CN108349856A - Utilize the alkene hydrating process of oscillation baffle reactor - Google Patents

Utilize the alkene hydrating process of oscillation baffle reactor Download PDF

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Publication number
CN108349856A
CN108349856A CN201680058988.4A CN201680058988A CN108349856A CN 108349856 A CN108349856 A CN 108349856A CN 201680058988 A CN201680058988 A CN 201680058988A CN 108349856 A CN108349856 A CN 108349856A
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China
Prior art keywords
butanol
production
process fluid
internal flow
oscillator
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Pending
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CN201680058988.4A
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Chinese (zh)
Inventor
阿比尔·阿尔加
卡里姆丁·M·沙伊克
W·徐
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Saudi Arabian Oil Co
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Saudi Arabian Oil Co
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Priority claimed from US14/879,601 external-priority patent/US10155707B2/en
Application filed by Saudi Arabian Oil Co filed Critical Saudi Arabian Oil Co
Publication of CN108349856A publication Critical patent/CN108349856A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/006—Baffles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0066—Stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0073—Sealings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1806—Stationary reactors having moving elements inside resulting in a turbulent flow of the reactants, such as in centrifugal-type reactors, or having a high Reynolds-number
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/185—Stationary reactors having moving elements inside of the pulsating type
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/12—Monohydroxylic acyclic alcohols containing four carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00761—Details of the reactor
    • B01J2219/00763—Baffles
    • B01J2219/00765—Baffles attached to the reactor wall
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a kind of production of butanol system and method for producing refined mixed butyl alcohol, include the interior panelling single pass reactors with the internal flow pipeline limited by inner wall.The internal flow pipeline accommodates the process fluid comprising water, mixed butene and mixed butyl alcohol, to form crude product.Along the length of internal flow pipeline, internal flow baffle is set.The outer diameter of baffle chamber is limited by inner wall, and its end is limited by internal flow baffle.Piece-rate system detaches water and mixed butene from crude product, to which production refines mixed butyl alcohol.Oscillator assembly is connect with interior panelling single pass reactors, and there is reciprocating oscillating end, the reciprocating oscillating end can be moved selectively in a manner of front and back linear movement, and it is connected to process fluid so that process fluid carries out substantially sine curve along interior panelling single pass reactors and moves.

Description

Utilize the alkene hydrating process of oscillation baffle reactor
The cross reference of related application
The application is entitled " using the olefin hydration process of oscillation baffle reactor " that September in 2013 is submitted on the 3rd U.S. Patent application No.14/016,798, existing United States Patent (USP) No.9,187,388 part continuation application, and require its priority And equity, wherein U.S. Patent application No.14/016,798 require the U.S. Provisional Application No.61/ that September in 2012 is submitted on the 5th 697,076 priority and right.For the purpose of United States patent law, the application is by integrally quoting by above-mentioned each application Complete disclosure be incorporated herein.
Technical field
The present invention relates to the fields of production of butanol.More specifically, technical field of the invention is related to passing through butylene hydration Produce the field of butanol.
Background technology
Butanol is the effective of traditional oxygenatedchemicals and fuel-raw material swelling agent (including methyl tertiary butyl ether(MTBE) and ethyl alcohol) Substitute.Butanol not only facilitates the raising of octane number grade, and the oxygen admixed is provided by fuel mixture.Mixing is total Mixed butanol is also relatively inexpensive.
The main method for producing butanol, especially mixed butyl alcohol is by butylene hydration technique.Known butylene hydration work Skill includes liquid-liquid diphasic system.Butylene and water are in low relative concentration (both butylene in water and the water in butylene) System in be unmixing each other.Unmixability will not be alleviated by promoting operating condition.The unmixability of reactant is known A low reason of conversion per pass.
In addition, unmixability has an effect on the distribution of hydration catalyst.Typical hydration catalyst tends to water phase or hydrocarbon phase- Not usually tend to both.This bad distribution of hydration catalyst will not promote the catalysis of entire diphasic system to react, But the main catalysis reaction only in single-phase.
Therefore it needs to improve conversion per pass of the butylene to butanol in butylene hydration system and technique.
Invention content
For including by the production of butanol system of water and the refined mixed butyl alcohol of mixed butene production：Interior panelling one way is reacted Device, the interior panelling single pass reactors have internal flow pipeline, and the internal flow pipeline is by inner wall and proximally and distally Between working length limit, the internal flow pipeline selectively accommodates and mixes comprising water, mixed butene and mixing The process fluid of butanol, to form crude product.The interior panelling single pass reactors further include internal flow baffle, along institute It states at least part of the working length of internal flow pipeline and is arranged, the internal flow baffle is annular and fixes The inner wall.Along the working length, continuously the outer diameter of setting and the baffle chamber is limited and the by the inner wall for baffle chamber One end and second end are limited by the internal flow baffle, wherein one of described internal flow baffle limits the baffle chamber One of second end and adjacent baffle chamber first end.Piece-rate system connects with the interior panelling single pass reactors fluid It is logical, and orient for selectively receiving the crude product, and the water and the mixing are detached from the crude product Butylene, to produce the refined mixed butyl alcohol.Oscillator assembly is connected to the described close of the interior panelling single pass reactors End, the oscillator assembly have the reciprocating oscillator head that can be selectively moved in a manner of front and back linear movement, and And it is connected to the process fluid so that the process fluid carries out substantially sinusoidal bent along the interior panelling single pass reactors Line moves.
