JP2018531255A6 - Olefin hydration process using reactor with vibrating baffle - Google Patents

Abstract

  A butanol production system and method for producing purified mixed butanol includes an internal baffle single pass reactor having an internal fluid conduit defined by an inner wall. The internal fluid conduit includes a process fluid that includes water, mixed butene and mixed butanol to produce a crude product. The internal flow baffle is located along the length of the internal fluid conduit. The baffle cell is defined at the outer diameter by an inner wall and at the end by an internal flow baffle. The separation system separates water and mixed butene from the crude product to produce purified mixed butanol. The vibrator assembly is connected to the internal baffle single pass reactor and is selectively movable in a back and forth linear motion so that the process fluid has a generally sinusoidal motion along the internal baffle single pass reactor. A reciprocating vibrator head in communication with the process fluid.

Description

[Cross-reference of related patent applications]
This application is filed on Sep. 3, 2013, U.S. Patent Application No. 14/016798 entitled “Olefin Hydration Process Using Vibrating Baffled Reactor”, now U.S. Pat. No. 9,187,388. (This claims priority and benefit to US Provisional Application No. 61/697076, filed Sep. 5, 2012.) Priority and benefit thereto Insist. For purposes of US patent practice, the entire disclosure of each such application is incorporated herein by reference in its entirety.

  The field of the invention relates to the production of butanol. More specifically, the field relates to the production of butanol by butene hydration.

  Butanol is an efficient alternative to conventional oxygenates and fuel storage extenders, including methyl tert-butyl ether and ethanol. Butanol not only contributes to increasing the octane number, but also supplies incorporated oxygen into the fuel mixture. Mixed butanol or formulated butanol is also relatively inexpensive.

  The primary means for producing butanol, especially mixed butanol, is by the butene hydration process. Known butene hydration processes include liquid-liquid two-phase systems. Butene and water are immiscible with each other in systems with low relative concentrations (both butene in water and water in butene). Increasing operating conditions does not relax immiscibility. The immiscibility of the reactants is one of the reasons for the known low single pass conversion.

  In addition, immiscibility affects the distribution of the hydration catalyst. A typical hydration catalyst prefers either an aqueous phase or a hydrocarbon phase, usually not both. This poor distribution of the hydration catalyst does not promote the catalytic reaction throughout the two-phase system, but rather promotes only in a single phase.

  Therefore, there is a need to improve the single pass conversion yield of butene to butanol in butene hydration systems and processes.

  A butanol production system for producing purified butanol from water and mixed butene is an internal baffle single pass reactor having an inner wall and an internal fluid conduit defined by an operating length between a proximal end and a distal end And the internal fluid conduit selectively contains and mixes a process fluid comprising water, mixed butene and mixed butanol to produce a crude product. The internal baffle single pass reactor also includes an internal flow baffle located along at least a portion of the operating length of the internal fluid conduit, the internal flow baffle being annular and secured to the inner wall. The baffle cell is located continuously along the operating length and is defined by the inner wall at the outer diameter and by the internal flow baffle at the first end and the second end, and one of the internal flow baffles. One defines both the second end of one of the baffle cells and the first end of an adjacent baffle cell. The separation system is in fluid communication with an internal baffle single pass reactor oriented to selectively accept the crude product such that purified mixed butanol is produced and to separate water and mixed butene from the crude product. doing. The vibrator assembly is connected to the proximal end of the internal baffle single-pass reactor so that the process fluid has a generally sinusoidal motion along the internal baffle single-pass reactor, and is selectively moved back and forth in a linear motion. A movable reciprocating vibrator head in communication with the process fluid.

  In an alternative embodiment, each of the internal flow baffles can be formed of a disk-shaped plate having an orifice extending through the disk-shaped plate. The outer diameter of the disk-shaped plate can be fixed to the inner wall. The orifices can be sized in the plate so as to generate vortices in the process fluid within the baffle cell. The baffle cell can be located along the entire operating length of the internal fluid conduit.

  In other alternative embodiments, the outer diameter of the vibrator head can be in sliding engagement with the inner wall. The separation system can be in fluid communication with the tip of the internal fluid conduit or can be in fluid communication with at least one of the baffle cells. The vibrator head can have a reciprocating frequency of 2-5 hertz and can have a reciprocating amplitude of 20-40 millimeters. The vibrator assembly can include an external motion driver mechanically coupled to the vibrator head and selectively driving the vibrator head. The vibrator assembly may include a vibrator seal that sealingly engages the internal baffle single pass reactor and the process fluid vibrator member, the process fluid vibrator member mechanically moving an external motion driver to the vibrator head. To join.

  In another embodiment of the present disclosure, a method for producing purified mixed butanol from a combination of water and mixed butene includes providing an internal baffle single pass reactor. The internal baffle single pass reactor has an internal fluid conduit defined by an inner wall and an operating length between the proximal and distal ends. The internal flow baffle is located along at least a portion of the operating length of the internal fluid conduit, is annular, and is fixed to the inner wall. The baffle cell is located continuously along the operating length and is defined at the outer diameter by the inner wall and at the first and second ends by the inner flow baffle, one of the inner flow baffles being Both a second end of one of the baffle cells and a first end of an adjacent baffle cell are defined. A process fluid comprising mixed butene, water and mixed butanol is passed through an internal baffle single pass reactor. Connected to the base end of the internal baffle single-pass reactor and into the process fluid along the internal baffle single-pass reactor including a vibrator assembly having a reciprocating vibrator head that is selectively movable back and forth in linear motion By inducing a generally sinusoidal motion, the process fluid is mixed in an internal baffle single pass reactor to produce a crude product. Water and mixed butene are separated from the crude product in a separation system in fluid communication with the internal baffle single pass reactor to produce purified mixed butanol.

  In an alternative embodiment, mixing the process fluid in the internal baffle single pass reactor may include inducing a vortex in the process fluid in the baffle cell by pushing the process fluid through the internal flow baffle. it can. The process fluid can be transferred to the separation system at the tip of the internal fluid conduit, or can be transferred to the separation system from the interior of at least one of the baffle cells.

  In other alternative embodiments, the vibrator assembly can be operated at a reciprocating frequency of 2-5 hertz and a reciprocating amplitude of 20-40 millimeters. The vibrator head can be driven using an external motion driver that is mechanically coupled to the vibrator head. The internal baffle single pass reactor and the process fluid vibrator member can be hermetically engaged with a vibrator seal that mechanically couples an external motion driver to the vibrator head.

  These and other features, aspects, and advantages of the present invention will be better understood with reference to the following detailed description, appended claims, and accompanying drawings.

FIG. 1A is a process flow diagram of an embodiment of a butanol production system. FIG. 1B is a process flow diagram of an embodiment of a butanol production system.

FIG. 2 is a process flow diagram of another embodiment of a butanol production system.

FIG. 3 is a process flow diagram of another embodiment of a butanol production system.

FIG. 4 is a schematic detailed view of a portion of an internal baffle single pass reactor according to an embodiment of the present disclosure.

FIG. 5 is a schematic diagram of an internal baffle single pass reactor and an external motion driver according to an embodiment of the present disclosure.

FIG. 6 is a graph showing the molar ratio of water to 1-butene introduced versus the conversion of butene to butanol in mole percent in a vibrating baffle reactor and an autoclave reactor.

  In the appended figures, similar components and / or features may have the same reference number. The figure and its description facilitate a better understanding of the butanol production system and how to use it. The figures should in no way limit or define the scope of the invention. The figure is a simple diagram for ease of explanation. Those skilled in the art will appreciate that such systems are complex structures with ancillary equipment and subsystems that enable them to be operated for their intended purpose.

  The present specification, including the summary of the invention, a brief description of the drawings, and the detailed description, and the appended claims, refer to certain features of the invention (including process or method steps). doing. Those skilled in the art will appreciate that the present invention includes all possible combinations and use of particular features described herein. One skilled in the art will appreciate that the present invention is not limited to or by description of the embodiments listed herein. The subject matter of the invention is not limited except as to the spirit of the specification and the appended claims.

