KR20180059541A - Olefin hydration process using vibration baffle reactor - Google Patents

Abstract

A butanol manufacturing system for producing purified mixed butanol comprises an internal baffle single pass reactor having an internal fluid conduit defined by an interior wall. The inner fluid conduit contains a process fluid comprising water, mixed butenes and mixed butanol to form a crude product. An inner flow baffle is located along the length of the inner fluid conduit. The baffle cell is defined by an outer diameter by the inner wall and defined by the inner flow baffle as an end. The separation system separates water and mixed butenes from the crude product for the production of purified mixed butanol. The transducer assembly has a reciprocating transducer head coupled to the inner baffle single pass reactor and selectively movable in forward and backward linear motion, the process fluid in communication with the process baffle, Get the movement.

Description

Olefin hydration process using vibration baffle reactor

Inventor: Alzach, Avir

Shake, Carimurdin, M.

Su, Wei

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

This application claims the priority of U.S. Provisional Application No. 61 / 697,076, filed September 3, 2013, U.S. Provisional Application No. 61 / 697,076, filed on September 5, 2012 and entitled "Olefin Hydration Process Using a Vibro-Baffle Reactor" US patent application Ser. No. 14 / 016,798, now U.S. Patent No. 9,187,388, the contents of which are incorporated herein by reference. For purposes of the United States patent system, this application is a reference in its entirety to the instant application.

Butanol is an effective alternative to typical oxygenate and fuel-stock extenders including methyl tert-butyl ether and ethanol. Butanol not only contributes to the increase in octane number but also supplies oxygen to the fuel mixture. Mixed or blended butanol is also relatively inexpensive.

The main means of producing butanol, especially mixed butanol, is through a butene hydration process. A known butene hydration process involves a liquid-liquid two-phase system. Butene and water do not mix with each other in low relative concentrations (both water-in-butene and butene-in-water) systems. The elevated operating conditions do not mitigate the incompatibility. The incompatibility of the reactants is one reason for the known low single pass conversion.

In addition, the incompatibility also affects the distribution of the hydration catalyst. Typical hydration catalysts favor either aqueous or hydrocarbon phase - usually not both. The poor distribution of these hydration catalysts does not constitute a catalytic reaction throughout the two-phase system, but usually only catalyzes a single phase.

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

A butanol manufacturing system for preparing purified butanol from water and mixed butenes comprises an inner baffle single pass reactor having an inner wall and an inner fluid conduit defined by the working length between the proximal and distal ends, Selectively contains and mixes process fluids, including water, mixed butenes and mixed butanol, to form a crude product. The inner baffle single pass reactor also includes an inner flow baffle located along at least a portion of the operating length of the inner fluid conduit, the inner flow baffle being annular and secured to the inner wall. The baffle cell is positioned continuously along the working length and defined by the inner wall as an outer diameter and defined by the inner flow baffle as a first end and a second end wherein one of the inner flow baffles is one of the baffle cells And the first end of the adjacent baffle cell. The separation system is in fluid communication with the inner baffle single pass reactor oriented to selectively receive the crude product and separate water and mixed butene from the crude product to produce purified mixed butanol. An oscillator assembly is coupled to the proximal portion of the inner baffle single pass reactor, the oscillator assembly having a reciprocating oscillator head selectively linearly movable forward and rearward, the process fluid having a generally sinusoidal curve along the inner baffle single pass reactor, Lt; RTI ID = 0.0 > fluid. ≪ / RTI >

In an alternative embodiment, each said internal flow baffle may be formed of a disc-shaped plate having an orifice, said orifice extending through said plate. The outer diameter of the disk-shaped plate can be fixed to the inner wall. The orifices may be sized and positioned according to the plate to form a vortex in the process fluid within the baffle cell. The baffle cell may be located along the entire working length of the inner fluid conduit.

In another alternative embodiment, the outer diameter of the vibrator head may engage slidingly with the inner wall. The separation system may be in fluid communication with the distal end of the inner fluid conduit or in fluid communication with at least one of the baffle cells. The vibrator head may have a reciprocating frequency of 2 to 5 hertz, and may have a reciprocating amplitude of 20 to 40 millimeters. The vibrator assembly may include an external motion driver that is mechanically coupled to the vibrator head and selectively drives the vibrator head. The vibrator assembly may include an oscillator seal section for sealing and engaging the inner baffle single pass reactor and the process fluid oscillator member, the process fluid oscillator member mechanically coupling the external motion driver to the vibrator head.

In another embodiment of the present disclosure, a method of making a purified mixed butanol from a combination of water and mixed butenes comprises providing an internal baffle single pass reactor. The inner baffle single pass reactor has an inner fluid conduit defined by an inner wall and an operating length between the proximal and distal ends. An inner flow baffle is positioned along at least a portion of the operating length of the inner fluid conduit, the inner flow baffle is annular and is secured to the inner wall. A baffle cell is positioned continuously along an operating length, defined by an outer diameter by the inner wall, and defined by a first end and a second end by the inner flow baffle, wherein one of the inner flow baffles Defines both the two ends and the first end of the adjacent baffle cell. A process fluid comprising mixed butenes, water and mixed butanol is passed through the inner baffle single pass reactor. The process fluid is mixed in the inner baffle single pass reactor to induce a generally sinusoidal movement in the process fluid along the inner baffle single pass reactor with the oscillator assembly coupled to the proximal portion of the inner baffle single pass reactor Wherein the oscillator assembly has a reciprocating oscillator head selectively movable in a forward and a backward linear motion. The water and mixed butenes are separated from the crude product in a separation system in fluid communication with the internal baffle single pass reactor to produce a purified mixed butanol.

In an alternate embodiment, mixing the process fluid in the inner baffle single pass reactor may include directing a vortex in the process fluid within the baffle cell by pushing the process fluid past the inner flow baffle have. The process fluid may be transferred from the distal end of the inner fluid conduit to the separation system or from at least one of the baffle cells to the separation system.

In yet another alternative embodiment, the oscillator assembly may be operated with a reciprocating frequency of 2 to 5 hertz and a reciprocating amplitude of 20-40 millimeters. The vibrator head may be driven by an external motion driver mechanically coupled to the vibrator head. The inner baffle single pass reactor and the process fluid oscillator member may be sealed to engage the vibrator seal section that mechanically couples the outer motion driver to the vibrator head.

These and other features, aspects, and advantages of the present invention are better understood with regard to the following detailed description of preferred embodiments, appended claims, and accompanying drawings.
Figures 1A-1B are process flow diagrams of an embodiment of the butanol manufacturing system:
Figure 2 is a process flow diagram of another embodiment of the butanol manufacturing system;
Figure 3 is a process flow diagram of another embodiment of the butanol manufacturing system;
4 is a schematic detail view of a portion of the inner baffle single pass reactor in accordance with embodiments of the present disclosure;
5 is a schematic diagram of the inner baffle single pass reactor and external motion driver in accordance with embodiments of the present disclosure; And
6 is a graph showing the molar ratios of the conversion of water to butene to butanol introduced into 1-butene for an oscillating baffle reactor and an autoclave reactor in molar percentages.
In the accompanying drawings, similar components or features, or both, may have the same reference label. The drawings and their description will enable a better understanding of the butanol manufacturing system and methods of use thereof. The drawings should not limit or define the scope of the invention. The drawings are simplified illustrations for convenience of explanation. Those of ordinary skill in the art will understand that such a system is a complex structure with auxiliary equipment and subsystems that enable it to operate in accordance with its intended purpose.

The specification, including the summary of the invention, a brief description of the drawings and the detailed description of the preferred embodiments, and the appended claims, refers to certain features of the invention, including the steps of the process or method. The skilled artisan will appreciate that the invention includes all possible combinations and uses of the particular features described in the specification. It will be understood by those skilled in the art that the present invention is not limited to or by the description of the embodiments given herein. The subject matter of the present invention is not limited except in the context of the description and the appended claims.