In an alternate embodiment, each internal flow baffle can be formed by dished plate, which, which has, prolongs Extend through the aperture of the plate.The outer diameter of dished plate can be fixed to the inner wall.Can be arranged the aperture size and By the position of the plate, to generate vortex in the process fluid in the baffle chamber.It baffle chamber can be along inside The whole operation length of fluid line and be arranged.
In other alternate embodiments, the outer diameter of oscillator head slidably engages inner wall.Piece-rate system can with it is interior The distal fluid of portion's fluid line is connected to, or can be in fluid communication at least one of baffle chamber.Oscillator head it is reciprocal Frequency can be 2 hertz to 5 hertz, and past complex amplitude can be 20 millimeters to 40 millimeters.Oscillator assembly may include mechanically connecting It is connected to and the selectively external movement driver of driving oscillator head.Oscillator assembly may include sealingly engaging internal gear The oscillator hermetic unit of plate single pass reactors and process fluid oscillator component, the process fluid oscillator component transport outside Dynamic driver is mechanically coupled to the oscillator head.
In the another embodiment of the disclosure, the side for refining mixed butyl alcohol by the combination production of water and mixed butene Method includes providing interior panelling single pass reactors.Between the interior panelling single pass reactors have by inner wall and proximally and distally Working length limit internal flow pipeline.Internal flow baffle along the internal flow pipeline the working length It is arranged at least partially, the internal flow baffle is annular and the fixed inner wall.It is grown along the operation baffle chamber The outer diameter of the continuous setting of degree and baffle chamber is limited by the inner wall and its first end and second end is kept off by the internal flow Plate limits, wherein one of described internal flow baffle limits the second end of one of described baffle chamber and adjacent baffle The first end of room.Including the process fluid of mixed butene, water and mixed butyl alcohol passes through interior panelling single pass reactors.By using The oscillator assembly being connect with the proximal end of the interior panelling single pass reactors, it is anti-along the interior panelling one way It answers device to cause substantially sine curve movement in the process fluid, the work is mixed in the interior panelling single pass reactors Skill fluid, to form crude product, the oscillator assembly is had and can selectively be moved in a manner of front and back linear movement Reciprocating oscillator head.From the crude product in the piece-rate system being in fluid communication with the interior panelling single pass reactors The water and the mixed butene are detached, to which production refines mixed butyl alcohol.
In an alternate embodiment, the step of mixing the process fluid in the interior panelling reactor includes passing through Push the process fluid by the internal flow baffle, to cause whirlpool in the process fluid in the baffle chamber Stream.Process fluid can be transferred to the piece-rate system of the far-end of internal flow pipeline, or can be by process fluid from baffle At least one of room is transferred to piece-rate system.
It, can be with the past of 2 hertz to 5 hertz of reciprocating frequence and 20 millimeters to 40 millimeters in other alternate embodiments Complex amplitude operated oscillator component.The external movement driver driving oscillator head for being mechanically connected to oscillator head can be used.It can Interior panelling single pass reactors and process fluid oscillator component are sealingly engaged using oscillator hermetic unit, oscillator is close External movement driver is mechanically connected to oscillator head by envelope part.
Brief Description Of Drawings
By below to the detailed description of preferred embodiment, appended claims and attached drawing, of the invention these It will become apparent to other features, aspect and advantage, wherein：
Figure 1A -1B are the process flow charts of the embodiment of production of butanol system；
Fig. 2 is the process flow chart of another embodiment of production of butanol system；
Fig. 3 is the process flow chart of another embodiment of production of butanol system；
Fig. 4 is the exemplary details figure according to a part for the interior panelling single pass reactors of the embodiment of the disclosure；
Fig. 5 is the signal according to the interior panelling single pass reactors and external movement driver of the embodiment of the disclosure Figure；With
Fig. 6 is shown for oscillation baffle reactor and autoclave reactor, mole of the water and 1- butylene of introducing Than the chart relative to butylene to mole % conversion ratios of butanol.
In the accompanying drawings, similar component or feature or the two can reference labels having the same.Attached drawing and its explanation help In more fully understanding production of butanol system and its application method.Attached drawing should not in any way limit the scope of the present invention Or it limits.For ease of description, attached drawing is schematic diagram.Those of ordinary skill in the art understand, this system be have can Effectively achieve the ancillary equipment of expected purpose and the labyrinth of subsystem.
The detailed description of preferred embodiment
Specification includes：The detailed description of brief summary of the invention, Brief Description Of Drawings and preferred embodiment, specification and accompanying Claims be related to particularly unique feature of the present invention (including technique or method and step).Those skilled in the art can manage Solution, the present invention includes all possible combination and application of specific features described in the specification.Those skilled in the art answers Work as understanding, the embodiment party that the embodiment description or the present invention provided the present invention is not limited to specification is not provided by specification The restriction of case description.Other than the spirit for being only limitted to specification and appended claims, subject of the present invention is unrestricted.
Those skilled in the art is also understood that is not intended to limit the present invention's for describing the term of particular embodiment Range or range.When being explained to specification and appended claims, all terms should according to each term in text In consistent possible broadest mode explain.All technical and scientific terms for specification and appended claims Meaning is identical as those skilled in the art's normally understood meaning of institute, unless otherwise specified.