  Those skilled in the art will also understand that the terms used to describe a particular embodiment do not limit the scope or breadth of the present invention. In interpreting this specification and the appended claims, all terms should be interpreted in the widest possible manner consistent with the context of each term. All technical and scientific terms used herein and in the appended claims have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs unless otherwise defined.

  As used in this specification and the appended claims, the singular forms “a”, “an”, and “the”, unless the context clearly indicates otherwise. , Including multiple references. The verb “comprises” and its conjugations should be construed to refer to elements, components or steps in a non-exclusive manner. Referenced elements, components or steps may exist, be utilized, and combined with other elements, components or steps not explicitly mentioned. The verb “couple” and its conjugations are required for any type including electrical, mechanical or fluid to form a singular object from two or more pre-coupled objects. It means to complete the joint. When coupling the first device to the second device, this connection can occur either directly or through a common connector. “Optionally” and its various forms mean that the event or situation described thereafter may or may not occur. This description includes examples where an event or situation occurs and where it does not occur. “Operable” and its various forms means that it is compatible with its proper functioning and can be used for its intended use. "Associated" and its various forms mean something that is related to something else, either as they occur together or one of them creates another .

  Spatial terms describe the relative position of an object, or a group of objects relative to another group of objects. Spatial relationships are applied along the vertical and horizontal axes. Orientation terms and correlation terms including "upstream" and "downstream" and other like terms are for descriptive convenience and are not limiting unless otherwise indicated.

  Where this specification or the appended claims provides a range of values, it is understood that the interval encompasses each intervening value between the upper and lower limits and the upper and lower limits. The present invention encompasses and combines a smaller range of intervals that serve any particular exclusion provided. “Substantially free” means less than 1% by the indicated unit of measurement. “Significant” means 10% or more by the indicated unit of measure.

  Where reference is made herein and in the appended claims to a method that includes two or more defined steps, the defined steps, unless the context excludes that possibility, It can be performed in any order or simultaneously.

[FIGS. 1A-1B]
1A-1B include a process flow diagram of an embodiment of a butanol production system. The butanol production process of FIGS. 1A-1B involves several feeds through a feed line including a mixed butene feed 102, a water feed 104, a hydration catalyst feed 106, and an entrainer feed 108 in a butanol production system. 100. The butanol production system 100 produces several products through a production line that includes spent catalyst 110, product water 112, butanol product 114, and spent entrainer 116.

  The butanol production system 100 includes several units that support the conversion of butene to butanol and the production of a purified butanol product. The internal baffle single pass reactor 120 supports the catalytically induced hydration of butene to mixed butanol. Mixed butene feed 102, water feed 104, and hydration catalyst feed 106 all enter butanol production system 100 through internal baffle single pass reactor 120. The internal baffle single pass reactor 120 produces a crude product stream useful for recovering the produced mixed butanol.

  The internal baffle single pass reactor 120 contains a process fluid that is a mixture of reactants, catalyst and reaction products. The process fluid passes through the internal baffle single pass reactor 120 from the proximal end 122 to the distal end 124 via an internal fluid conduit defined by the inner wall 125. The composition of the process fluid changes along the operable length of the internal baffle single pass reactor 120 when the butene hydration reaction occurs, forming the product mixed butanol, and the water and mixed butene reactants. Consume.

  Separation system 160 is in fluid communication with internal baffle single pass reactor 120. Separation system 160 is oriented to selectively accept the crude product such that purified mixed butanol is produced and to separate water and mixed butene from the crude product. In the separation system 160 (dashed box), the cooler 170 is connected to the internal baffle single pass reactor 120, accepts the crude product from the internal baffle single pass reactor 120, and removes the crude product for separation processing. It can be operated to lower the temperature. In the embodiment of FIG. 1A, the separation system 160 is coupled to and in fluid communication with the tip 124 of the internal baffle single pass reactor 120. In the embodiment of FIG. 1B, the separation system 160 is connected to and in fluid communication with another region of the internal baffle single pass reactor 120. As an example, the separation system 160 can be coupled to the internal baffle single pass reactor 120 in at least one of the baffle cells 147.

  In the butanol production system 100, the cyclone 172 is coupled to the cooler 170 to accept the cooled crude product and remove any residual heterogeneous hydration catalyst. The cyclone 172 produces both spent catalyst through the spent catalyst 110 and non-catalytic crude product.

  The debutizer tower 180 is connected to the cyclone 172, accepts the uncatalyzed crude product, and removes unreacted butene. The debutizer tower 180 produces recovered butene and a crude product free of butene. The recovered butene is recycled to the proximal end of the internal baffle single pass reactor 120 via the butene recycle 182 by the butanol production system 100.

  The butanol extraction column 184 is connected to the debutanizer column 180 and receives the butene-free crude product and also receives the entrainer through the entrainer feed 108. The butanol extraction tower 184 operates by using an entrainer introduced to extract butanol from the butene-free crude product aqueous phase to form a butanol-poor aqueous phase and a butanol-rich entrainer and a butanol phase. . Water passes from the butanol extraction tower 184 via product water 112. The entrainer and butanol phases pass as the bottom liquid of butanol extraction tower 184.

  A butanol separation tower 186 connects to the butanol extraction tower 184, receives the entrainer and butanol phases, and separates butanol from the entrainer. The butanol separation column 186 produces purified mixed butanol that is substantially free of water, butene, and entrainers. The purified butanol mixture passes from the butanol separation tower 186 via the butanol product 114. The recovered entrainer passes from the butanol separation tower 186 via the spent entrainer 116.

  As shown in FIGS. 1A-1B, the internal baffle single pass reactor 120 configuration is a serpentine conduit having a proximal end 122 and a distal end 124, where the distal end 124 connects to a cooler 170. . Some ports 126 are for access to the inside of the internal baffle single pass reactor 120. Some injection ports provide a feed passage to the inside of the internal baffle single pass reactor 120 and include a water injection port 128, a butene injection port 130, and a catalyst injection port 132.

  The process fluid also provides latent heat to assist the hydration reaction by conveying heat transferred through the external heat exchange system and into the reactor. For example, FIGS. 1A-1B show a temperature control jacket 140 that covers a portion of the internal baffle single pass reactor 120. The temperature control jacket 140 is operable to provide heat to the covered portion of the internal baffle single pass reactor 120 to facilitate the hydration reaction within the process fluid. The temperature control fluid supply conduit 142 introduces a new temperature control fluid and the temperature control fluid return conduit 144 passes the depleted temperature control fluid.

  The internal baffle single pass reactor 120 has an internal flow baffle 146 along its operable length. Each internal flow baffle 146 can be an annular member that is fixed to the inner wall 125 and is thus fixed so that it cannot move within the internal baffle single pass reactor 120. A baffle cell 147 is located between successive internal flow baffles 146. A baffle cell 147 is defined at the outer diameter by an inner wall 125 and at a first end and a second end by an internal flow baffle 146, one of the internal flow baffles 146 being one of the baffle cells 147. Both one second end and the first end of an adjacent baffle cell 147 are defined. The baffle cell 147 is located continuously along the operating length of the internal baffle single pass reactor 120.

  The internal flow baffle 146 disrupts the fluid momentum and changes the fluid flow path as the process fluid flows through the reactor 120. Flow momentum splits and fluid flow path changes produce a homogeneous mixing in the baffle cell 147 that combines butene, water, and catalyst in the process fluid. Fluid flow that is not in line with the central axis of the internal baffle single pass reactor 120 also facilitates heat transfer to the fluid by transferring heat from the inner wall 125 of the internal baffle single pass reactor 120 into the bulk process fluid. To do. The fixed internal flow baffle 146 also increases the process residence time, which improves the conversion of butene to butanol.