It will also be appreciated by those skilled in the art that the terms used to describe certain embodiments do not limit the scope or breadth of the present invention. In interpreting the specification and the appended claims, all terms should be interpreted as broad as possible in the context of each term. All technical and scientific terms used in the specification and the appended claims have the same meanings as commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise defined.

As used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. The word "comprise" and its conjugated form should be construed to refer to an element, element, or step in a non-exclusive manner. The referenced elements, components, or steps may be present, utilized, or combined with other elements, components, or steps not expressly stated. The verb "couple" and its associated form means completing any type of necessary coupling, including electrical, mechanical, or fluid, to form a single object in two or more previous non-combined objects. If the first device is coupled to the second device, the connection can occur either directly or through a common connection. "Optionally ", and its various forms, means that the subsequently described event or circumstance may or may not occur. The description includes instances where an event or circumstance occurs and instances where it does not. "Operable ", and its various forms, means that it can perform its intended function and be used for its intended use. "Associated" and its various forms mean something connected with something else because it occurs together or because one manufactures the other.

A spatial term describes the relative position of an object or object to another object and a group of objects. The spatial relationship is applied along the vertical and horizontal axes. Directional and relative terms including "upstream" and "downstream" and other like terms are for convenience of description and are not limiting unless otherwise indicated.

Where the specification or appended claims provide a range of values, it is understood that the interval includes the upper and lower limits as well as each intervening value between the upper and lower limits. The present invention encompasses a smaller range of spacing and boundaries in which any particular exclusion is provided. "Substantially free" means less than 1% in the indicated unit of measurement. "Significant" means at least 10% of the indicated units of measure.

Where reference is made to a method comprising two or more defined steps in the specification and the appended claims, the defined steps may be performed in any order or concurrently, except where the context excludes the possibility.

Figures la-1b

Figures 1A-1B include a process flow diagram of one embodiment of the butanol manufacturing system. The butanol manufacturing process of FIGS. 1A-1B is similar to the butanol manufacturing system 100 through a feed line comprising a mixed butene feed 102, a water feed 104, a hydration catalyst feed 106, Lt; / RTI > The butanol manufacturing system 100 manufactures several products through a product line that includes the spent catalyst 110, the product 112, the butanol product 114, and the consumed entrainer 116.

The butanol manufacturing system 100 includes several units that support the conversion of butene to butanol and the production of a refined butanol product. An internal baffle single pass reactor 120 aids catalytically induced hydration of butene to mixed butanol. Both the mixed butene feed 102, the water feed 104 and the hydration catalyst feed 106 enter the butanol manufacturing system 100 via the inner baffle single pass reactor 120. The internal baffle single pass reactor 120 produces a crude product stream useful for the recovery of the mixed butanol produced.

The internal baffle single pass reactor 120 contains a process fluid which is a mixture of reactants, catalysts, and reaction products. The process fluid traverses the inner baffle single pass reactor 120 from the proximal portion 122 to the distal portion 124 through an inner fluid conduit defined by the inner wall 125. The composition of the process fluid changes along the operating length of the internal baffle single pass reactor 120 while forming the product mixed butanol while consuming the reactants water and mixed butene as the butene hydration reaction takes place.

The separation system 160 is in fluid communication with the inner baffle single pass reactor 120. The separation system 160 is oriented to selectively receive the crude product and separate water and mixed butene from the crude product to produce purified mixed butanol. In the separation system 160 (dashed box), a cooler 170 is coupled to the inner baffle single pass reactor 120 and receives the crude product from the inner baffle single pass reactor 120, And is operable to reduce the temperature of the crud product. In the embodiment of FIG. 1A, the separation system 160 is coupled to, and in fluid communication with, the distal end 124 of the inner baffle single pass reactor 120. In the embodiment of FIG. 1B, the separation system 160 is coupled to, and in fluid communication with, another region of the inner baffle single pass reactor 120. By way of example, the separation system 160 may couple with the inner baffle single pass reactor 120 in at least one of the baffle cells 147.

In the butanol manufacturing system 100, the cyclone 172 is coupled to the cooler 170, receives the cooled crud product, and removes any residual heterogeneous hydration catalyst. Cyclone 172 produces both spent catalyst and spent catalyst products through spent catalyst 110.

A debutizer column 180 is coupled to the cyclone 172 to receive the catalyst free crude product and to remove unreacted butenes. The deuttenizer column 180 produces recovered butene and butene-free crude products. The recovered butenes are recycled to the proximal portion of the inner baffle single pass reactor 120 via a butene recycle 182 by the butanol manufacturing system 100.

The butanol extraction column 184 couples with the dituctizer column 180, receives the butene-free crude product, and also receives the entrainer through the entrainer feed 108. The butanol extraction column 184 operates by extracting butanol from the aqueous phase of the butene free crude product using the introduced entrainer to form an butanol-poor aqueous phase and an butanol-rich butanol-and-butanol-rich butanol phase. The water is passed through the product 112 from the butanol extraction column 184. The entrainer and butanol phases pass to the bottom of the butanol extraction column 184.

The butanol separation column 186 is coupled with a butanol extraction column 184, receives the entrainer and butanol phase, and separates butanol from the entrainer. The butanol separation column 186 produces the purified mixed butanol substantially free of water, butene and the entrainer. The purified butanol mixture passes from the butanol separation column 186 through the butanol product 114. The recovered entrainer passes through the consumed entrainer 116 from the butanol separation column 186.

1A-1B, the arrangement of the inner baffle single pass reactor 120 has a proximal portion 122 and a distal portion 124 and the distal portion 124 has a serpentine It is a conduit. Some ports 126 are for accessing the interior of the inner baffle single pass reactor 120. Some injection ports provide feed access to the interior of the inner baffle single pass reactor 120, which includes a water injection port 128, a butene injection port 130 and a catalyst injection port 132.

The process fluid also provides latent heat to support the hydration reaction by transferring the heat transferred to the reactor through an external heat exchange system. For example, FIGS. 1A-1B show a temperature control jacket 140 wrapping a portion of an inner baffle single pass reactor 120. A temperature control jacket 140 is operable to provide heat to the enclosed portion of the inner baffle single pass reactor 120 to facilitate the hydration reaction in 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 discharged temperature control fluid.

Internal baffle single pass reactor 120 has an internal flow baffle 146 along its operable length. Each of the inner flow baffles 146 may be a ring member that is secured to the inner wall 125 so as to be immovably fixed within the inner baffle single pass reactor 120. Baffle cell 147 is positioned between successive inner flow baffles 146. Baffle cell 147 is defined by an inner wall 125 as an outer diameter and defined by inner flow baffle 146 as a first end and a second end wherein one of the inner flow baffles 146 is connected to the baffle cell 147 and the first end of the adjacent baffle cell 147. The first end of the baffle cell 147, The baffle cells 147 are positioned continuously along the operating length of the inner baffle single pass reactor 120.

The inner flow baffle 146 interferes with the momentum of the fluid and alters the flow path of the process fluid as it flows through the inner baffle single pass reactor 120. Interruption of the flow momentum and alteration of the fluid flow path cause intimate mixing of the butenes, water, and catalyst in the process fluid within the baffle cell 147. The flow of fluid that is not aligned with the central axis of the inner baffle single pass reactor 120 also transfers heat from the inner wall 125 of the inner baffle single pass reactor 120 to the bulk process fluid, Transmission. The inner flow baffle 146 also increases the process residence time and improves the conversion of butene to butanol.

The oscillator assembly 149 is coupled to the proximal portion 122 of the inner baffle single pass reactor 120. The vibrator assembly 149 includes a process fluid oscillator member 148 located near the proximal portion 122 of the inner baffle single pass reactor 120. The vibrator assembly 149 also includes a process fluid oscillator member 148 for mechanically coupling an external motion driver 152 to the vibrator head 151 and a seal section 148 for sealing and engaging the internal baffle single pass reactor 120 150). The process fluid oscillator member 148 is configured to allow the process fluidic vibrator member 148 to pass from the exterior to the interior of the inner baffle single pass reactor without exposing the process fluid to the external environment, Coupled to the inner baffle single pass reactor (120) through the vibrator seal section (150). The process fluidic vibrator member 148 couples with the inner wall 125 of the inner baffle single pass reactor 120 at the vibrator head 151 such that the outer diameter of the vibrator head 151 slidingly engages the inner wall. The transducer head 151 reciprocates in a forward and aft linear motion and is in fluid communication with the process fluid such that the process fluid undergoes a general sinusoidal movement along the inner baffle single pass reactor 120. The vibrator head 151 may indirectly contact the process fluid or fluid such as a diaphragm or other member that may be in direct contact with the process fluid or may transfer motion of the vibrator head 151 in a general sinusoidal motion of the process fluid. Can communicate with each other.