In specification and appended book, the "an" of used singulative, "one" and it is " described " packet The referring to thing of plural form is included, unless in addition explicitly pointing out herein.Verb " comprising " and its version should be construed as with non- Exclusive mode refers to component, assembly unit or step.What mentioned component, assembly unit or step can be not expressly mentioned with other Component, assembly unit or step exist jointly, use or combination.Verb " connection " and its version refer to completing any type of institute It needs to engage, including electricity, machinery or fluid engagement, to form single object by two or more aforementioned not connected objects.Such as Fruit first device is connected to second device, then the connection can directly occur or be occurred by conventional attachments." optional " and Its version, which refers to the event then described or situation, can occur or can not occur.It is described description include the event or The situation that the situation and the event or situation happened does not occur." can effectively (Operable) " and its various shapes Formula refers to that suitable for its suitable function and can be used in its desired use." relevant (Associated) " and its various forms are It is related to other things to refer to something, because they occur simultaneously or one generates another one.
Spatial terminology describes the relative position of an object or one group of object relative to another object or another group of object. Spatial relationship is applicable in along vertical axis and trunnion axis.Indicate that the word of orientation and relationship includes " upstream " and " downstream " and other classes It is unrestricted purpose for ease of description, unless otherwise specified like term.
When providing numberical range in specification or appended claims, it should be appreciated that numerical intervals include Each interval value between upper and lower bound and upper and lower bound.Based on any specific exclusion provided, the present invention includes And define the more small range in the section.Substantially free refers to the signified units of measurement less than 1%.It is " significant " to indicate Signified units of measurement equal to or more than 10%.
When mentioning the method including two or more limited steps in specification and appended claims, institute The step of restriction, can carry out or be carried out at the same time in any order, unless context eliminates this possibility.
Figure 1A -1B
Figure 1A -1B are the process flow charts of the embodiment of production of butanol system.If the production of butanol technique of Figure 1A -1B will Dry kind of feed is introduced into production of butanol system 100, including mixed butene feed 102, water feed 104, hydration by feed line Catalyst feed 106 and entrainer feed 108.Production of butanol system 100 generates several product by product line, including useless Catalyst 110, output water 112, butanol product 114 and useless entrainer 116.
Production of butanol system 100 supports conversion and refined butanol product of the butylene to butanol including several units Production.It is mixed butyl alcohol that interior panelling single pass reactors 120, which support that catalysis causes butylene hydration,.Mixed butene feed 102, water supply Material 104 and hydration catalyst feed 106 all enter production of butanol system 100 by interior panelling single pass reactors 120.It is internal The crude product stream of the mixed butyl alcohol for recycling output is made in baffle single pass reactors 120.
Interior panelling single pass reactors 120 include process fluid, which is reactant, catalyst and reaction product Mixture.The process fluid is proximally 122 anti-by interior panelling one way by the internal flow pipeline that is limited by inner wall 125 Device 120 is answered to reach distal end 124.With the reactants water of the generation of butylene hydration reaction, formation product mixed butyl alcohol and consumption And mixed butene, the composition of process fluid change along the working length of interior panelling single pass reactors 120.
Piece-rate system 160 is fluidly connected to interior panelling single pass reactors 120.Piece-rate system 160 is oriented for selecting Property receive crude product, and water and mixed butene are detached from the crude product, to which production refines mixed butyl alcohol.In segregative line In 160 (dotted line frames) of uniting, cooler 170 is connected to interior panelling single pass reactors 120, and can be efficiently received and come from The crude product of interior panelling single pass reactors 120, and the temperature for reducing crude product is used for separating treatment.In the embodiment of Figure 1A In, piece-rate system 160 is connected to and is fluidly connected to the distal end 124 of interior panelling single pass reactors 120.In the implementation of Figure 1B In scheme, piece-rate system 160 is connected to and is fluidly connected to other regions of interior panelling single pass reactors 120.For example, point It can be connected to interior panelling single pass reactors 120 from least one of baffle chamber 147 from system 160.
In production of butanol system 100, cyclone separator 172 is connected to cooler 170, receives cooling crude product, and Remove any remaining heterogeneous hydration catalyst.Cyclone separator 172 generates the waste catalyst obtained by dead catalyst 110 And the crude product without catalyst.
Debutenizer 180 is connected to cyclone separator 172, receives the crude product without catalyst, and remove unreacted Butylene.Debutenizer 180 generates the butylene of recycling and the crude product without butylene.The butylene of recycling is by production of butanol system 100 The proximal end of interior panelling single pass reactors 120 is recycled to by butylene cycle 182.
Butanol extraction column 184 is connected to debutenizer 180, receives the crude product without butylene, and also pass through entrainer Feed 108 receives entrainer.Butanol extraction column 184 can be effectively by using the entrainer of introducing from the thick production without butylene Butanol is extracted in the water phase of object, forms the water phase for wherein lacking butanol and is wherein rich in the entrainer and butanol phase of butanol.Water is logical It crosses output water 112 and is transmitted from butanol extraction column 184.Entrainer and butanol mutually as the tower bottom product of butanol extraction column 184 and Transmission.
Butanol knockout tower 186 is connected to butanol extraction column 184, receives entrainer and butanol phase, and by butanol from entrainer Middle separation.Butanol knockout tower 186, which generates, refines mixed butyl alcohol, substantially free of water, butylene and entrainer.Refined butanol mixing Object is transmitted by butanol product 114 from butanol knockout tower 186.The entrainer of recycling is by useless entrainer 116 from butanol knockout tower 186 transmission.
As seen in figs. 1 a-1b, the construction of interior panelling single pass reactors 120 is with proximal end 122 and distal end 124 and remote End 124 is connected to the serpentine duct of cooler 170.Several ports 126 are used for into the interior of interior panelling single pass reactors 120 Portion.Several inlets provide feed, to enter the inside of interior panelling single pass reactors 120, including water inlet 128, fourth Alkene inlet 130 and catalyst inlet 132.