  Vibrator assembly 149 is coupled to proximal end 122 of internal baffle single pass reactor 120. The vibrator assembly 149 includes a process fluid vibrator member 148 located near the proximal end 122 of the internal baffle single pass reactor 120. The vibrator assembly 149 also includes a vibrator seal 150 that sealingly engages the internal baffle single pass reactor 120 and a process fluid vibrator member 148 that mechanically couples the external motion driver 152 to the vibrator head 151. . The process fluid vibrator member such that the process fluid vibrator member 148 advances from the outside to the inside of the internal baffle single pass reactor 120 without exposing external contaminants to the process fluid and without leaking the process fluid to the external environment. 148 is connected to the internal baffle single pass reactor 120 via a vibrator seal 150. The process fluid vibrator member 148 connects with the inner wall 125 of the internal baffle single pass reactor 120 at the vibrator head 151 such that the outer diameter of the vibrator head 151 is in sliding engagement with the inner wall. Vibrator head 151 is in reciprocating linear motion back and forth and is in communication with the process fluid such that the process fluid has a generally sinusoidal motion along the length of internal baffle single pass reactor 120. The vibrator head 151 can be in direct contact with the process fluid or indirectly with the process fluid, such as by a diaphragm or other member that can change the movement of the vibrator head 151 into a generally sinusoidal motion of the process fluid. You can communicate with

  Changes to the relative position of the process fluid vibrator member 148 impart a change in position of the process fluid due to its contact with the vibrator head 151 and the incompressibility of the process fluid. The process fluid relocation imparts instabilities in the flow momentum of the process fluid flow along the operable length of the internal baffle single pass reactor 120. Instabilities in process fluid flow increase mixing and heat absorption. Pushing and pulling the incompressible process fluid causes the process fluid flow to rise and retract relative to a fixed position inside the reactor 120. This mixing of the process fluid in the internal baffle single pass reactor 120 induces a generally sinusoidal motion in the process fluid along the internal baffle single pass reactor 120 that includes the vibrator assembly 149 to produce a crude product. Produces.

  The vibrator assembly 149 also includes an external motion driver 152. The external motion driver 152 is coupled to the vibrator head 151 by a process fluid vibrator member 148 and can be used to selectively drive the process fluid vibrator member 148 and the vibrator head 151. The configuration of the vibrator seal 150, the connection with the external motion driver 152, and the contact of the vibrator head 151 with the inner wall 125 of the internal baffle single pass reactor 120 causes the process fluid vibrator member 148 to have a limited range of motion. to bound. When the process fluid vibrator member 148 is operable, it moves the vibrator head 151 in a front-to-back linear direction.

[Figure 2]
FIG. 2 is a process flow diagram of another embodiment of a butanol production system. The butanol production process of FIG. 2 introduces several feeds into the butanol production system 200, including a combined mixed butene and water feed 201 and a hydrated catalyst feed 106. The combined mixed butene and water feed 201 enters the internal baffle single pass reactor 120 through the butene and water injection port 203. The butanol production system 200 produces several products, including a purification vent 292 and a butanol product 114. Both system recirculation flow butene recirculation 182 and water recirculation 288 contribute to minimizing the mix butene and water replenishment in the combined feed 201.

  The separation system 260 of FIG. 2 is configured differently from the separation system 160 of FIGS. 1A-1B. A high pressure (HP) water separator 272 is coupled to the cooler 170 to receive the cooled crude product and remove a significant portion of the water to form a crude product with less water. The recovered water and hydration catalyst pass through a water recycle 288 for reintroduction into the internal baffle single pass reactor 120.

  The debutizer tower 180 is connected to the HP water separator 272 and is operated to accept the crude product with less water and to remove unreacted butene from the crude product with less water, and to remove the crude product without butene. Form. The recovered butene passes through the butene recirculation 182 to the proximal end of the internal baffle single pass reactor 120.

  The pervaporation unit 284 includes a pervaporation membrane 286. The pervaporation unit 284 is coupled to the debutanizer tower 180 and is operable to receive the butene-free crude product and separate butanol from the butene-free crude product as permeation using the pervaporation membrane 286. is there. The pervaporation unit 284 forms a residual liquid mainly composed of butanol vapor on the permeate side and water mainly on the supply side of the pervaporation film 286. The water retentate passes through the water recycle 288 to the internal baffle single pass reactor 120.

  The butanol separation column 290 is connected to the pervaporation unit 284 and operates to receive butanol vapor and purify the butanol vapor into purified mixed butanol. The purified mixed butanol is substantially free of water and butene and is conveyed through the butanol product 114. The butanol separation tower 290 emits light and non-condensable gases. A portion of the light and non-condensable gas is discharged through the purified vent stream 292 and the remainder is recycled through the distillation recycle 294 to the pervaporation unit 284 for butanol recovery.

[Fig. 3]
FIG. 3 is a process flow diagram of another embodiment of a butanol production system. The butanol production process of FIG. 3 introduces a feed similar to that shown in the process of FIG. The butanol production system 300 produces several products, including a waste catalyst 110 and a butanol product 114. Both the butene recirculation 182 and the water recirculation 288 of the system 300 recirculation stream contribute to minimizing the mixed butene and water replenishment in the combined feed 201.

  The separation system 360 of FIG. 3 is configured differently than the separation systems 160 and 260. Cyclone 172 connects to cooler 170 and receives the cooled crude product and removes any residual heterogeneous hydration catalyst, polymer, and other solids through spent catalyst 110. The cyclone 172 produces both a spent catalyst via the spent catalyst 110 and a crude product that does not contain the catalyst. A high pressure (HP) water separator 272 connects to the cyclone 172, receives the crude product without catalyst, and separates the organic phase containing butanol and butene from the aqueous phase under high pressure. The aqueous phase still contains some butanol, but much less than the organic phase. The debutizer tower 180 is connected to the HP water separator 272, receives the organic butanol and butene phases, and separates the organic phase into recyclable butene and purified mixed butanol. The recovered butene is conveyed to the front of the process via butene recycle 182 and the purified mixed butanol is passed through the butanol product 114. An azeotropic tower 390 connects to the HP water separator 272, receives the aqueous phase, and separates the aqueous phase into a butanol / water azeotrope and recyclable water. The butanol / water azeotrope is recycled to the front of the separation system 360 via butanol / water recycle 392 and recyclable water is conveyed to the front of the process via water recycle 288.

[Fig. 4]
FIG. 4 is a detailed view of an embodiment of the internal flow baffle 146 along the operable length of the internal baffle single pass reactor 120. In the example embodiment of FIG. 4, each of the internal flow baffles 146 may be formed of a disk-shaped plate having an orifice 394 that extends through the disk-shaped plate. The outer diameter of the disk-shaped plate is fixed to the inner wall 125. As the process fluid passes through the baffle cell 147, the interaction between the process fluid and the internal flow baffle 146 creates vortices in the process fluid. The orifices 394 can be sized to generate vortices in the process fluid in the baffle cell 147 and placed in each internal flow baffle 146 so that mixing of the process fluid is optimized. As an example, the diameter of the orifice 394 relative to the diameter of the internal flow baffle 146 as well as the position of the orifice 394 within the internal flow baffle 146 can be selected to optimize mixing of the process fluid.

  As the process fluid flows through the internal baffle single pass reactor 120, a portion of the process fluid passes through the orifice 394 of the internal flow baffle 146. Other process fluids contact the hard ring portion of the internal flow baffle 146 and turn in the baffle cell 147 to form vortices in the process fluid. The vortices formed in the baffle cell 147 improve process fluid mixing.

