the catalyst deactivation compound is capable of deactivating the catalyst used for MTBE synthesis. Embodiment 13 is a method as described in embodiment 1, further comprising distilling the unreacted portion to produce a second distillate stream containing isobutane and a second bottom stream mainly containing 1-butene. Embodiment 14 is a method as described in embodiment 13, wherein the distillation of the unreacted portion is carried out under operating conditions including: a bottom boiling temperature range of 40 to 70°C, a top boiling range of 30 to 60°C, a molar reflux ratio in the range of 1 to 100, and a theoretical plate number in the range of 20 to 120. Embodiment 15 is a method as described in any one of embodiments 13 or 14, wherein the distillation of the unreacted portion is carried out at a pressure of 3 to 10 bar. Embodiment 16 is a method as described in any one of embodiments 13 to 15, wherein the second bottom stream contains 95 to 99.9 wt.% of 1-butene. Embodiment 17 is a method as described in any one of embodiments 1 to 16, wherein the crude C 4 The hydrocarbon stream contains 0 to 1 wt.% of catalyst deactivating compounds. Embodiment 18 is a method as described in any one of Embodiments 1 to 17, wherein the distillate stream further contains 0 to 10 ppm of catalyst deactivating compounds. Embodiment 19 is a method as described in any one of Embodiments 1 to 18, wherein MTBE is separated in the separation step at a recovery rate of 95 to 100%.

[0055] Although the embodiments of the present application and advantages thereof have been described in detail, it should be understood that various changes, substitutions and modifications can be made therein without departing from the spirit and scope of the embodiments defined by the appended claims. In addition, the scope of the present application is not limited to the specific embodiments of the processes, machines, manufactures, material compositions, devices, methods and steps described in the specification. As will be easily understood by those of ordinary skill in the art from the above disclosure, processes, machines, manufactures, material compositions, devices, methods or steps that currently exist or will be developed later to function substantially the same as the corresponding embodiments described herein or to achieve substantially the same results as the corresponding embodiments described herein can be utilized. Therefore, the appended claims are intended to include such processes, machines, manufactures, material compositions, devices, methods or steps within their scope.

Claims

1. A method for producing methyl tert-butyl ether (MTBE) and / or 1-butene, the method comprising: Distilled crude C 4 hydrocarbon feed stream, said crude C 4 hydrocarbon feed stream contains n-butane, 1-butene, 2-butene, isobutane and isobutene, and contains one or more of 1,2-butadiene and 1,3-butadiene, and a catalyst deactivating compound capable of deactivating the catalyst used in MTBE synthesis to produce: (1) a distillate stream containing isobutene, isobutane and 1-butene, and (2) a bottoms stream containing 2-butene, n-butane and the catalyst deactivating compound; reacting isobutene in a distillate stream with methanol in the presence of a catalyst for MTBE synthesis to produce methyl tert-butyl ether and an unreacted portion of the distillate stream; separating methyl tert-butyl ether from the unreacted portion of the distillate stream, the unreacted portion containing isobutane and 1-butene; feeding a bottoms stream to an olefin conversion technology unit, wherein the olefin conversion technology unit comprises one or more metathesis reactors and one or more separation units; reacting at least some 2-butene in the bottoms stream with ethylene in the one or more metathesis reactors to form a reaction stream containing propylene and liquefied petroleum gas; separating the reaction stream in the one or more separation units to form a propylene stream mainly containing propylene and an LPG stream containing n-butane and unreacted 2-butene; and distilling the unreacted portion of the distillate stream to produce a second distillate stream containing isobutane and a second bottoms stream mainly containing 1-butene; wherein the catalyst deactivating compound comprises dimethylformamide, N-methyl-2-pyrrolidone, acetonitrile, furfural, methoxypropionitrile or a combination thereof.

2. The method according to claim 1, further comprising: isomerizing at least some 2-butene in the bottoms stream in an isomerization unit to form an isomerization recycle stream containing 1-butene, non-isomerized 2-butene and n-butane; and Combine the isomerization recycle stream with the crude C 4 hydrocarbon stream for the distillation step.

3. The method according to claim 2, wherein the isomerization unit comprises a catalyst selected from the group consisting of an iridium pincer complex catalyst, or a supported catalyst containing at least one Group VIII noble metal, the at least one Group VIII noble metal being selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum or nickel, and the catalyst is treated with a sulfur-containing compound before use and then with hydrogen.

4. The method according to any one of claims 2 and 3, wherein the isomerization is carried out at a temperature of 100 to 700 °C.

5. The method according to any one of claims 2 to 4, wherein the isomerization is carried out at a pressure of 3 to 40 bar.

6. The method according to claim 1, wherein the olefin conversion technology unit contains a catalyst selected from the group consisting of a Schrock catalyst, tungsten oxide on silica or alumina, molybdenum oxide on silica or alumina, rhenium oxide on silica or alumina, cobalt molybdate on alumina and combinations thereof.

7. The method according to any one of claims 1 and 6, wherein the olefin conversion technology unit operates at a temperature of 100 to 500 °C.

8. The method according to any one of claims 1, 6 and 7, wherein the olefin conversion technology unit operates at a pressure of 10 to 100 bar.

9. The method according to any one of claims 1 to 8, wherein the distillation of the crude C 4 hydrocarbon feed stream is carried out under operating conditions including: a bottoms boiling range of 50 to 100 °C, a tops boiling range of 30 to 60 °C, a molar reflux ratio in the range of 0.5 to 100, and a number of theoretical plates in the range of 25 to 120.

10. The method according to any one of claims 1 to 9, wherein the distillation of the crude C 4 hydrocarbon feed stream is carried out at a pressure of from 3 to 10 bar.

11. The method according to claim 1, wherein the distillation of the unreacted portion is carried out under operating conditions including: a bottom boiling range of 40 to 70 °C, a top boiling range of 30 to 60 °C, a molar reflux ratio in the range of 1 to 100 and a number of theoretical plates in the range of 20 to 120.

12. The method according to any one of claims 1 and 11, wherein the distillation of the unreacted portion is carried out at a pressure of 3 to 10 bar.

13. The method according to any one of claims 1, 11 and 12, wherein the second bottoms stream comprises 95 to 99.9 wt.% of 1-butene.

14. The method according to any one of claims 1 to 13, wherein the crude C 4 hydrocarbon feed stream contains from 0 to 1 wt.% of catalyst deactivating compounds.

15. The method according to any one of claims 1 to 14, wherein the distillate stream further comprises 0 to 10 ppm of a catalyst deactivation compound.

16. The method according to any one of claims 1 to 15, wherein MTBE is separated in the separation step with a recovery rate of 95 to 100%.

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