The change of the process fluidic vibrator member 148 to its relative position imparts a change in position of the process fluid due to contact with the vibrator head 151 and incompressibility of the process fluid. The change in position of the process fluid imparts anomalies to the flow momentum of the process fluid flow along the operable length of the inner baffle single pass reactor 120. The non-uniformity of the process fluid flow improves mixing and heat absorption. Pushing and pulling the incompressible process fluid causes a surge and retraction of the flow of the process fluid to a fixed location inside the internal baffle single pass reactor 120. This mixing of the process fluid within the inner baffle single pass reactor 120 may be accomplished by inducing generally sinusoidal movement in the process fluid along the inner baffle single pass reactor 120 with the oscillator assembly 149, To form a product.

The oscillator assembly 149 also includes an external motion driver 152. An external motion driver 152 may be coupled to the vibrator head 151 via the process fluidic vibrator member 148 and may be used to selectively drive the process fluid vibrator member 148 and the vibrator head 151. The arrangement of the transducer seal sections 150 with the coupling with the outer motion driver 152 and the transducer head 151 being in contact with the inner wall 125 of the inner baffle single pass reactor 120 is controlled by a process fluid oscillator member 148) to a limited range of motion. The process fluid transducer member 148, when operable, moves the transducer head 151 in a linear front-rear fashion.

2

2 is a process flow diagram of another embodiment of the butanol manufacturing system. The butanol manufacturing process of FIG. 2 introduces multiple feeds including the combined mixed butenes and water feed 201 and hydration catalyst feed 106 into the butanol manufacturing system 200. The combined mixed butene and water feeds 201 flow into the inner baffle single pass reactor 120 through butene and water injection ports 203. The butanol manufacturing system 200 manufactures a variety of products including the refining vents 292 and the butanol product 114. The system recycle stream butene recycle 182 and water recycle 288 both contribute to minimizing the amount of make up of mixed butenes and water in the water feed 201.

The separation system 260 of FIG. 2 is arranged differently than the separation system 160 of FIGS. 1A-1B. A high pressure (HP) water separator 272 couples to the cooler 170, receives the cooled crud product, and removes a substantial portion of the water to form a water-lean crud product. The recovered water and hydration catalyst passes through a water recycle 288 for reintroduction into the internal baffle single pass reactor 120.

The dituctizer column 180 is coupled with the HP water separator 272 to receive the water-lean crude product and to remove unreacted butenes from the water-lean crude product to produce a butene- Lt; / RTI > The recovered butene passes through a proximal portion of the inner baffle single pass reactor 120 via a butene recycle 182.

The pervaporation unit 284 includes a pervaporation membrane 286. A pervaporation unit 284 couples with the dituctizer column 180 and receives the butene free crud product and separates the butanol from the butene free crud product using a pervaporation membrane 286 as the permeate . The pervaporation unit 284 forms butanol vapor on the permeate side and forms a permeate retentate consisting mainly of water on the feed side of the pervaporation membrane 286. The water-permeate artifact passes through an internal baffle single pass reactor 120 through a water recycle 288.

A butanol separation column 290 is coupled to the pervaporation unit 284 and operates to receive the butanol vapor and purify the butanol vapor to purified mixed butanol. The purified mixed butanol is substantially free of water and butenes and is conveyed through the butanol product 114. The butanol separation column 290 emits light and non-condensable gas. A portion of the light and non-condensable gas is vented through a stream of purified effluent 292 and the remainder is recycled to the pervaporation unit 284 via a distillation recycle 294 for butanol recovery.

3

Figure 3 is a process flow diagram of another embodiment of the butanol manufacturing system. The butanol manufacturing system of FIG. 3 introduces a feed similar to that shown in the process of FIG. The butanol manufacturing system 300 produces some products including spent catalyst 110 and butanol product 114. The system 300 recycle stream butene recycle 182 and water recycle 288 all contribute to minimizing the amount of makeup mixed butenes and water in the combined feed 201.

The separation system 360 of FIG. 3 is arranged differently than the separation systems 160 and 260. The cyclone 172 couples with the cooler 170, receives the cooled crud product, and removes any remaining heterogeneous hydration catalyst, polymer, and other solids through the spent catalyst 110. The cyclone 172 produces both spent catalyst and spent catalyst products through spent catalyst 110. A high pressure (HP) water separator 272 is coupled to the cyclone 172 to receive the catalystless crude product and to separate the organic phase containing butanol and butene from the water phase under high pressure. The water phase still contains some butanol, but much less than the organic phase. The diteritizer column 180 is coupled to the HP water separator 272 and receives the organic butanol and butene phases and separates the organic phase into recycled butene and purified mixed butanol. The recovered butenes are transferred to the front end of the process via a butene recycle 182 and the purified mixed butanol is passed through the butanol product 114. An azeotropic column 390 is coupled with the HP water separator 272 to receive the water phase and separate the water phase into a butanol / water azeotrope and recycleable water. The butanol / water azeotrope is recycled to the front end of the separation system 360 via butanol / water recycle 392 and the recycled water is transferred to the front end of the process via water recycle 288.

4

4 is a detail view of an embodiment of the inner flow baffle 146 along the operable length of the inner baffle single pass reactor 120. FIG. In the exemplary embodiment of FIG. 4, each of the inner flow baffles 146 may be formed of a disc-shaped plate having an orifice 394, which extends through the 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 of the process fluid with the inner flow baffle 146 generates a vortex in the process fluid. Orifice 394 is sized and positioned through each of the inner flow baffles 146 to create a vortex in the process fluid within baffle cell 147 which results in an optimal mixing of the process fluid . By way of example, the diameter of the orifice 394 relative to the diameter of the inner flow baffle 146 and the position of the orifice 394 through the inner flow baffle 146 may be selected to optimize the mixing of the process fluid.

As process fluid flows through the inner baffle single pass reactor 120, some of the process fluids pass through the orifices 394 of the inner flow baffle 146. The other process fluid contacts the solid ring portion of the inner flow baffle 146 and is redirected in the baffle cell 147 to form a vortex in the process fluid. The vortex formed in the baffle cell 147 improves the mixing of the process fluid.

5

5 shows an exemplary embodiment of an external motion driver 152 according to embodiments of the present disclosure. In the example of FIG. 5, the outer motion driver 152 includes a rotating disk 396. The first end of the process fluid oscillator member 148 is connected to a rotating disk 396. In the embodiment of FIG. 5, process fluid oscillator member 148 is a member of a jointed. As the outer motion driver 152 rotates, the second end of the process fluid oscillator member 148 moves linearly back and forth relative to the proximal portion 122 of the inner baffle single pass reactor 120. The second end of the process fluidic vibrator member 148 is attached to the vibrator head 151 and causes the vibrator head 151 to reciprocate within the inner baffle single pass reactor 120.

As the vibrator head 151 moves further into the inner baffle single pass reactor 120, the vibrator head 151 pushes the process fluid out of the proximal portion 122 toward the distal portion 124. As the vibrator head 151 moves in the opposite direction toward the proximal portion 122, the vibrator head 151 moves the process fluid from the distal portion 124 to the proximal portion 122, as indicated by the directional arrows in FIG. Push it out. Due to this forward and backward movement of the oscillator head 151, the process fluid moves in a general full sinusoidal forward and backward motion within the internal baffle single pass reactor 120. In this way, the oscillatory motion is superimposed on all reactants in the inner baffle single pass reactor 120. This sinusoidal type of motion allows for unique radial mixing.