Process fluid is also transferred to the heat in reactor to provide latent heat by transmission by means of external heat-exchanging system, uses In support hydration reaction.For example, Figure 1A -1B show the temperature control of a part for encapsulating interior panelling single pass reactors 120 Chuck 140.Temperature control chuck 140 effectively can provide heat for the encapsulating part of interior panelling single pass reactors 120, with Promote the hydration reaction in process fluid.Temperature controlled fluid supply line 142 introduces fresh temperature controlled fluid, and temperature controlled fluid returns Transmit used temperature controlled fluid in flow tube road 144.
Interior panelling single pass reactors 120 have the internal flow baffle 146 along its working length.Each internal flow Baffle 146 can be the annular construction member for being fixed to inner wall 125 so that it is anti-that each internal flow baffle is fixed on interior panelling one way It answers irremovable in device 120.Baffle chamber 147 is set between continuous internal flow baffle 146.The outer diameter of baffle chamber 147 by Inner wall 125 limits and first end and second end is limited by internal flow baffle 146, wherein one in internal flow baffle 146 Person limits the first end of the second end and adjacent baffle chamber 147 of one of baffle chamber 147.It is reacted along interior panelling one way The working length of device 120 is continuously provided baffle chamber 147.
As process fluid flows through interior panelling single pass reactors 120, internal flow baffle 146 interferes fluid momentum, and Change the flow path of process fluid.The change of the interference and fluid flow path of flowing momentum makes the fourth in process fluid Mixing closely occurs in baffle chamber 147 together for alkene, water and catalyst.Not with the central shafts of interior panelling single pass reactors 120 Consistent fluid flowing is also beneficial to by the way that heat is transmitted to ontology work from the inner wall 125 of interior panelling single pass reactors 120 Skill fluid.Internal flow baffle 146 also adds process residence time, this improves conversion of the butylene to butanol.
Oscillator assembly 149 is connected to the proximal end 122 of interior panelling single pass reactors 120.Oscillator assembly 149 includes setting Set the process fluid oscillator component 148 near the proximal end of interior panelling single pass reactors 120 122.Oscillator assembly 149 is also It include the oscillator hermetic unit for sealingly engaging interior panelling single pass reactors 120 and process fluid oscillator component 148 150, which is mechanically connected to oscillator head 151 by external movement driver 152.Technique stream Oscillation body device component 148 is connected to interior panelling single pass reactors 120 by oscillator hermetic unit 150 so that process fluid Oscillator component 148 leads to inside from the outside of interior panelling single pass reactors 120, without making process fluid be externally exposed Pollutant, and will not be by fluid process leak to external environment.Process fluid oscillator component 148 is at oscillator head 151 It is connect with the inner wall 125 of interior panelling single pass reactors 120, therefore the outer diameter of oscillator head 151 is sliding engaged inner wall.Oscillation Device head 151 is reciprocal in the mode of front and back linear movement, and is connected to process fluid so that process fluid is along interior panelling list The length of journey reactor 120 carries out substantially sine curve and moves.Oscillator head 151 can be in direct contact process fluid, or can (example As) be indirectly connected to process fluid by diaphragm or other components, the diaphragm or other components can be by oscillator heads 151 Movement is transmitted to the substantially sine curve movement of process fluid.
Due to process fluid and the contact of oscillator head 151 and the Incoercibility of process fluid, process fluid oscillation The variation of the relative position of device component 148 is so that the position of process fluid generates variation.The change in location of process fluid makes edge The flowing momentum for the process fluid of the working length of interior panelling single pass reactors 120 generates unstable state.Process fluid flows Unstable state enhance mixing and heat absorption.The pulling and promotion of incompressible process fluid make the mobile phase pair of process fluid Fixed position inside interior panelling single pass reactors 120 springs up and retreats.By using oscillator assembly 149 along Interior panelling single pass reactors 120 cause substantially sine curve movement in process fluid so that interior panelling single pass reactors Process fluid in 120 is mixed to form crude product.
Oscillator assembly 149 further includes external movement driver 152.External movement driver 152 shakes via process fluid It swings device component 148 and is connected to oscillator head 151, and can be used for selectively driving process fluid oscillator component 148 and oscillation Device head 151.The construction of oscillator hermetic unit 150, with the connection of external movement driver 152 and oscillator head 151 with it is interior Process fluid oscillator component 148 is limited in limited motion range by the contact of the inner wall 125 of portion's baffle single pass reactors 120 It is interior.When operated, process fluid oscillator component 148 makes oscillator head 151 be moved with the reciprocating manner of linear direction.
Fig. 2
Fig. 2 is the process flow chart of another embodiment of production of butanol system.The production of butanol technique of Fig. 2 will be several Kind feed introduces production of butanol system 200, includes combination 201 and the hydration catalyst feed 106 of mixed butene and water feed. The combination 201 of mixed butene and water feed enters interior panelling single pass reactors 120 by butylene and water inlet 203.Butanol Several product, including refined exhaust 292 and butanol product 114 is made in production system 200.System circulation stream butylene cycle 182 The amount for water cycle 288 both contributing to that water is made to be fed the supplement mixed butene and water in 201 minimizes.
Piece-rate system 260 in Fig. 2 is different from the composition of piece-rate system 160 in Figure 1A -1B.High pressure (HP) separator 272 are connected to cooler 170, receive cooling crude product, and remove most water, to form the crude product of poor-water.It returns The water and hydration catalyst of receipts are through 288 transmission of water cycle for being again introduced into interior panelling single pass reactors 120.