[Fig. 5]
FIG. 5 illustrates an example embodiment of an external motion driver 152 according to an embodiment of the present disclosure. In the example of FIG. 5, the external motion driver 152 includes a rotating disc 396. A first end of the process fluid vibrator member 148 is connected to the rotating disc 396. In the embodiment of FIG. 5, the process fluid vibrator member 148 is a connected member. As the external motion driver 152 rotates, the second end of the process fluid vibrator member 148 moves linearly back and forth with respect to the proximal end 122 of the internal baffle single pass reactor 120. The second end of the process fluid vibrator member 148 is attached to the vibrator head 151 which causes the vibrator head 151 to reciprocate linearly within the internal baffle single pass reactor 120.

  As the vibrator head 151 moves further in the internal baffle single pass reactor 120, the vibrator head 151 pushes the process fluid in a direction from the proximal end 122 toward the distal end 124. When the vibrator head 151 moves in the opposite direction toward the proximal end portion 122, the vibrator head 151 pushes the process fluid from the distal end portion 124 toward the proximal end portion 122 as indicated by an arrow indicating the direction of FIG. . This back-and-forth motion of the vibrator head 151 causes the process fluid to move within the internal baffle single pass reactor 120, generally in a generally sinusoidal back-and-forth motion. In this way, the oscillating motion is superimposed on all reactants in the internal baffle single pass reactor 120. This sinusoidal motion allows specific radial mixing.

[Process fluids and crude products]
The process fluid is a two-phase process of butene and water that is immiscible at the operating conditions of the butanol production process between the internal baffle single pass reactors. At a given point along the operating length of the reactor, the process fluid comprises butene, water, optionally a butene hydration catalyst and a butene hydration product, particularly butanol.

  Butene hydration occurs in an internal baffle single pass reactor. The process fluid assists in the hydration reaction of the mixed butene to the mixed butanol in the presence of the butene hydration catalyst in the reactor. As part of the butanol production process, the process fluid proceeds as a crude product from the reactor at a location adjacent to the tip of the reactor.

  The crude product is a combination of the products butanol, water, butene and optionally a butene hydration catalyst that may still be active. The crude product is the process fluid after traveling from the tip of the internal baffle single pass reactor.

[Mixed butene]
Mixed butene is introduced as a reactant as part of the butanol production process. Mixed butene can be purified or combined as a product of FCC unit or pyrolysis unit, raffinate from MTBE or TBA process, as part of liquefied petroleum gas (LPG), or from several similar sources It can come from sources within the petrochemical refinery that it contains as a stream. The mixed butene comprises one or more of 1-butene, one or both 2-butenes (ie cis or trans) and isobutylene. The mixed butene can also contain other alkanes and alkenes.

  In one embodiment of butanol production, the mixed butene comprises 1-butene. One embodiment of the butanol production process includes the case where the mixed butene consists essentially of 1-butene. Fresh or “replenished” 1-butene is preferably polymerized grade. The new 1-butene is at least 99% by volume 1-butene, or 99.5% by volume 1-butene, or 99.9% by volume 1-butene, or 99.95% by volume 1-butene, or Furthermore, it is highly pure. The impurity in new 1-butene is 5 volume ppm or less.

  Recycling butene from other parts of the butanol production system maximizes the conversion efficiency of butene. The butanol production system includes a separation system that selectively separates recoverable mixed butene from the crude product. One embodiment of a butanol production system includes the case where the butanol production system is operable to introduce the selectively separated mixed butene into the internal baffle single pass reactor. One embodiment of the butanol production process includes operating the butanol production system such that separately selectively separated mixed butenes are introduced into the internal baffle single pass reactor. Because the recycled material is already inside the butanol production system and cannot introduce new inerts or contaminants, the recycled butene can have a lower component purity than the fresh butene.

  The mixed butene is introduced as a pressurized gas, a liquid, a supercritical fluid, or a combination thereof. The critical temperature of 1-butene is 146.4 ° C. and the critical pressure is 40.2 bar. The critical temperature of isobutylene is 144.7 ° C. and the critical pressure is 40.01 bar. Preheating the introduced mixed butene provides the process fluid with heat that promotes hydration.

[water]
Water is introduced as a reactant as part of the butanol production process. New or makeup water introduced into the butanol production system is at least 99% by volume water, or 99.5% by volume water, or 99.9% by volume water, or 99.95% by volume water, or Furthermore, it is highly pure. The water should be degassed, desalted and deionized so as not to introduce contaminants into the butanol production system. Impurities are 5 ppm by volume or less.

  Recirculating water from other parts of the butanol production system minimizes the amount of makeup water introduced. Water is typically used in excess within the butanol production process. The separation system selectively separates recoverable water from the crude product traveling from the internal baffle single pass reactor. One embodiment of a butanol production system includes the case where the butanol production system is operable to introduce selectively separated water into an internal baffle single pass reactor. One embodiment of the butanol production process involves operating the butanol production system such that separately selectively separated water is introduced into the internal baffle single pass reactor. When using a non-neutralized homogeneous catalyst, the recycled water can carry the active hydrated catalyst to the front of the butanol production system. Embodiments of the butanol production process include the case where separately selectively separated water also includes a homogeneous butene hydration catalyst.

  One embodiment of the butanol production process includes the case where water and mixed butene are introduced into the internal baffle single pass reactor such that the value of the molar ratio of water to 1-butene is in the range of about 1 to about 21. .

[Hydration catalyst]
The butene hydration catalyst is introduced as a reactant as part of the butanol production process when the butanol production system does not include a given heterogeneous acid catalyst. The introduction of a butene hydration catalyst is optional when the butanol production system does not contain a given heterogeneous acid catalyst. One embodiment of the butanol production process includes introducing a butene hydration catalyst into an internal baffle single pass reactor of the butanol production system so that a process fluid forms proximate to the proximal end, where The hydration catalyst is selected from homogeneous acids, heterogeneous acids, and combinations thereof.

Useful butene hydration catalysts that are homogeneous acids include, for example, sulfuric acid and phosphoric acid. One embodiment of the butanol production process includes the introduced butene hydration catalyst being homogeneous. Examples of useful phosphoric acids include orthophosphoric acid, polyphosphoric acid (PPA), and superphosphoric acid (SPA). Polyphosphoric acid is a phosphorus oxyacid having the general chemical formula H (PO ₃ H) _n OH, where n is an integer representing the number of phosphorus units in the molecule. A commercial mixture of PPA has a mixture of ortho- (n = 1), pyro- (n = 2), tri- (n = 3), tetra- (n = 4), and higher order condensed chain acids. . A PPA concentration in the range of equivalent concentrations of phosphoric acid (H ₃ PO ₄ ) of about 95% to about 118% represents the same amount of phosphoric acid produced during the complete hydrolysis of polyphosphoric acid. One example is orthophosphoric acid _{(H 3 PO 4) (Sigma} -Aldrich Corp.; St.Louis, Mo.) Is.

Useful butene hydration catalysts also include heterogeneous acidic catalysts. One embodiment of the butanol production process includes the heterogeneous butene hydration catalyst introduced. Such acids have acid functionality incorporated into their metal, ceramic, particulate, or polymeric structure. Recovery processes including evaporation, vaporization, distillation, and centrifugation systems can extract solid catalyst from the process fluid or crude product. One embodiment of the butanol production process includes operating the butanol production system such that the separation system selectively separates the butene hydration catalyst from the crude product separately, where the butene hydration catalyst is heterogeneous. System catalyst. Examples include D008-1 and D008-2 (KaiRui Chemical Co. Ltd .; Hebei City, China), which is a polymer resin with added sulfonic acid (SO ₃ H) functional groups.

  One embodiment of the method includes selecting a butene hydration catalyst introduced from the group consisting of a homogeneous butene hydration catalyst, a heterogeneous hydration catalyst, and combinations thereof. It is known that several homogeneous / heterogeneous acid coupling systems provide a synergistic effect with respect to alkene to alcohol conversion efficiency and / or both. In an embodiment of a butanol generation system that includes a heterogeneous hydration catalyst in a baffle cell, one embodiment of the butanol generation process includes introducing a homogeneous butene hydration catalyst into an internal baffle single pass reactor. .