Process fluids and crude products

The process fluid is a two-phase process of incompatible butenes and water in operating conditions of the butanol manufacturing process in the inner baffle single pass reactor. At any given point along the operating length of the reactor, the process fluids include butene, water, an optional butene hydration catalyst, and butene hydrate products, especially butanol.

The butene hydration reaction occurs in the inner baffle single pass reactor. The process fluid supports the hydration of mixed butenes to mixed butanol in the presence of the butene hydration catalyst in the reactor. As part of the butanol manufacturing process, the process fluid passes from the proximal position of the reactor to the distal end as a crude product.

The crude product is a combination of the products butanol, water, butene and optionally butene hydration catalyst, and the butene hydration catalyst may still be active. The crud product is the process fluid after passing through the distal end of the inner baffle single pass reactor.

Mixed butene

Mixed butenes are introduced as reactants as part of the butanol manufacturing process. The mixed butenes may be purified or derived from a source in a petrochemical feedstock comprising a product of an FCC unit or a thermal cracking unit, a raffinate of an MTBE or TBA process, a fraction of liquefied petroleum gas (LPG) Or from a combined stream from a source. Mixed butenes include one or more 1-butenes, one or two 2-butenes (i.e., cis or trans forms), and isobutylene. Mixed butenes may also include other alkanes and alkenes.

In the butanol product manufacturing embodiment, the mixed butenes include 1-butene. A specific example of the butanol manufacturing process includes the case where the mixed butenes are essentially composed of 1-butene. Fresh or "make-up" 1-butene is preferably a polymerization grade. The new 1-butene has at least 99% by volume of 1-butene, or 99.5% by volume of 1-butene, or 99.9% by volume of 1-butene, or 99.95% by volume of 1-butene or even higher purity. The impurity of the new 1-butene is 5 ppm or less by volume.

The recycling of buten from other parts of the butanol manufacturing system maximizes the butene conversion efficiency. The butanol production system includes a separation system for selectively separating recoverable mixed butenes from the crude product. An embodiment of the butanol manufacturing system includes a case where the butanol manufacturing system is operable to introduce the selectively separated mixed butene into the inner baffle single pass reactor. An embodiment of the butanol manufacturing process includes operating the butanol manufacturing system such that the separately selectively mixed butene is introduced into the internal baffle single pass reactor. Recycled butenes may have a lower compositional purity than new butenes because the recycle material already exists in the butanol manufacturing system and can not introduce new inert or contaminants.

The introduction of mixed butenes occurs as a pressurized gas, liquid, 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 heat to the process fluid that promotes hydration.

water

Water is introduced as a reactant as part of the butanol manufacturing process. New or makeup water introduced into the butanol manufacturing system has at least 99% by volume of water, or 99.5% by volume of water, or 99.9% by volume of water, or 99.95% by volume of water, or even higher purity. The water should be degassed, demineralized, and deionized to prevent contaminants from entering the butanol manufacturing system. The impurities are not more than 5 ppm by volume.

Recirculation of water from other parts of the butanol manufacturing system minimizes the amount of makeup introduced. Water is generally used in excess in the butanol manufacturing process. The separation system selectively separates recoverable water from the crucible product passing from the inner baffle single pass reactor. An embodiment of the butanol manufacturing system includes the case where the butanol manufacturing system is operable to introduce the selectively separated water into the internal baffle single pass reactor. An embodiment of the butanol manufacturing process includes operating the butanol manufacturing system such that the separately optionally separated water is introduced into the inner baffle single pass reactor. When using an unneutralized homogeneous catalyst, the recycled water may transport the active hydration catalyst to the front end of the butanol manufacturing system. Examples of the butanol manufacturing process include the case where the separately and selectively separated water also contains a homogeneous butene hydration catalyst.

Examples of the butanol manufacturing process include the case where the water and the mixed butene are introduced into the inner baffle single pass reactor such that the molar ratio of water to 1-butene ranges from about 1 to about 21.

Hydration catalyst

When the butanol manufacturing system does not include a fixed heterogeneous acid catalyst, the butanol hydration catalyst is introduced as a reactant as part of the butanol manufacturing process. If the butanol manufacturing system does not include a fixed heterogeneous acid catalyst, the introduction of the butene hydration catalyst is optional. An embodiment of the butanol manufacturing process comprises introducing the butene hydration catalyst into the inner baffle single pass reactor of the butanol manufacturing system such that the process fluid is formed proximate to the proximal portion, wherein the butene hydration catalyst is homogeneous Acid, heterogeneous acid, and combinations thereof.

Useful butene hydration catalysts which are homogeneous acids include, for example, sulfuric acid and phosphoric acid. Specific examples of the butanol manufacturing process include a case where the butene hydration catalyst introduced is homogeneous. Examples of useful phosphoric acids include orthophosphoric acid, polyphosphoric acid (PPA) and superphosphate (SPA). Polyphosphoric acid is phosphorus oxyacid having the general formula H (PO ₃ H) _n OH, where n is an integer representing the number of phosphorus units in the molecule. Commercially available mixtures of PPA have blends of ortho (n = 1), pyro- (n = 2), tri- (n = 3), tetra- (n = 4) and higher order condensation chain acids. About 95% to about 118% phosphoric acid (H ₃ PO ₄₎ PPA concentration of the concentration equivalent of a denotes the equivalent weight of the acid that is formed during the decomposition the complete hydrolysis of the polyphosphate. An example thereof is orthophosphoric acid (H ₃ PO ₄ ) (Sigma-Aldrich Corp., St. Louis, Mo.).

Useful butene hydration catalysts also include heterogeneous acid catalysts. Specific examples of the butanol manufacturing process include a case where the introduced hydration catalyst is inhomogeneous. Such acids have acid-functional groups included in metal, ceramic, particulate or polymer structures. Recovery processes, including evaporation, vaporization, distillation and centrifugation systems, can extract the solid catalyst from the process fluid or crude product. An embodiment of the butanol manufacturing process includes operating the butanol manufacturing system such that, if the butene hydration catalyst is an inhomogeneous catalyst, the separation system selectively separates the butene hydration catalyst separately from the crude product. Examples include polymeric resins D008-1 and D008-2 (KaiRui Chemical Co. Ltd., Hebei City, China) with sulfonic acid (SO ₃ H) functional groups attached.

Embodiments of the method include selecting the introduced butene hydration catalyst from the group consisting of a homogeneous butenhydration catalyst, a heterogeneous hydration catalyst, and combinations thereof. Some homogeneous / heterogeneous acid combination systems are known to generate synergistic effects with respect to conversion efficiency and / or selectivity of alkene to alcohol. In embodiments of the butanol production system containing a heterogeneous hydration catalyst in the baffle cell, embodiments of the butanol manufacturing process include introducing a homogeneous hydration catalyst into the inner baffle single pass reactor.

The introduction of the hydration catalyst occurs as a pure substance or is diluted with a delivery solution. The hydration catalyst may be diluted with water or mixed butene to enhance dispersion into the process fluid.

Butanol manufacturing process products

The main product is purified mixed butanol. The purified butanol product has a composition of at least 99% by volume of mixed butanol, or 99.5% by volume of mixed butanol, or 99.7% by volume of mixed butanol, or 99.9% by volume of mixed butanol, or even higher purity to be. An embodiment of the butanol manufacturing system includes a case in which the separation system is operable to produce a purified mixed butanol having a mixed butanol purity of at least 99 volume percent. Butane, butane and the dissolved gas containing the inert components are small impurities that may be present in the purified mixed butanol product.

The butanol manufacturing system is capable of recovering solids from the crude product. Such solids may comprise a catalytically-active hydration catalyst. The butanol manufacturing process can recover the hydration catalyst, neutralize it, and dispose of it outside of the butanol manufacturing process. The external process can process or regenerate the recovered hydration catalyst and recycle it for reintroduction into the internal baffle single pass reactor.

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

The butanol manufacturing system may discharge gas as part of the separation system. The exhausted gas acts as a system purge. The discharged gas contains an inert gas and a light organic gas containing some butenes.