Debutenizer 180 is connected to HP separators 272, receives the crude product of poor-water, and runs with from the poor-water Unreacted butylene is removed in crude product, and forms the crude product without butylene.The butylene of recycling is passed via butylene cycle 182 It is sent to the proximal end of interior panelling single pass reactors 120.
Pervaporation module 284 includes osmotic evaporation film 286.Pervaporation module 284 is connected to debutenizer 180, connects The crude product without butylene is received, and osmotic evaporation film 286 can be effectively utilized from the crude product without butylene by butanol It is detached as penetrant.Pervaporation module 284 forms butanol steam in penetrant side, and in osmotic evaporation film 286 Feed-side forms most of retentate being made of water.To be transmitted to interior panelling one way anti-by water cycle 288 for water retentate Answer device 120.
Butanol knockout tower 290 is connected to pervaporation module 284, receives butanol steam, and runs with by butanol steam It refines to refine mixed butyl alcohol.Refined mixed butyl alcohol is conveyed substantially free of water and butylene, and by butanol product 114.Fourth Lightweight and uncondensable gas is discharged in alcohol knockout tower 290.A part of uncondensable gas of lightweight is discharged by refined exhaust 292, Remaining is recycled to pervaporation module 284 by the distillation cycle 294 that butanol recycles.
Fig. 3
Fig. 3 is the process flow chart of another embodiment of production of butanol system.The production of butanol technique of Fig. 3 introduce with Similar feed shown in the technique of Fig. 2.Production of butanol system 300 generates several product, including dead catalyst 110 and butanol Product 114.300 recycle stream butylene of system cycle 182 and water cycle 288 both contribute to the mixed butene for making combination be fed in 201 It is minimized with the magnitude of recruitment of water.
Piece-rate system 360 in Fig. 3 is different from the composition of piece-rate system 160 and 260.Cyclone separator 172 is connected to cooling Device 170 receives cooling crude product, and removes any remaining heterogeneous hydration catalyst, polymer via dead catalyst 110 With other solids.Cyclone separator 172 is by the generation waste catalyst of dead catalyst 110 and without the crude product of catalyst. High pressure (HP) separator 272 is connected to cyclone separator 172, receives the crude product without catalyst, and under high pressure will packet Organic phase containing butanol and butylene is detached from water phase.Water phase still includes some butanol, but than much less in organic phase.It is de- Butylene tower 180 is connected to HP separators 272, receives organic butanol and butylene phase, and organic phase is separated into recyclable Butylene and refined mixed butyl alcohol.The butylene of recycling is transported to technique leading portion via butylene cycle 182, and refined mixed butyl alcohol by Butanol product 114 transmits.Azeotrope column 390 is connected to HP separators 272, receives water phase, and aqueous phase separation is become butanol/water Azeotropic mixture and recyclable water.Butanol/water azeotropic mixture is recycled to piece-rate system 360 via butanol/water cycle 392 Leading portion, and recyclable water is delivered to the leading portion of technique via water cycle 288.
Fig. 4
Fig. 4 is the embodiment along the internal flow baffle 146 of the working length of interior panelling single pass reactors 120 Detailed view.In the example embodiment of Fig. 4, each internal flow baffle 146 can be formed by dished plate, which has Extend through the aperture 394 of the plate.The outer diameter of dished plate is fixed to inner wall 125.When process fluid passes through baffle chamber 147 When, the interaction of process fluid and internal flow baffle 146 generates vortex in process fluid.The aperture 394 is set Size and position by each internal flow baffle 146, to be generated in the process fluid in the baffle chamber 147 Vortex, the vortex cause the optimization of process fluid to mix.For example, aperture 394 can be selected relative to internal flow baffle 146 The diameter of diameter and aperture 394 are by the position of internal flow baffle 146 with the mixing of optimize technique fluid.
When process fluid is flowed through interior panelling single pass reactors 120, some process fluids are kept off by internal flow The aperture 394 of plate 146.The solid loop section of other process fluid contact internal flow baffles 146, and in baffle chamber 147 It is redirected to, to form vortex in process fluid.The vortex formed in baffle chamber 147 improves the mixed of process fluid It closes.
Fig. 5
Fig. 5 shows the example embodiment of the external movement driver 152 according to the embodiment of the disclosure.In Fig. 5 Example in, external movement driver 152 include rotating disk 396.The first end of process fluid oscillator component 148 is connected to rotation Turntable 396.In the embodiment of Fig. 5, process fluid oscillator component 148 is engagement member.When external movement driver turns When dynamic, the second end of process fluid oscillator component 148 relative to the proximal end 122 of interior panelling single pass reactors 120 it is linear before It is mobile afterwards.The second end of process fluid oscillator component 148 is connected to oscillator head 151, and including causing oscillator head 151 It is moved back and forth in portion's baffle single pass reactors 120.
When oscillator head 151 moves further into interior panelling single pass reactors 120, oscillator head 151 is with from close End 122 pushes process fluid to the direction of distal end 124.As shown in the direction arrow of Fig. 5, when oscillator head 151 round about (when proximally facing 122) are mobile, oscillator head 151 with from distal end 124 proximally 122 direction push process fluid.Due to shaking It swings this of device head 151 to move forward and backward so that process fluid carries out substantially whole sinusoidal in interior panelling single pass reactors 120 Curve moves forward and backward.In this way, oscillation is moved superimposed on to all reactions in interior panelling single pass reactors 120 On object.This sinusoidal movement can realize unique radial mixing.