  The introduction of the hydration catalyst either occurs as a pure substance or is diluted in the delivery solution. Hydration catalysts can be diluted in water or mixed butene to enhance dispersion and introduced into the process fluid.

[Butanol production process product]
The primary product is purified mixed butanol. The composition of the purified butanol product is at least 99% by volume mixed butanol, or 99.5% by volume mixed butanol, or 99.7% by volume mixed butanol, or 99.9% by volume mixed butanol, or even High purity. One embodiment of a butanol production system includes the separation system being operable to produce purified mixed butanol having a purity of at least 99 volume percent mixed butanol. Dissolved gases containing butene, butane, and inert components are trace impurities that may be present in the purified mixed butanol product.

  The butanol production system can recover solids from the crude product. Such solids can include catalytically active hydration catalysts. The butanol production process can recover the hydration catalyst, neutralize it, and then dispose it outside the butanol production process. An external process can treat or regenerate the recovered hydration catalyst and recirculate it for reintroduction into the internal baffle single pass reactor.

  The butanol production process selectively separates water from the crude product as part of the purification process. The recovered water can be treated for organics, acid catalysts, and solids and then disposed of as a system purge.

  The butanol production system can release gas as part of the separation system. The vent gas serves as a system purge. The vent gas includes an inert component that includes a small portion of butene and a light organic gas.

[Internal baffle single pass reactor]
The internal baffle single pass reactor is a tubular having an internal fluid conduit defined by an inner wall operable to support mixed butene hydration in a pressurized, heated, fluid-filled environment. The tubular has an inner surface or wall that partially encloses a certain volume between a first end (base end or upstream end) and a second end (tip end or downstream end). . The operable length of the reactor is the tubular fluid length between the proximal and distal ends. The length of the tubular is much larger than its diameter. Tubular also has an outer surface or wall along its operating length where heat is transferred between the interior and exterior.

  The internal baffle single pass reactor is operable so that the reactants and optionally the hydration catalyst enter the reactor near the proximal end to mix and form the process fluid. Process fluid passes along the fluid flow path through the operable length of the reactor from near the proximal end to the distal end. The crude product passes from the reactor close to the tip.

  1-3 show a serpentine internal baffled single-pass reactor, but the reactor takes any number of physical configurations based on the use of connected linear and non-linear fluid conduit sections including standard tubes be able to. One skilled in the art can envision the overall shape of the internal baffle single-pass reactor based on operational preferences and performance including temperature control, physical space, maintenance, and capital costs.

  The main flow factors for the process fluid through the internal baffle single pass reactor are the coordinated introduction of reactants and hydration catalyst around the proximal end and the passage of the crude product around the tip. Although not required, auxiliary flow drivers including pumps and rotating in-line blades can provide supplemental momentum to the process fluid.

  The internal baffle single pass reactor has at least one reactant feed location near the proximal end of the reactor. The introduction of mixed butene and water may be a combined stream or a separate stream. The fresh and recirculated mixed butene and water streams can be mixed or fed separately into the reactor.

  The internal baffle single pass reactor has at least one hydration catalyst feed position. The hydration catalyst feed position is downstream of at least one reactant feed position near the proximal end of the internal baffle single pass reactor. This position relative to the reactant feed position allows the reactants to mix with each other prior to the introduction of the hydration catalyst, which facilitates improved selectivity and conversion.

  One embodiment of a butanol production system includes multiple reaction zones along the operable length of the internal baffle single pass reactor. In one embodiment, the reaction zone is an operable length between the first mixed butene introduction position and the second mixed butene introduction position. In other embodiments, the reaction zone is between the mixing butene introduction position and the tip of the reactor. In another embodiment, the reaction zone is an operable length between the first butene hydration catalyst introduction position and the second butene hydration catalyst introduction position. In other embodiments, the reaction zone is between the butene hydration catalyst introduction location and the tip of the internal baffle single pass reactor. Introducing multiple butenes or one butene hydration catalyst mixed through multiple locations along the operable length of the reactor allows for increased levels of process control and butene conversion efficiency To do. Each reaction zone has different internal and external process support devices that facilitate production, including internal baffle structure, process fluid flow rate, computer control system, and reaction zone temperature manipulation, and pressure manipulation.

  At any given point along the operable length of the internal baffle single pass reactor, the internal fluid conduit axis is perpendicular to the cross-sectional area of the internal fluid conduit at that point. Without internal additions (eg, internal flow baffles), fluid passes through the operable length of the internal baffle single pass reactor and remains generally in line with the internal fluid conduit axis while flowing.

[Internal flow baffle and baffle cell]
An internal baffle single pass reactor has a series of internal flow baffles along at least a portion of its operable length. One embodiment of a butanol production system includes a set of internal flow baffles located along the entire operable length of the internal fluid conduit.

  For each internal flow baffle in the internal baffle single pass reactor, the baffle is directed to one side (upstream side) directed toward the proximal end of the reactor and toward the tip of the reactor. Opposite side (downstream side). The baffle is conventionally oriented to extend vertically from a position along the inner wall of the reactor and project inward into the internal fluid conduit. The baffle is typically oriented to be perpendicular to the internal fluid conduit axis, although other configurations are feasible for those skilled in the art. The baffle prevents the process fluid from flowing in line with the internal fluid conduit axis for the majority of the length of the process fluid flow path to facilitate heat transfer and mixing.

  Internal flow baffles can have many physical shapes, including rods, perforated plates, mesh screens, orifice plates (central flow windows and off-flow flow windows), and sectioned plates. Each baffle has a window edge that at least partially defines a flow window for each baffle. In some baffles, such as an orifice plate, the window edge completely defines a circular void in the baffle through which the process fluid flows. In other baffles, the window edge partially defines a void through which the process fluid flows. When such a baffle is installed in the reactor, the inner wall of the reactor defines the remainder of the flow window. The size of the flow window relative to the size of the baffle, its position relative to the center of the internal fluid conduit, and its shape relative to other adjacent internal baffles (parallel, skewed, vertical) are important factors in changing the direction of travel of the process fluid It is.

  The fluid flow path through the interior of the internal baffle single pass reactor is defined by both the inner wall of the reactor and the arrangement of internal flow baffles, including the shape, flow window, spacing, and orientation of the adjacent baffle relative to the internal fluid conduit axis. Is done. The length of the process fluid flow path is longer than the operable length of the reactor. The baffle increases the distance that the process fluid passes through the reactor by not only having the process fluid flow through the distance from the proximal end to the tip, but also moving around the internal baffle. Let

  In a reactor with multiple reaction zones, different sets of baffles may exist within each reaction zone. The internal flow baffle arrangement is arranged in series within each set along the length of the operable length where the baffle is located and spaced equidistantly between each adjacent baffle in the set. . One embodiment of a butanol production system includes an internal baffle single pass reactor having one or more sets of internal flow baffles along its operable length.

  An internal flow baffle with an inner wall defines a set of baffle cells within the internal fluid conduit of the internal baffle single pass reactor. Each baffle cell is joined in a set of baffles by the downstream side of the upstream baffle and the upstream side of the downstream baffle, and the inner wall of the reactor. The number of baffle cells associated with a set of internal flow baffles is always less than the number of baffles in the set.

  As the process fluid passes through the internal baffle single pass reactor, the process fluid enters the baffle cell through a flow window defined at least in part by the upstream baffle. Upon entering the baffle cell, the process fluid circulates in the cell through both vortex formation and generally sinusoidal motion induced in the process fluid by pushing the process fluid through the internal flow baffle, and the reactants, The catalyst, product are mixed together, as well as between different parts of the process fluid, but both transfer heat internally between the process fluid and the inner wall of the reactor. The process fluid then passes from the baffle cell through a flow window defined at least in part by the downstream baffle. The process passing through the baffle cell is repeated as the process fluid passes from baffle cell to baffle cell along the operable length of the reactor.