Internal baffle single pass reactor

The inner baffle single pass reactor is a tubular having an inner fluid conduit defined by an inner wall operable to assist hydration of the mixed butenes in a pressurized, heated, and fluid-filled environment. The tube has an inner surface or wall that partially surrounds the volume fixed between the first end (proximal or upstream end) and the second end (distal or downstream end). The working length of the reactor is the fluid length of the tube between the proximal and distal ends. The length of the tube is much longer than its diameter. The tube also has an outer surface or wall along its working length, where heat is transferred between the interior and the exterior.

The internal baffle single pass reactor may operate to allow reactants and optionally a hydration catalyst to pass into the reactor near the proximal portion to mix and form the process fluid. The process fluid traverses the operable length of the reactor from proximal to distal along the fluid flow path. The crude product passes from the reactor proximate the end.

Figures 1 to 3 show the inner baffle single pass reactor of the serpentine type; However, the reactor can take any number of physical arrangements based on the use of connected linear and non-linear fluid conduit segments including standard pipes. Those skilled in the art will be able to conceive the overall shape of the inner baffle single pass reactor based on operating preferences and capabilities, including temperature control, physical space, maintenance and capital costs.

The main flow motive for the process fluid through the inner baffle single pass reactor is the coordinated introduction of the reactants and hydration catalyst to the proximal end and the passage of the crude product from the distal end. Auxiliary flow drivers, including but not limited to pumps and rotary in-line blades, may provide supplemental momentum to the process fluid.

The inner baffle single pass reactor has at least one reactant feed location near the reactor proximal. The introduction of mixed butenes and water can be made up of a combined stream or a separate stream. The new and recycled mixed butenes and water streams may be fed separately into the reactor.

The inner baffle single pass reactor has at least one hydration catalyst feed position. The hydration catalyst feed location is downstream from at least one reactant feed location near the proximal portion of the inner baffle single pass reactor. This position relative to the reactant feed position allows the reactants to intermix before introduction of the hydration catalyst to improve selectivity and conversion.

Embodiments of the butanol manufacturing system include multiple reaction zones along the operating length of the inner baffle single pass reactor. In one embodiment, the reaction zone is the working length between the first mixed butene introduction position and the second mixed butene introduction position. In another embodiment, the reaction zone is between the mixed butene introduction site and the end of the reactor. In another embodiment, the reaction zone is an operating length between the first butene hydration catalyst introduction site and the second butene hydration catalyst introduction site. In another embodiment, the reaction zone is between the butene hydration catalyst introduction site and the end of the inner baffle single pass reactor. Introducing a mixed butene or butene hydrogenation catalyst through multiple locations according to the operating length of the reactor allows for a higher level of process control and butene conversion efficiency. Each reaction zone may have other internal and external process support equipment, including an internal baffle structure to support manufacturing, manipulation of process fluid flow rates, computer control systems, and temperature and pressure manipulation of the reaction zone.

At any given point along the operating length of the inner baffle single pass reactor, the internal fluid conduit axis is perpendicular to the cross sectional area of the internal fluid conduit at that point. In the absence of an internal additive (e.g., an internal flow baffle), the fluid will traverse the operating length of the internal baffle single pass reactor and will generally maintain alignment with the internal fluid conduit during flow.

Internal flow baffle and baffle cell

The inner baffle single pass reactor has a series of internal flow baffles along at least a portion of its operating length. An embodiment of the butanol manufacturing system includes a case in which a set of internal flow baffles is located along the entire working length of the internal fluid conduit.

For each inner flow baffle in the inner baffle single pass reactor, the baffle has a side (upstream facing side) facing the proximal portion of the reactor and an opposite side (downstream facing side) facing the distal end of the reactor. The baffle is typically oriented such that the baffle extends vertically from a position along the inner wall of the reactor and protrudes into the interior fluid conduit. The baffle is generally oriented perpendicular to the internal fluid conduit axis, although other arrangements are feasible to those of ordinary skill in the art. The baffle prevents the process fluid from flowing in alignment with the inner fluid conduit axis during most of the process fluid flow path to promote heat transfer and mixing.

The inner flow baffle may have a plurality of physical arrangements including a rod, a perforated plate, a mesh screen, an orifice plate (a central and off-center flow window), and a segmented plate. Each baffle has a window edge that at least partially defines the flow window for each baffle. In some baffles, such as an orifice plate, the window edges completely define a circular void in the baffle through which the process fluid flows. In another baffle, the window edge partially defines the 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 arrangement (parallel, oblique, vertical) relative to other adjacent internal baffles are important factors in changing the direction of the process fluid.

Wherein the flow path of the fluid through the interior of the inner baffle single pass reactor comprises an orientation of the inner flow baffle including the inner wall and shape of the reactor, the flow window, the spacing, and the orientation of the adjacent baffle with respect to the inner fluid conduit axis Array. The length of the flow path of the process fluid is longer than the operating length of the reactor. The baffle increases the distance the process fluid traverses through the reactor because the process fluid must travel around the inner baffle as well as flow through the distance from the proximal to the distal end.

In a reactor having multiple reaction zones, a different set of baffles may be present in each reaction zone. The arrangement of the inner flow baffles is arranged in series along a portion of the operating length in which the baffles are disposed within each set and is disposed equidistantly spaced between each adjacent baffle in the set. Embodiments of the butanol manufacturing system include an internal baffle single pass reactor having at least one set of internal flow baffles along the working length.

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

When the process fluid traverses the inner baffle single pass reactor, the process fluid enters the baffle cell at least partially through the flow window defined by the upstream baffle. When entering a baffle cell, the formation of a vortex and pushing of the process fluid passing through the inner flow baffle, mixing the reactants, the catalyst and the product together, and not only between the other parts of the process fluid, but also between the process fluid and the interior of the reactor Circulating in the cell through all of the general sinusoidal motion induced in the process fluid by internally transferring heat between the walls. The process fluid then passes through the flow window defined by the downstream baffle at least partially from the baffle cell. The process across the baffle cell is repeated as the process fluid passes from the baffle cell to the baffle cell along the operating length of the reactor.

In an embodiment of the butanol manufacturing process, the introduction of the butene hydration catalyst is optional. In this process, the inner baffle single pass reactor contains a heterogeneous butenhydrating catalyst, which is solid, to selectively convert the mixed butenes in the process fluid to mixed butanol. The catalyst can be contained in any position within the internal fluid conduit of the reactor, but the most efficient location for placing the catalyst in order to maximize the mixing and conversion of the reactants is within each baffle cell.

The location of the solid, inhomogeneous butenol hydration catalyst in each baffle cell may vary depending on the material, structure, and application of the catalyst to the baffle cell component. In a pellet, sphere, or other loose, generally unstructured configuration, the catalyst may be contained in a vessel or other physical constraining means, wherein the vessel or other physical constraining means comprises a structured frame having a flow orifice or slot, A wire mesh bag that allows the process fluid to flow freely from the accumulation of catalyst and into the accumulation while not allowing the catalyst to be transported out of the vessel. This prevents the catalyst from moving with the process fluid flow downstream towards the end of the inner baffle single pass reactor and fouling the separation system. The free-form structure of the unstructured catalyst allows for their direct placement in the flow path of the process fluid including the flow window of the inner flow baffle. A specific example of the butanol manufacturing system includes the case where the heterogeneous butene hydration catalyst is positioned so that the process fluid flowing through the flow window of the downstream baffle is in contact with the heterogeneous butene hydration catalyst, Comprises the case where the reaction of the mixed butenes and water occurs in each baffle cell adjacent to the downstream flow window. The location of the catalyst may be at a location where the process fluid flowing through the flow window of the upstream baffle may contact the heterogeneous butene hydration catalyst. Other forms of the catalyst, including structured forms such as gratings, matrices and sheets, and "amorphous" forms, such as hardenable, thermoplastic and other malleable forms, Adhered, painted, or spray coated to a surface-to-face and an inner flow baffle. An embodiment of the butanol manufacturing system includes a case in which the catalyst is located on the inner wall defining the baffle cell, wherein the reaction of the mixed butene and water occurs along the inner wall And occurs in each baffle cell. For each baffle cell, the downstream facing side of the upstream baffle and the upstream facing side of the downstream baffle face inward toward the baffle cell. An embodiment of the butanol manufacturing system includes the case where the catalyst is located on the side of the inner flow baffle that faces inward toward the baffle cell.