Process fluid and crude product
Process fluid does not mix when being inside interior panelling single pass reactors under the service condition of production of butanol technique The dual-phase process fluid of molten butylene and water.At any given point of the working length along reactor, process fluid includes Butylene, water, optional butylene hydration catalyst and butylene hydration product, especially butanol.
Butylene hydration reaction is happened in interior panelling single pass reactors.In butylene hydration in process fluid supporting reactions device Mixed butene is converted into the hydration reaction of mixed butyl alcohol in the presence of catalyst.As part production of butanol technique, process fluid The remote location of reactor is transmitted in the form of crude product by reactor proximal location.
Crude product is product butanol, water, butylene and optional butylene hydration catalyst (it still can be active) Combination.Crude product is the process fluid after being transmitted from the distal end of interior panelling single pass reactors.
Mixed butene
As a part for production of butanol technique, introduced using mixed butene as reactant.Mixed butene can be carried Pure, or petrochemical refinery factory house sources are may come from, include the product as FCC unit or thermal cracking unit, Come from the raffinate of MTBE or TBA techniques, the fraction of liquefied petroleum gas (LPG), or as several species like the group in source Interflow.Mixed butene includes one or more 1- butylene, one or two kinds of butylene (that is, cis or trans) and isobutene.Mixing Butylene can also include other alkane and alkene.
In the embodiment of production of butanol process, mixed butene includes 1- butylene.The embodiment of production of butanol technique The case where being substantially made of 1- butylene including wherein mixed butene.Fresh or " supplement " 1- butylene is preferably polymer grade 's.The 1- butylene that fresh 1- butylene is at least 99 volume % either the 1- butylene of 99.5 volume % or 99.9 volume % 1- butylene either the 1- butylene of 99.95 volume % or even higher purity.Impurity in fresh 1- butylene be equal to or Less than 5ppm (by volume).
Coming from the cycle butylene of the other parts of production of butanol system makes butenc efficiency maximize.Production of butanol system System include piece-rate system, by recyclable mixed butene from crude product Selective Separation.The embodiment party of production of butanol system Case, which includes wherein production of butanol system, effectively to introduce the reaction of interior panelling one way by the mixed butene of Selective Separation The case where device.The embodiment of production of butanol technique includes operation production of butanol system, to independently by Selective Separation Mixed butene is introduced into interior panelling single pass reactors.Compared with fresh butylene, the butylene of cycle can have lower composition Purity cannot introduce the substance of new inertia or pollution because recycled material is already present on the inside of production of butanol system.
The introducing of mixed butene is carried out in the form of compressed gas, liquid, supercritical fluid or combinations thereof.1- butylene faces Boundary's temperature is 146.4 DEG C, and critical pressure is 40.2 bars.The critical-temperature of isobutene is 144.7 DEG C, and critical pressure is 40.01 bars. Heat can be provided for the process fluid of promotion hydration by being preheated to the mixed butene of introducing.
Water
As a part for production of butanol technique, introduced using water as reactant.It is introduced in production of butanol system Fresh water or supplement water are at least water or 99.95 bodies of the water of the water of 99 volume % or 99.5 volume % or 99.9 volume % The water of product % or even higher purity.Water should be degassing, remove minerals and it is deionized, to not to butanol Pollutant is introduced in production system.Impurity is equal to or less than 5ppm (by volume).
Coming from the recirculated water of the other parts of production of butanol system makes the amount of the supplement water of introducing minimize.Water usually exists It is excessively used in production of butanol technique.Piece-rate system is by recyclable water from the crude product Jing Guo interior panelling single pass reactors Selective Separation.The embodiment of production of butanol system includes wherein production of butanol system can be effectively by Selective Separation Water is introduced into the case where interior panelling single pass reactors.The embodiment of production of butanol technique includes operation production of butanol system, To which the water of Selective Separation is independently introduced into interior panelling single pass reactors.When the unneutralized homogeneous catalyst of use When, the hydration catalyst of activation can be delivered to the leading portion of production of butanol system by recirculated water.The embodiment party of production of butanol technique Case includes the case where water of wherein being selected independently property separation also includes homogeneous butylene hydration catalyst.
The embodiment of production of butanol technique includes that water and mixed butene are introduced into interior panelling single pass reactors so that The molar ratio of water and 1- butylene is in the range of about 1 to about 21.
Hydration catalyst
It, will as a part for production of butanol technique when production of butanol system does not include fixed heterogeneous acid catalyst Butylene hydration catalyst is introduced as reactant.When production of butanol system does not include fixed heterogeneous acid catalyst, butylene The introducing of hydration catalyst is optional.The embodiment of production of butanol technique includes the interior panelling list to production of butanol system Journey reactor introduces butylene hydration catalyst so that proximally to distal end formation process fluid, wherein butylene hydration catalyst selects From in homogeneous acid, heterogeneous acid and combinations thereof.
Include (for example) sulfuric acid and phosphoric acid useful as the butylene hydration catalyst of homogeneous acid.The reality of production of butanol technique The scheme of applying includes that wherein introduced butylene hydration catalyst is homogeneous situation.The example of useful phosphoric acid include orthophosphoric acid, Polyphosphoric acids (PPA) and peroxophosphoric acid (SPA).Polyphosphoric acids is with chemical general formula H (PO3H)n(wherein n is integer to OH, indicates to divide The number of phosphorous unit in son) contain phosphorus oxyacid.Commercially available PPA mixtures have n- (n=1), burnt-(n=2), tripoly- (n=3), four poly- (n=4) and more advanced condensation chain type acid.PPA concentration is in about 95% to about 118% phosphoric acid (H3PO4) dense The equivalents of the phosphoric acid formed through the complete hydrolysis of polyphosphoric acids is indicated in degree equivalent weight range.One example is orthophosphoric acid (H3PO4) (St. Louis Sigma-Aldrich companies).