  In one embodiment of the butanol production process, the introduction of a butene hydration catalyst is optional. In such a process, the internal baffle single-pass reactor includes a solid heterogeneous butene hydration catalyst that selectively converts mixed butene in the process fluid to mixed butanol. Although the catalyst can be included anywhere within the internal fluid conduit of the reactor, the most effective location for positioning the catalyst to maximize reactant mixing and conversion is within each baffle cell.

  The location of the solid heterogeneous butene hydration catalyst within each baffle cell can vary depending on the material, structure, and application of the catalyst to the baffle cell components. In pellet shapes, spheres, or other loose, generally unstructured forms, the catalyst is contained within a container or other physical restraining means that includes a structured frame having flow holes or slots and a wire mesh bag. This may allow the process fluid to flow freely in and out of the catalyst build-up while not allowing the process fluid to be transported from the vessel. This prevents the catalyst from moving with the process fluid flow downstream toward the tip of the internal baffle single pass reactor and contaminating the separation system. The free-form structure of the unstructured catalyst can allow direct placement in the process fluid flow path, including the flow window of the internal flow baffle. One embodiment of the butanol production system includes positioning the heterogeneous butene hydration catalyst such that the process fluid flowing through the flow window of the downstream baffle is in contact with the heterogeneous butene hydration catalyst, Embodiments include the reaction of mixed butene with water occurring in each baffle cell proximate to a downstream flow window. The position of the catalyst may be such that the process fluid flowing through the upstream baffle flow window contacts the heterogeneous butene hydration catalyst. Other forms of the catalyst, including structured forms such as lattices, matrices, and sheets, and “amorphous” forms such as curable, thermoplastic, and other malleable shapes, include the catalyst on the inner wall Can be mounted on, attached to, painted on, or spray coated onto an internal flow baffle that defines an inwardly facing surface and baffle cell. One embodiment of the butanol production system includes the catalyst being located on the inner wall defining the baffle cell, and an embodiment of the butanol production process is the reaction of the mixed butene with water in each baffle cell along the inner wall. Including what happens. In each baffle cell, the downstream side of the upstream baffle and the upstream side of the downstream baffle are oriented inward toward the baffle cell. One embodiment of a butanol production system includes the catalyst being located on the side of an internal flow baffle that is directed inward toward the baffle cell.

[External exercise driver]
A butanol production system is a device external to the internal baffle single pass reactor that induces instabilities in the flow of the process fluid without changing other operating parameters of the butanol production process, including temperature, mass flow, and pressure. Including. Inducing instabilities in the flow of the process fluid by transferring motion directly to the process fluid uses an external motion driver. The external motion driver can be operated with a reciprocating frequency of 2-5 hertz and a reciprocating amplitude of 20-40 millimeters.

  External motion drivers include electrical, electromechanical, hydraulic, pneumatic, gas injection, compressed gas, chemical reaction, and any other system or device to impart or transfer motion to the process fluid.

  During the butanol production process, an external motion driver induces instability in the process fluid flow by disrupting the fluid momentum as the fluid flows through the internal baffle single pass reactor. The external motion driver acts on the process fluid in a physical manner as it passes from the proximal end of the reactor to the distal end. The external motion driver uses the part of the device that contacts the process fluid to transmit motion, including vibration, reciprocation, variables, and asynchronous fluid motion, to the process fluid. The movement of the connected devices within the internal fluid conduit creates instabilities in the process fluid flow.

  Without inducing instability, the butanol production process can maintain “steady state” conditions in the internal baffle single pass reactor. A steady state condition is a condition in which the fluid properties at any point in the system do not change when compared to time. Those of ordinary skill in the fields of petroleum, petrochemical, and chemical operations will find that “steady state operation” sometimes involves some slight process variations, but generally operating conditions, feed rates, production Understand that rates do not change significantly.

  Application of motion by an external motion driver changes the steady state flow conditions to be unsteady by disrupting the fluid momentum of the process fluid flow. Unsteady conditions react to fluid momentum destabilization and result in cascading effects that affect other processes and production conditions, including system heat transfer, reaction efficiency, and overall productivity. Instability occurs during the introductory moment of the destabilizing motion and lasts for a period of time, after which the effect decreases as a function of time. By maintaining consistent operating conditions without additional labile interactions and otherwise, a new steady state condition, one that can resemble the original steady state, can be achieved. Repeated, periodic, or intermittent application of unstable motion directed to the process fluid presents a continuous condition of instability.

  Induced unsteady flow conditions of the process fluid change the relative motion (eg, acceleration, delay) of the process fluid as compared to a fixed position within the internal baffle single pass reactor. Induction of unsteady conditions does not affect the total volume or mass flow per unit time by the reactor when the feed introduction and the crude product passing through affects the overall volume or mass flow of the process.

  Transient formation and dissipation of fluid vortices and backflow in the process fluid occurs during unsteady flow. Similar to the random flow associated with turbulent flow, unsteady flow can also occur in the low Reynolds number flow regime characteristic of stratified flow. Unsteady flow of the process fluid is the mixing, reaction, and propagation in the baffle cell by causing a portion of the process fluid moving through the internal baffle single-pass reactor to flow in a transient, unpredictable and unsteady manner. Promotes heat.

  The external motion driver is coupled to a device that is operable to impart motion directly to the process fluid. Operation of an operating element such as a piston further raises and retracts process fluid flow during the flow of the internal fluid conduit from the proximal end to the distal end. A device such as a diaphragm in fluid contact with the process fluid expands and contracts relative to the incompressible process fluid, displaces a similar volume in the internal fluid conduit, and creates the desired process fluid flow instability. .

  One embodiment of a butanol production system includes a vibrator assembly having a vibrator head having a reciprocating frequency of 2-5 hertz. In such an embodiment, the external motion driver is operable to induce unsteadiness in the process fluid flow by oscillating at a frequency of 2-5 hertz, and in an alternative embodiment, the external motion driver The driver vibrates at about 3 Hz. An embodiment of a butanol production system includes a vibrator assembly having a vibrator head having a reciprocal amplitude of 20-40 millimeters. In such embodiments, the external motion driver is operable to induce non-stationarity in the process fluid flow by oscillating with an amplitude of 20-40 millimeters; in an alternative embodiment, the external motion driver Vibrates with an amplitude of about 30 millimeters.

  One embodiment of a butanol production system includes two or more external motion drivers that are coupled to a device that is operable such that each external motion driver imparts momentum directly to the process fluid. One embodiment of the butanol production process includes operating the first and second external motion drivers synchronously. Another embodiment of the butanol production process includes operating the first and second external motion drivers asynchronously.

[Temperature control system]
The temperature control system conveys the temperature correction fluid to the outside of the internal baffle single pass reactor to maintain an appropriate temperature for the butane hydration reaction. Examples of temperature control systems useful for maintaining the temperature within the internal baffle single pass reactor include heat exchangers, cooling jackets, and blowers. Examples of useful temperature correction fluids include water, ethylene glycol, and air. A forced convection of temperature corrected fluid is typical.

[Separation system]
The butanol production system includes a separation system operable to separate mixed butanol, mixed butene, and water from the crude product.

  The butanol production system is operable to selectively separate mixed butene from the crude product to produce a crude product free of butene and recovered mixed butene. The recovered mixed butene is useful for recycling into the butanol production system and introduction into the internal baffle single pass reactor as reactant feed. Recirculation of unreacted mixed butene improves butene process efficiency.

  The butanol production system is also operable to selectively separate water from the crude product to produce a crude product free of water. The recovered water is useful for recycle through the butanol production system and introduction into the internal baffle single pass reactor as reactant feed. Water can also be disposed of as part of the system purge.