External motion driver

The butanol manufacturing system includes an apparatus external to the internal baffle single pass reactor that induces instability of flow of the process fluid without altering other operating parameters including temperature, mass flow rate and pressure of the butanol manufacturing process . And directs motion into the process fluid using the external motion driver to induce anomalies in the flow of the process fluid. The external motion driver may be operated with a reciprocating frequency of 2 to 5 hertz and a reciprocating amplitude of 20-40 millimeters.

External motion drivers include electrical, electronic-mechanical, hydraulic, pneumatic, gas injection, compressed gas, chemical-reaction and other systems and devices for imparting or delivering motion to the process fluid.

During the butanol manufacturing process, the outer motion driver induces anomalies in the process fluid flow by interfering with the momentum of the fluid as it flows through the inner baffle single pass reactor. The outer motion driver acts on the process fluid in a physical manner when the process fluid traverses from the proximal portion of the reactor to the distal portion. The external motion driver transfers a motion including vibration, reciprocating, variable, and asynchronous fluid motion to the process fluid using a portion of the apparatus in contact with the process fluid. Movement of the coupled device within the inner fluid conduit creates an abnormality in the process fluid flow.

Without any abnormal induction, the butanol manufacturing process can maintain "steady state" conditions within the inner baffle single pass reactor. A steady state condition is one in which the properties of the fluid at any point in the system do not change compared to time. Those skilled in the art of petroleum, petrochemical and chemical operations understand that "steady state operation" sometimes involves some small process variability but generally does not significantly change operating conditions, feed and production rates.

The application of motion by the external motion driver changes the steady state flow condition to an unsteady state by interfering with the fluid momentum of the process fluid flow. The anomalous condition results in a cascade effect on manufacturing conditions and other processes, including heat transfer, reaction efficiency and overall productivity of the system, in response to destabilization of fluid momentum. The abnormality occurs at the moment when the abnormal motion is introduced and lasts for a subsequent period with the effect of decreasing as a function of time. By maintaining a constant operating condition without additional unsteady interaction, a new steady state condition - which may resemble the original steady state - can be achieved. Repeated, periodic, or continuous application of the abnormal motion to the process fluid causes the abnormal condition to continue to exist.

The induced unsteady flow conditions of the process fluid change the relative motion (e.g., accelerated, retarded motion) of the process fluid relative to a fixed position within the inner baffle single pass reactor. The derivation of the abnormal conditions does not affect the overall volume or mass flow per unit time through the reactor as feed introduction and the passage of the crude product influences the overall volume or mass flow rate of the process.

The temporary formation and disappearance of fluid vortex and backwash in the process fluid occurs during the unsteady flow. Similar to the flow in any direction associated with turbulence, the unsteady flow can also occur in a low Reynolds number flow system, which is a typical laminar flow. Wherein the unsteady flow of the process fluid causes a portion of the process fluid traveling through the inner baffle single pass reactor to flow in an unpredictable and non-steady manner only during transient periods, thereby causing mixing, .

The external motion driver is coupled to an apparatus operable to impart motion directly to the process fluid. Actuation of the piston-like actuator causes the process fluid flow to surge and retract while still generally flowing through the internal fluid conduit from the proximal end to the distal end. A diaphragm-like device in fluid communication with the process fluid expands and contracts with respect to the incompressible process fluid and directly displaces it with a similar volume within the internal fluid conduit to produce the desired process fluid flow instability.

An embodiment of the butanol manufacturing system includes an oscillator assembly having an oscillator head having a reciprocating frequency of 2 to 5 hertz. In such an embodiment, the outer motion driver is operable to induce an abnormality of the process fluid by vibrating at a frequency of 2 to 5 Hertz, and in an alternative embodiment, the outer motion driver is oscillated at a frequency of about 3 Hertz do. An embodiment of the butanol manufacturing system includes a vibrator assembly having an oscillator head with a reciprocating amplitude of 20-40 millimeters. In such an embodiment, the outer motion driver may be actuated to induce an abnormality of the process fluid flow by oscillating with a reciprocating amplitude of 20-40 millimeters, and in an alternative embodiment, the outer motion driver may be operated at a velocity of about 30 millimeters It oscillates with amplitude.

Embodiments of the butanol manufacturing system include one or more external motion drivers, wherein each external motion driver is coupled to an apparatus operable to impart direct momentum to the process fluid. Embodiments of the butanol manufacturing process include synchronously operating the first and second external motion drivers. Another embodiment of the butanol manufacturing process includes operating the first and second external motion drivers asynchronously.

Temperature control system

The temperature control system transfers temperature-regulating fluid to the exterior of the inner baffle single pass reactor to maintain a suitable temperature for the butene hydration reaction. Examples of temperature control systems useful for maintaining the temperature in the internal baffle single pass reactor include a heat exchanger, a cooling jacket and a blower. Examples of useful temperature-regulating fluids include water, ethylene glycol, and air. Forced convection of the temperature-regulating fluid is typical.

Separation system

The butanol manufacturing system includes a separation system that can be operated to separate mixed butanol, mixed butenes, and water from the crude product.

The butanol manufacturing system can selectively separate mixed butene from the crude product to produce butene-free crude product and recovered mixed butene. The recovered mixed butenes are useful for recycle by a butanol manufacturing system and for introduction into the internal baffle single pass reactor as a reactant feed. Recirculation of the unreacted mixed butene improves the efficiency of the butene process.

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

Embodiments of the butanol manufacturing system may operate to selectively separate the butene hydration catalyst from the crude product. The cyclone separation system induces centrifugal force on the crucible product such that heavy liquids and solids are separated from the light product. Cyclone separation systems are particularly useful in solid, heterogeneous catalysts because the solids are easily separated from the rest of the liquid by the application of each momentum. The in-line filtration also performs a similar task of removing solids from the crud product, allowing the solids to accumulate under their own weight from the filter surface and flow down. A vaporizer may introduce heat to the crucible product such that a portion of the crucible product forms a vapor. The evaporator comprising a thin film evaporator can separate the hot boiling product and the solids from the portion of the crucible product from which the vapor condition can be obtained at a lower operating pressure. The hydration catalyst and the recovered other solids or very heavy liquid may be withdrawn from the butanol manufacturing system for recovery or disposal.

The yen training fluid is useful for selectively extracting butanol from the crude product. Because the crude product contains some water, water-incompatible organic compounds that are readily separable from water and have an affinity for the mixed butanol relative to water are useful for performing the extraction. An entrainer fluid having a lower distillation boiling point than the mixed butanol at atmospheric pressure is also useful for separating the entrainer from the relatively theoretical mixed butanol. Examples of useful entrainer fluids include pentane, hexane, hexene, cyclohexane, benzene, toluene, xylene, and mixtures thereof.

The introduction of a rare water-immiscible entrainer feed in the crude product separates the crude product into two phases: a butanol-rich organic phase containing the entrainer, and a butanol-poor organic phase. The butanol extraction column may separate the water phase from the entrainer phase. Figures 1a-1b show a butanol extraction column 184 that produces an butanol-rich butanol mixture that passes through a butanol-poor aeration and butanol separation column 186, Other purification system processes convert the butanol-rich entrainer fluid into purified mixed butanol and lean entrainer fluid.

The pervaporation membrane can separate the directly mixed butanol from the crude product. The butanol manufacturing process comprising a pervaporation membrane selectively vaporizes the mixed butanol and does not selectively vaporize the water. The pervaporated material is a steamed mixed butanol that can be condensed and distilled to form the purified mixed butanol. The residue is a liquid consisting mostly of water containing some butanol. In this type of purification system, the residues are useful not only to recapture the desired butanol but also to recycle to conserve water for reuse.