Useful butylene hydration catalyst further includes heterogeneous acid catalyst.The embodiment of production of butanol technique includes it In introduced butylene hydration catalyst be heterogeneous situation.It is this kind of acid have be introduced into they metal, ceramics, particle or Sour function in paradigmatic structure.Recovery process including evaporation, vaporization, distillation and centrifugation systems can be effectively by solid catalysis Agent is extracted from process fluid or crude product.The embodiment of production of butanol technique includes operation production of butanol system, is made Piece-rate system independently by butylene hydration catalyst from crude product Selective Separation, wherein butylene hydration catalyst be it is non- Phase catalyst.Example includes D008-1 and D008-2 (County, Hebei Province, China KaiRui Chemical Co., Ltd.s), for sulfonic acid (SO3H) the fluoropolymer resin of functional group.
The embodiment of the method includes from homogeneous butylene hydration catalyst, heterogeneous hydration catalyst and combinations thereof Select introduced butylene hydration catalyst.Some homogeneous/heterogeneous sour combined systems are imitated for generating the conversion of alcohol by alkene Rate or selectivity or both synergy generated are known.Include the butanol of heterogeneous hydration catalyst in baffle chamber In the embodiment of production system, the embodiment of production of butanol technique includes that homogeneous butylene hydration catalyst is introduced into inside Baffle single pass reactors.
Hydration catalyst can be introduced as pure substance or the form being diluted in conveying solution.Hydration catalyst can be dilute It releases in water or is introduced into mixed butene, to enhance the dispersibility in process fluid.
Production of butanol process products
Primary product is refined mixed butyl alcohol.The group of refined butanol product becomes at least mixed butyl alcohol of 99 volume %, or The mixed butyl alcohol or even higher of the mixed butyl alcohol or 99.9 volume % of the mixed butyl alcohol of 99.5 volume % or 99.7 volume % Purity.The embodiment of production of butanol system, which includes wherein piece-rate system, can effectively generate and have at least 99 volume % The case where refined mixed butyl alcohol of the purity of mixed butyl alcohol.Dissolved gas (including butylene, butane and inert gas) is can to deposit The a small amount of impurity being in refined mixed butyl alcohol product.
Production of butanol system can effectively recycle solid from crude product.This kind of solid may include the hydration of catalytic activity Catalyst.Production of butanol technique can effectively recycle hydration catalyst, be neutralized, and production of butanol technique is then emitted into It is external.External process can effectively handle the hydration catalyst of recycling or make its regeneration, and be recycled use to draw again Enter to interior panelling single pass reactors.
As a part for refinery practice, production of butanol technique Selective Separation from crude product by water.The water of recycling can To carry out organic matter, acid catalyst and the processing of solid, then discharged in the form of system purge object.
As a part for piece-rate system, production of butanol system being capable of effectively discharge gas.Discharge gas is used as system Purge gas.Discharge gas includes inert gas and lightweight organic gas, including least a portion of butylene.
Interior panelling single pass reactors
Interior panelling single pass reactors are the tube with the internal flow pipeline limited by inner wall, can be effectively The hydration of mixed butene is supported in the environment that pressurization, heating, fluid are filled.The tube has inner surface or inner wall, Fixed volume between part encapsulating first end (proximal end or upstream end) and second end (distal end or downstream).The operation of reactor Length be proximally and distally between tube fluid length.The length of tube is much larger than its diameter.The tube edge Its working length also has outer surface or outer wall, is conducted heat between inside and outside by outer surface or outer wall.
Run interior panelling single pass reactors so that reactant and optional hydration catalyst can be effectively conveyed into The near proximal ends of reactor mix simultaneously formation process fluid.Process fluid proximally nearby passes through along fluid flow path anti- It answers the working length of device and reaches distal end.Crude product is transmitted to distal end from reactor proximal end.
Fig. 1-3 shows snakelike interior panelling single pass reactors；However, the linear and nonlinear fluid hose based on connection Any number of physique can be presented in the purposes of road section (including standard pipe), reactor.Those of ordinary skill is based on behaviour Make parameter and performance (including temperature control, physical space, repair and investment cost), can effectively be contemplated to interior panelling list The overall shape of journey reactor.
For the process fluid by interior panelling single pass reactors, main mobilization dynamic is to coordinate to introduce near proximal ends Reactant and hydration catalyst and from proximate distal ends transmit crude product.Although not requiring, auxiliary flow driver (packet Include pump and rotation blade) can effectively supplement momentum be provided for process fluid.
Interior panelling single pass reactors have at least one reactant for discharge position in the near proximal ends of reactor.Mix fourth Alkene and water can be used as group interflow or be introduced as independent stream.Fresh or cycle mixed butene and flow can be combined Or reactor is individually supplied.
Interior panelling single pass reactors have at least one hydration catalyst for discharge position.Hydration catalyst for discharge position at In interior panelling single pass reactors near proximal ends at least one reactant for discharge position downstream.It is this relative to reactant It is arranged such that reactant can be mixed with another reactant before introducing hydration catalyst for discharge position, this is conducive to Improve selectivity and conversion.