  One embodiment of the butanol production system is operable to selectively separate the butene hydration catalyst separately from the crude product. The cyclone separation system induces a centrifugal force on the crude product that causes heavier liquids and solids to separate from the more trait product. Cyclone separation systems are particularly useful with solid heterogeneous catalysts so that the solid easily separates from the remaining liquid upon application of angular momentum. In-line filtration can also perform a similar task of removing solids from the crude product, allowing the solids to accumulate and peel off from the filter surface by their own weight. The vaporizer can introduce heat into the crude product such that a portion of the crude product forms steam. Evaporators, including thin film evaporators, can separate hot boiling products and solids from the portion of the crude product that can achieve gas phase conditions at lower operating pressures. The hydration catalyst and any other solid or very heavy liquid recovered can be discharged from the butanol production system for recovery or disposal.

  The entrained fluid is useful for selectively extracting butanol from the crude product. The crude product contains some water and therefore contains water immiscible organic compounds that are easily separable from water, with mixed butanol having an immediate affinity compared to water useful for carrying out the extraction. Entrainer fluids having a boiling point lower than mixed butanol at atmospheric pressure are also useful when this makes it relatively academic to separate the entrainer from mixed butanol. Examples of useful entrainer fluids include pentane, hexane, hexene, cyclohexane, benzene, toluene, xylene, and mixtures thereof.

  The introduction of a dilute entrainer fluid that is immiscible with water in the crude product causes the crude product to separate into a two-phase, butanol-rich organic phase containing the entrainer, and a butanol-poor aqueous phase. A butanol extraction tower can separate the aqueous phase from the entrainer phase. FIGS. 1A-1B illustrate a butanol extraction column 184 that produces a butanol-poor aqueous phase that passes as product water 112 and a butanol-rich entrainer and butanol mixture that is transferred to a butanol separation column 186. Other purification system processes convert butanol-enriched entrainer fluids into purified mixed butanol and lean entrainer fluids.

  The pervaporation membrane can directly separate mixed butanol from the crude product. The butanol production process involving pervaporation membranes selectively pervaporates mixed butanol and does not selectively pervaporate water. This pervaporate is a vaporous mixed butanol that can be condensed and distilled to form purified mixed butanol. This filtrate is a liquid mainly composed of water containing some mixed butanol. The filtrate from this type of purification system is useful not only to recapture the desired butanol, but also to recycle to store water for reuse.

[Supporting equipment]
Embodiments include many additional standard components or equipment that enable and operate the described apparatus, process, method, and system. Examples of such standard equipment known to those skilled in the art include heat exchange, pumps, blowers, reboilers, steam generation, condensate operations, membranes, single and multistage compressors, separation and fractionation equipment, valves, switches , Controllers, and pressure sensing devices, temperature sensing devices, level sensing devices, and flow sensing devices.

  Operation, control, and performance of a process or method portion, or all steps of a process or method, can occur through human interaction, pre-programmed computer control and response systems, or combinations thereof.

[Operation of butanol production system]
The butene hydration catalyst is operable to selectively convert mixed butene in the process fluid to mixed butanol at the operating conditions of the internal baffle single pass reactor. One embodiment of the butanol production process includes operating the butanol production system such that the temperature of the process fluid in the internal baffle single pass reactor is maintained in the range of about 80 ° C to about 150 ° C. One embodiment of the butanol production process includes operating the butanol production system such that the temperature of the process fluid in the internal baffle single pass reactor is maintained in the range of about 100 ° C to about 120 ° C. One embodiment of the butanol production process includes operating the butanol production system such that the pressure of the process fluid in the internal baffle single pass reactor is maintained in the range of about 5 bar to about 70 bar.

  Maintaining mixed butanol or some of the components of mixed butanol, or a combination of both, in a liquid or critical fluid state can enhance mixing in the internal baffle single pass reactor. One embodiment of the butanol generation process involves operating the butanol generation system such that the temperature and pressure of the process fluid in the internal baffle single pass reactor is maintained in a range such that the mixed butene is in a liquid state. Including. One embodiment of the butanol production process is to operate the butanol production system such that the temperature and pressure of the process fluid in the internal baffle single pass reactor is maintained in a range such that the mixed butene is in a supercritical state. including.

  The improved mixing that occurs within the internal baffle single pass reactor allows for higher material throughput than those with standard constant volume reactor systems. One embodiment of the butanol production process operates the butanol production system such that the residence time of the process fluid in the internal baffle single pass reactor is maintained in the range of about 0.1 hours to about 0.2 hours. including. Short residence times result in higher space velocities and minimize exposure of 1-butene to temperatures that can cause isomerization to the less useful 2-butene.

[Example]
Examples of specific embodiments facilitate a better understanding of butanol production systems and processes. The examples should in no way limit or define the scope of the invention.

[Examples 1 to 4 and Comparative Examples 1 to 4]
An oscillating baffle reactor (OBR) processes the five example mixtures (1-4). The autoclave reactor processes a mixture of five comparative examples (1-4). Each example has a comparative example of similar water: 1-butene molar ratio and catalyst: 1-butene relative relationship. For example, Example 1 can be compared with Comparative Example 1, Example 2 can be compared with Comparative Example 2, and so on. Table 1 shows the compositions of Examples 1 to 4 and Comparative Examples 1 to 4. Introduced 1-butene, water, and total volume are in milliliters (mL). The molar ratio is a number without a value.

  To process each example and comparative example, the amount of butene hydration catalyst (D008; KaiRui Chemical Co. Ltd .; Hebei City, China) for each example or comparative example and the amount of water specified reaction Is introduced into the vessel type (OBR, autoclave). The amount of 1-butene under nitrogen pressure is introduced into the reactor type specified for each experiment. When the reactor is sealed, the reactor is heated to the operating temperature (100-110 ° C.). In experiments in an autoclave reactor, the heating jacket maintains the operating temperature throughout the experiment. In experiments within OBR, the high temperature silicone oil bath maintains the operating temperature. The reaction time is 1 hour in both autoclave and OBR. During the example process, the OBR reactor mixes the example composition at a frequency of 3 hertz (Hz) and an amplitude of 30 millimeters, while the autoclave moves at a rate of 200 revolutions per minute (RPM). The composition of the comparative example is stirred. Both reactors mix these compositions to form a heterogeneous mixture of immiscible reactants. After 1 hour, each type of reactor interrupts mixing, cools to room temperature, and releases unreacted 1-butene. Analyzing the liquid products of each example and comparative example helps to determine the amount of 2-butanol present and the conversion efficiency of 1-butene.

Table 1 shows the results of processing the feed compositions of the examples and comparative examples in OBR and autoclave reactors under similar processing conditions (ie, temperature, time, feed composition). In all four tests, both the weight percent amount and the converted mole percent of 1-butene are higher for the OBR treated material than for the autoclaved material.

  As can be seen in Table 1, all of the OBR experimental runs have a higher 1-butene conversion relative to the comparable autoclave example run.

  FIG. 6 illustrates the molar ratio of water: 1-butene introduced versus the conversion of butene to butanol in mole percentages in a vibrating baffle reactor (Example) and an autoclave reactor (Comparative Example). FIG. 6 is a plot of the data from Table 3 of the molar ratio introduced into the reactor versus the measured 1-butene conversion. Information data for each set (examples and comparative examples) is curve fitted using a quadratic polynomial using Microsoft Excel 2010 (Redmond, Wash.).

FIG. 6 also shows the quadratic polynomial relationship between the water: 1-butene mole ratio introduced and the 1-butene mole percent conversion. In OBR, the determined quadratic relationship is well fitted with R ² values greater than 0.99. The second order polynomial of the OBR experimental run is expressed as Equation 1.
(Formula 1)
_Where MCR _{C4 = / BtOH} is the molar conversion of 1-butene to butanol in mole percent and MR _{H2O: C4 =} is the molar ratio of water to 1-butene in the introduced mixture. . Equation 1 is determined for a molar ratio range of about 1 to about 21.