Supporting equipment

The embodiments include many additional standard components or equipment that enable and enable the described devices, processes, methods, and systems. Examples of such standard equipment known to those skilled in the art are heat exchangers, pumps, blowers, reboilers, steam generators, condensate handling devices, membranes, single and multistage compressors, separation and sorting equipment, valves, Pressure-, temperature-, level-, and flow-sensor devices.

The operation, control and performance of some or all steps of a process or method may occur through human interaction, preprogrammed computer control and response systems, or a combination thereof.

The operation of the butanol manufacturing system

The butene hydration catalyst may be operable to selectively convert the mixed butenes in the process fluid to the mixed butanol under operating conditions of the inner baffle single pass reactor. An embodiment of the butanol manufacturing process includes operating the butanol manufacturing system such that the temperature of the process fluid in the inner baffle single pass reactor is maintained in the range of about 80 캜 to about 150 캜. An embodiment of the butanol production process includes operating the butanol manufacturing system such that the temperature of the process fluid in the inner baffle single pass reactor is maintained in the range of about 100 캜 to about 120 캜. An embodiment of the butanol manufacturing process includes operating the butanol manufacturing system such that the pressure of the process fluid in the inner baffle single pass reactor is maintained in the range of about 5 bar to about 70 bar.

Maintaining the mixed butanol, or some of the components of the mixed butanol, in a liquid or critical fluid state, or a combination of the two, may improve mixing in the inner baffle single pass reactor. An embodiment of the butanol manufacturing process includes operating the butanol manufacturing system such that the temperature and pressure of the process fluid within the inner baffle single pass reactor remain within a range to cause the mixed butene to be in a liquid state. An embodiment of the butanol manufacturing process includes operating the butanol manufacturing system such that the temperature and pressure of the process fluid in the inner baffle single pass reactor is such that the mixed butene is in a supercritical state.

The improved mixing that occurs in the internal baffle single pass reactor allows higher material throughput than standard fixed volume reactor systems. An embodiment of the butanol manufacturing process includes operating the butanol manufacturing system such that the residence time of the process fluid in the inner baffle single pass reactor is maintained in the range of about 0.1 hours to about 0.2 hours. A shorter residence time ensures a higher space velocity that minimizes the exposure of 1-butene to a temperature that can cause isomerization to less useful 2-butene.

Example

Certain embodiments of embodiments enable a better understanding of the butanol manufacturing system and process. The above embodiments should not limit or define the scope of the present invention.

Examples 1 to 4 and Comparative Examples 1 to 4

An oscillating baffle reactor (OBR) treats five example mixtures (1-4). The autoclave reactor treats five comparative mixtures (1-4). Each example has a comparative example of the molar ratio of similar water: 1-butene and the relative relationship of catalyst: 1-butene. For example, Example 1 is similar to Comparative Example 1, Example 2 is similar to Comparative Example 2, and so on. Table 1 shows compositions of Examples 1 to 4 and Comparative Examples 1 to 4. The introduced 1-butene, water and total volume are in millimeters (mL). The molar ratio is a number without units.

(D008; KaiRui Chemical Co. Ltd., Hebei Province, China) and the amount of water for each of the Examples and Comparative Examples were measured for the respective reactor types (OBR; autoclave ). The amount of 1-butene under nitrogen pressure is introduced into the designated reactor type for each experiment. When the reactor is sealed, the reactor is heated to operating temperature (100-110 ° C). In experiments in the autoclave reactor, the heating jacket maintained the operating temperature throughout the experiment. In the experiments in the OBR, a hot silicone oil bath maintained the operating temperature. The reaction time is 1 hour in both the autoclave and OBR. During the processing of the example, the OBR reactor mixes the composition of the example above at 3 hertz (Hz) frequency and 30 millimeter amplitude, while the autoclave stirs each comparative composition at a rate of 200 revolutions per minute (RPM). Both reactors mix the compositions to form a homogeneous mixture of immiscible reactants. After one hour, each type of reactor is stopped, cooled to room temperature, and unreacted 1-butene is discharged. Analyzing the liquid product for 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 treating the feed compositions of the above Examples and Comparative Examples in the OBR and the autoclave reactor under similar processing conditions (i.e., temperature, time, feed composition). For all four examples, both the weight percent and the 1-butene conversion mole percentage are higher for the OBR-treated material than for the autoclaved-treated material.

Experiments of Examples 1 to 4 and Comparative Examples 1 to 4. Conduct OBR Autoclave operation Condition unit Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Hydration Catalyst D008 grams 10.0 7.5 5.0 2.5 5.0 3.8 2.5 1.3 The introduced 1-butene mL 40.0 30.0 20.0 10.0 20.0 15.0 10.0 5.0 Introduced water mL 8.0 12.0 40.0 40.0 4.0 6.0 20.0 20.0 Water: 1-butene molar ratio --- 1.0 2.1 10.4 20.7 1.0 2.1 10.4 20.7 Total volume introduced mL 48.0 42.0 60.0 50.0 24.0 21.0 30.0 25.0 Total product weight of sec-butanol wt. % 93 50 23 10 32 31 12 5 1-butene conversion rate mol. % 22 24 55 48 8 15 29 24

As can be seen in Table 1, all of the above OBR experimental runs have higher 1-butene conversion rates than comparable autoclave comparative examples.

6 graphically illustrates the molar ratio of water: 1-butene introduced to the vibrating baffle reactor (example) and the autoclave reactor (comparative example) to butanol to butanol. Figure 6 is a plot of the data from Table 3 of the molar ratio introduced into the reactor versus the determined 1-butene conversion. The data for each information set (Examples and Comparative Examples) is a curve fit using a quadratic polynomial using Microsoft Excel 2010 (Redmond, Wash.).

Figure 6 also shows a quadratic polynomial relationship between the molar percent conversion of 1-butene and the molar ratio of the introduced water: 1-butene. In the case of the OBR, the determined second order relationship has an R2 value of greater than 0.99 and is well suited. The second polynomial for the OBR experiment is given by Equation 1:

MCR _{C4 = / BtOH} = -0.002173 * (MR _{H2O: C4 =} ) ² + 0.061323 * MR _{H2O: C4 =} + 0.14264 (Formula 1)

Where MCR _{C4 = / BtOH} is the molar conversion of 1-butene to the butanol in mole percent, and MR _{H2O: C4 =} is the molar ratio of water to 1-butene in the introduced mixture. Formula 1 is determined for a molar ratio range of from about 1 to about 21.

In addition, the overall molar conversion values for the OBR experimental runs (Examples 1 to 4) fit between two quadratic polynomial relationships useful for estimating the molar conversion of 1-butene to butanol. The above two formulas, which are similar to the formula 1, (Low) " and " Poly. (High) ". Equations 2 and 3 show the molar conversion values of Examples 1 to 4 for the molar ratio ranges of the above examples.

_{EMCR C4 = / BtOH ≥-0.002173} * (MR H2O: C4 =) 2 + 0.061323 * MR H2O: C4 = + 0.045 ( formula 2) and _{EMCR C4 = / BtOH ≤-0.002173} * (MR H2O: C4 =) 2 + 0.061323 * MR _{H2O: C4 =} + 0.24028, (Formula 3),

Wherein EMCR _{C4 = / BtOH} is the estimated molar conversion in molar percent of 1-butene to butanol, and MR _{H2O: C4 =} is in the range of about 1 to about 21. The molar ratio of water to 1-butene It is rain. An example of the butanol manufacturing process includes operating the butanol manufacturing system such that the molar conversion rate of 1-butene to butanol is within the estimated molar conversion value range as determined by Equations 2 and 3, do. An embodiment of the butanol manufacturing process comprises operating the butanol manufacturing system such that the molar conversion rate, expressed in mole percent, of 1-butene to butanol is approximately greater than the estimated molar conversion value as determined by Equation 2. [ In addition, two equations similar to equations 1-3 are plotted as dashed lines "Poly. (MedLow)" and "Poly. (MedHigh)" in FIG. Equations 4 and 5 are close to Equation 1 and show the molar conversion values of Examples 1 to 4 for the molar ratios of the Examples between Equations 2 and 3:

_{EMCR C4 = / BtOH ≥-0.002173} * (MR H2O: C4 =) 2 + 0.061323 * MR H2O: C4 = + 0.09382 ( Equation 4) and _{EMCR C4 = / BtOH ≤-0.002173} * (MR H2O: C4 =) 2 + 0.061323 * MR _{H2O: C4 =} + 0.19146, (Formula 5),

Where EMCR _{C4 = / BtOH} is the molar conversion of 1-butene to molar percent estimated, and MR _{H2O: C4 =} is the range of about 1 to about 21, for 1-butene in the introduced mixture It is the molar ratio of water. The embodiment of the butanol manufacturing process comprises operating the butanol manufacturing system such that the molar conversion rate as a mole percentage of 1-butene to butanol is within a range of estimated molar conversion values as determined by equations 4 and 5 do. An embodiment of the butanol manufacturing method includes operating the butanol manufacturing system such that the molar conversion rate expressed in mole percent of 1-butene to butanol is approximately greater than the estimated molar conversion value as determined by equation (4).

Example 5 and Comparative Example 5

The OBR used in Examples 1 to 4 treats the mixture of Example 5. The autoclave reactor used in Comparative Examples 1 to 4 treats the mixture of Comparative Example 5. The Examples and Comparative Examples have similar molar ratios of water: 1-butene and catalyst: 1-butene. Table 2 shows the compositions of Example 5 and Comparative Example 5. The introduced 1-butene, water and total volume are in millimeters (mL). The molar ratio is a number without units.

The processes of Example 5 and Comparative Example 5 are similar to the processes of Examples 1 to 4 and Comparative Examples 1 to 4, respectively, except that the butene hydration catalyst is orthophosphoric acid (H ₃ PO ₄ ) (Sigma-Aldrich Corp St. Louis, Mo.).

Conduct of Example 5 and Comparative Example 5 Conduct OBR Autoclave operation Condition unit Example 5 Comparative Example 5 Hydration catalyst H3PO4 grams 5.0 2.5 The introduced 1-butene mL 20.0 10.0 Introduced water mL 20.0 10.0 Water: 1-butene molar ratio --- 5.2 5.2 Total volume introduced mL 45.0 20.0
Total product weight of sec-butanol wt. % 15 2
1-butene conversion rate mol. % 18 2

Table 2 shows the results of processing the compositions of the Examples and Comparative Examples in OBR for the autoclave reactor under similar processing conditions (i.e., temperature, time, composition). In the experiments, the weight percent and 1-butene conversion mole percent are higher than the OBC-treated material above the autoclave-treated material. The use of an acid-hydrocatalyst catalyst confirms the superiority of using the OBR under similar processing conditions as the autoclave reactor described above for the hydration of 1-butene.

Claims (20)

1. A butanol manufacturing system for producing a purified butanol from water and mixed butenes,
An internal baffle single pass reactor,
An inner fluid conduit defined by an inner wall and an operative length between the proximal and distal ends, the inner fluid conduit selectively containing and admixing process fluids comprising water, mixed butenes and mixed butanol to form a crude product,
An inner flow baffle located along at least a portion of an operating length of the inner fluid conduit, the inner flow baffle being annular and secured to the inner wall, and
A baffle cell positioned continuously along the working length and defined by the inner wall as an outer diameter and defined by the inner flow baffle as a first end and a second end, An inner baffle single pass reactor defining both a first end of one baffle cell and a second end;
A separation system for selectively containing a crude product and separating water and said mixed butene from the crude product to form a purified mixed butene, said separation system being in fluid communication with said internal baffle single pass reactor;
A proximal portion of the inner baffle single pass reactor having a reciprocating vibrator head capable of selective linear motion back and forth and communicating with the process fluid such that the process fluid undergoes a general sinusoidal movement along the inner baffle single pass reactor And a coupled oscillator assembly. The method according to claim 1,
Wherein each of said internal flow baffles is formed of a disc-shaped plate having an orifice, wherein said orifice extends through said plate. The method of claim 2,
Wherein an outer diameter of the disk-shaped plate is fixed to the inner wall. The method of claim 2,
Wherein the orifice is sized and positioned through the plate in the baffle cell to form a vortex in the process fluid. 5. The method according to any one of claims 1 to 4,
Wherein the outer diameter of the vibrator head slides and engages the inner wall. 6. The method according to any one of claims 1 to 5,
Wherein the separation system is in fluid communication with a distal end of the inner fluid conduit. 7. The method according to any one of claims 1 to 6,
Wherein said separation system is in fluid communication with at least one said baffle cell. The method according to any one of claims 1 to 7,
Wherein the baffle cell is located along the entire working length of the inner fluid conduit. The method according to any one of claims 1 to 8,
Wherein the vibrator head has a reciprocating frequency of 2 to 5 hertz. The method according to any one of claims 1 to 9,
Wherein the vibrator head has a reciprocating amplitude of 20-40 millimeters. The method according to any one of claims 1 to 10,
Wherein the vibrator assembly includes an external motion driver that is mechanically coupled to the vibrator head and selectively drives the vibrator head. The method of claim 11,
The vibrator assembly includes an inner baffle single pass reactor and an oscillator seal section for sealing and engaging a fluid oscillator member of the process, wherein the fluid oscillator member mechanically connects the outer motion driver to the oscillator head . CLAIMS What is claimed is: 1. A process for preparing a purified mixed butanol from a combination of water and mixed butenes,
Providing an internal baffle single pass reactor,
An inner fluid conduit defined by an inner wall and an operating length between the proximal and distal ends,
An inner flow baffle located along at least a portion of the operating length of the inner fluid conduit, the inner flow baffle being annular and secured to the inner wall,
A baffle cell positioned continuously along an operating length and defined by an outer diameter by the inner wall and defined by a flow baffle as a first end and a second end, Defines both the two ends and the first end of the adjacent baffle cell;
Passing a process fluid including mixed butenes, water and mixed butanol through the internal single pass reactor;
Wherein the inner baffle single pass reactor has an oscillator assembly coupled to the proximal portion of the inner baffle single pass reactor within the process fluid to induce generally sinusoidal movement along the inner baffle single pass reactor, Mixing the process fluid in a reactor, the oscillator assembly having a reciprocating oscillator head selectively capable of linearly moving forward and backward; And
And separating said water and mixed butene from the crude product in a separation system in fluid communication with said inner baffle single pass reactor to produce purified mixed butanol. ≪ / RTI > 14. The method of claim 13,
Wherein mixing the process fluid in the inner baffle single pass reactor comprises introducing a vortex by pushing the process fluid past the flow baffle to produce a purified < RTI ID = 0.0 > A method for producing mixed butanol. 14. The method according to claim 13 or 14,
A method of making a purified mixed butanol from a combination of water and mixed butene, further comprising transferring the process fluid from the distal end of the inner fluid conduit to the separation system. The method according to any one of claims 13 to 15,
A method of making purified mixed butanol from a combination of water and mixed butene, further comprising transferring the process fluid from the at least one baffle cell to the separation system. The method according to any one of claims 13 to 16,
A method of making a purified mixed butanol from a combination of water and mixed butene, further comprising operating the oscillator assembly at a reciprocating frequency of 2 to 5 hertz. The method according to any one of claims 13 to 17,
A method of making purified mixed butanol from a combination of water and mixed butene, further comprising operating the oscillator assembly with a reciprocating amplitude of 20-40 millimeters. The method according to any one of claims 13 to 18,
Wherein the method for producing purified mixed butanol from a combination of water and mixed butenes further comprises driving the vibrator head with an external motion driver that is mechanically coupled to the vibrator head. The method of claim 19,
A method of making purified mixed butanol from a combination of water and mixed butenes comprises sealing an oscillator chamber section that mechanically couples the outer motion driver to the vibrator head and the inner baffle single pass reactor and process fluid oscillator member ≪ / RTI >

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