In addition, the total molar conversion values for the OBR experimental run (Examples 1-4) fit between two quadratic polynomial relationships useful for estimating the molar conversion of 1-butene to butanol. Two equations similar to Equation 1 are illustrated in FIG. 4 as dashed lines “Polynomial (Low)” and “Polynomial (High)”. Equations 2 and 3 contain the molar conversion values of Examples 1-4 for the molar ratio range of the Examples.
(Formula 2)
(Formula 3)
Where EMCR _{C4 = / BtOH} is the estimated molar conversion of 1-butene to butanol in mole percent, and MR _{H2O: C4 =} is the molar ratio of water to 1-butene in the introduced mixture. Yes, this ranges from about 1 to about 21. One embodiment of the butanol production method is such that the molar conversion of 1-butene to butanol in mole percent is within the range of estimated molar conversion values as determined by Equations 2 and 3. Including operating a butanol production system. One embodiment of a butanol production method operates the butanol production system such that the molar conversion of 1-butene to butanol in mole percent is substantially above the estimated molar conversion value as determined by Equation 2. Including doing. In addition, two more equations similar to Equations 1-3 are illustrated in FIG. 6 as dashed lines “Polynomial (Medium Low)” (Poly. (MedLow)) and “Polynomial (Medium High)” (Poly. (MedHigh)). Is done. Equations 4 and 5 are close to Example 1 and include the molar conversion values of Examples 1-4 for the molar ratio range of Examples intermediate between Equations 2 and 3.
(Formula 4)
(Formula 5)
Where EMCR _{C4 = / BtOH} is the estimated molar conversion of 1-butene to butanol in mole percent, and MR _{H2O: C4 =} is the molar ratio of water to 1-butene in the introduced mixture. Yes, this ranges from about 1 to about 21. One embodiment of the butanol production method is such that the molar conversion of 1-butene to butanol in mole percent is within the range of estimated molar conversion values as determined by Equations 4 and 5. Including operating a butanol production system. One embodiment of the butanol generation method is to provide a butanol generation system such that the molar conversion of 1-butene to butanol in mole percent is substantially above the range of estimated molar conversion values as determined by Equation 4. Operation.

[Example 5 and Comparative Example 5]
The OBR used in Examples 1-4 treats Example Mixture 5. The autoclave reactor used for Comparative Examples 1-4 treats the mixture 5 of the Comparative Example. The examples and comparative examples have similar water: 1-butene molar ratios and catalyst: 1-butene volume relationships. Table 2 shows the compositions of Example 5 and Comparative Example 5. Introduced 1-butene, water, and total volume are in milliliters (mL). The molar ratio is a number without a value.

The treatments of Example 5 and Comparative Example 5 were the same as in Examples 1-4 except that the butene hydration catalyst was orthophosphoric acid (H ₃ PO ₄ ) (Sigma-Aldrich Corp .; St. Louis, Mo.). And similar to the processes for Comparative Examples 1-4.

  Table 2 shows the results of treatment of the example and comparative compositions in an OBR vs. autoclave reactor under similar treatment conditions (ie, temperature, time, composition). In these operations, both the weight percent amount and the converted mole percentage of 1-butene are higher for the OBR treated material than for the autoclaved material. The use of an acid hydration conversion catalyst confirms that the use of OBR at similar processing conditions is superior to an autoclave reactor for hydrating 1-butene.

Claims (20)

A butanol production system for producing purified mixed butanol from water and mixed butene,
An internal fluid conduit defined by an inner wall and an operating length between the proximal and distal ends that selectively contains and mixes a process fluid comprising water, mixed butene and mixed butanol to produce a crude product When,
An internal flow baffle that is annular and secured to the inner wall, located along at least a portion of the operating length of the internal fluid conduit;
A baffle cell located continuously along the operating length and defined by the inner wall at an outer diameter and by the internal flow baffle at a first end and a second end, One of the flow baffles has an internal baffle single path having a baffle cell that defines both the second end of one of the baffle cells and the first end of an adjacent baffle cell. A reactor,
The internal baffle single pass reactor oriented to selectively receive the crude product and to separate the water and the mixed butene from the crude product so that purified mixed butanol is produced. A separation system in fluid communication with the
A reciprocating vibrator head in communication with the process fluid that is selectively movable in a back-and-forth linear motion such that the process fluid has a generally sinusoidal motion along the internal baffle single pass reactor; A butanol assembly coupled to the proximal end of the internal baffle single pass reactor.   The butanol production system of claim 1, wherein each of the internal flow baffles is formed of a disk-like plate having an orifice extending into the interior of the plate.   The butanol generation system according to claim 2, wherein an outer diameter of the disk-shaped plate is fixed to the inner wall.   The butanol generation system of claim 2, wherein the orifice is sized to generate a vortex in the process fluid within the baffle cell and is disposed within the plate.   The butanol generation system according to claim 1, wherein an outer diameter of the vibrator head is slidingly engaged with the inner wall.   6. A butanol production system according to any one of claims 1 to 5, wherein the separation system is in fluid communication with the tip of the internal fluid conduit.   The butanol production system according to any one of the preceding claims, wherein the separation system is in fluid communication with at least one of the baffle cells.   The butanol production system according to any one of the preceding claims, wherein the baffle cell is located along the entire operating length of the internal fluid conduit.   The butanol production system according to any one of claims 1 to 8, wherein the vibrator head has a reciprocating frequency of 2 to 5 hertz.   The butanol production system according to any one of claims 1 to 9, wherein the vibrator head has a reciprocating amplitude of 20 to 40 millimeters.   The butanol generation system according to any one of the preceding claims, wherein the vibrator assembly includes an external motion driver mechanically coupled to the vibrator head and selectively driving the vibrator head. .   The vibrator assembly includes a vibrator seal that sealingly engages the internal baffle single pass reactor and a process fluid vibrator member that mechanically couples the external motion driver to the vibrator head. Item 12. The butanol production system according to Item 11. A method for producing purified mixed butanol from a combination of water and mixed butene, comprising:
An inner fluid conduit defined by an inner wall and an operating length between the proximal and distal ends; and
An internal flow baffle that is annular and secured to the inner wall, located along at least a portion of the operating length of the internal fluid conduit;
A baffle cell located continuously along the operating length and defined by the inner wall at an outer diameter and by the internal flow baffle at a first end and a second end, One of the flow baffles is an internal baffle single pass reaction having a baffle cell that defines both the second end of one of the baffle cells and the first end of an adjacent baffle cell. Providing a vessel;
Passing a process fluid comprising mixed butene, water and mixed butanol through the internal baffle single pass reactor;
Connected to the proximal end of the internal baffle single pass reactor, having a reciprocating vibrator head that mixes the process fluid in the internal baffle single pass reactor and is selectively movable in a back-and-forth linear motion. Generating a crude product by inducing a generally sinusoidal motion in the process fluid along the internal baffle single pass reactor including a vibrator assembly comprising:
Separating the water and the mixed butene from the crude product in a separation system in fluid communication with the internal baffle single pass reactor to produce purified mixed butanol.   Mixing the process fluid in the internal baffle single pass reactor includes inducing a vortex in the process fluid in the baffle cell by pushing the process fluid through the internal flow baffle. Item 14. The method according to Item 13.   15. The method of claim 13 or claim 14, further comprising transferring the process fluid to the separation system at the tip of the internal fluid conduit.   16. The method of any one of claims 13-15, further comprising transferring the process fluid from the interior of at least one of the baffle cells to the separation system.   17. A method according to any one of claims 13 to 16, further comprising operating the vibrator assembly at a reciprocating frequency of 2 to 5 hertz.   18. A method according to any one of claims 13 to 17, further comprising operating the vibrator assembly with a reciprocating amplitude of 20 to 40 millimeters.   19. The method of any one of claims 13-18, further comprising driving the vibrator head using an external motion driver mechanically coupled to the vibrator head.   20. The method of claim 19, further comprising sealingly engaging the internal baffle single pass reactor and a process fluid vibrator member with a vibrator seal that mechanically couples the external motion driver to the vibrator head. Method.