The embodiment of production of butanol system includes multiple reactions along the working length of interior panelling single pass reactors Area.In one embodiment, the reaction zone is to introduce position and the second mixed butene introducing position between the first mixed butene Working length between setting.In another embodiment, reaction zone is to introduce the remote of position and reactor between mixed butene Between end.In another embodiment again, reaction zone is to introduce position and the second butylene between the first butylene hydration catalyst Hydration catalyst introduces the working length between position.Also in another embodiment again, reaction zone is between butylene hydration Catalyst introduces between position and the distal end of interior panelling single pass reactors.Pass through multiple positions along the working length of reactor It introduces mixed butene or butylene hydration catalyst makes the level that technology controlling and process and butenc efficiency can be improved.Each reaction zone can With different inside and outside process support equipments to be conducive to produce, including the structure of interior panelling, flow of process fluid Manipulation, computer control system and the reaction zone temperature and pressure management of speed.
At any given point of the working length along interior panelling single pass reactors, internal flow pipeline axis is in the point Transverse cross-sectional area relative to internal flow pipeline is vertical.In no internal additive (for example, internal flow baffle), Fluid will pass through the working length of interior panelling single pass reactors, and can generally be protected with internal flow pipeline axis in flowing It holds consistent.
Internal flow baffle and baffle chamber
Interior panelling single pass reactors have a series of internal flow baffle along at least part of its working length. The embodiment of production of butanol system includes one of which internal flow baffle positioned at the whole operation along internal flow pipeline The case where position of length.
For each internal flow baffle in interior panelling single pass reactors, baffle has the one of the proximal end of orientating reaction device The opposite side (side for facing downstream) of side (side for facing upstream) and the distal end of orientating reaction device.Baffle is routinely fixed To so that they are extended vertically from along the position of reactor wall, and are inwardly projected in internal fluid pipe road.It usually will gear Plate orients so that they are perpendicular to internal flow pipeline axis, but other constructions be also for those of ordinary skill in the art can Capable.For most of process fluid flow path length for, baffle prevent process fluid along with internal fluid pipe The consistent direction flowing of road axis, to promote to conduct heat and mix.
Internal flow baffle can have a variety of physiques, including stick, porous plate, mesh screen, orifice plate (placed in the middle and biasing stream Dynamic window) and section plate.Each baffle has the window edge for the mobile window at least partly limiting each baffle.In some baffles In (such as orifice plate), window edge completely defines the annular space that process fluid flows through baffle.In other baffles, window edge Part defines the gap that process fluid flows through.When such baffle is installed in reactor, the inner wall of reactor defines The rest part of mobile window.Mobile window is relative to the sizes of baffle dimensions, mobile window relative in internal flow pipeline The construction (parallel, crooked, vertical) of the position of the heart and the mobile window interior panelling adjacent relative to other is to correct technique An important factor for direction of travel of fluid.
By the fluid flow path inside interior panelling single pass reactors by the inner wall and internal flow baffle of reactor Arrangement (including the orientation of shape, mobile window, interval and adjacent screen relative to internal flow pipeline axis) limit.Technique stream The length of body flow path is longer than the working length of reactor.Baffle increases the distance that process fluid passes through reactor, because Process fluid not only has to proximally flow to distal end, it is necessary to advance around interior panelling.
In the reactor with multiple reaction zones, may exist different baffle groups in each reaction zone.Internal flow The arrangement of baffle so that the baffle is along part operation length arranged in series in each group, wherein being arranged in described group each adjacent Baffle and spaced at equal intervals.The embodiment of production of butanol system includes interior panelling single pass reactors, is had along its working length There is the internal flow baffle more than one group.
Internal flow baffle along inner wall defines one group of gear in the internal flow pipeline of interior panelling single pass reactors Plate room.Each baffle chamber is by the downstream in face of upstream baffle side in baffle group and the upstream in face of downstream damper side and instead The inner wall of device is answered to define.With the number of the relevant baffle chamber of internal flow baffle group always than described group in baffle number it is few One.
When process fluid passes through interior panelling single pass reactors, which limits via at least part upstream baffle Fixed mobile window enters baffle chamber.Once into baffle chamber, process fluid is passed through by the formation and promotion process fluid of vortex Internal flow baffle is crossed to which substantially sine curve caused by process fluid is mobile and recycle indoors, with reactant, urge Agent and product mix, and not only in the different piece of process fluid internal heat transfer and also in process fluid and It mutually conducts heat between reactor wall.Then process fluid passes through the flowing that is limited by least part downstream damper from baffle chamber Window transmits.Transmission with process fluid along the working length of reactor from baffle chamber to baffle chamber, passes through baffle The process of room.
In the embodiment of production of butanol technique, the introducing of butylene hydration catalyst is optional.In this kind of technique, Interior panelling single pass reactors include solid heterogeneous butylene hydration catalyst, and the mixed butene in process fluid is selected It is converted into mixed butyl alcohol to property.Although from anywhere in the catalyst can be contained in the internal flow pipeline of reactor, It is for utmostly mixed reactant and conversion, the most effective position location of catalyst is in each baffle chamber.
Depending on the material of catalyst, structure and the application in baffle chamber's component, solid heterogeneous in each baffle chamber It the position of butylene hydration catalyst can be different.When forming granular, spherical or other loose and usually amorphous shapes, urge Agent can be encapsulated in container or other physical restraints, include structural framing and metal with flow orifice or slit Silk screen packet allows process fluid to flow freely into at outflow catalyst accumulation, while not allowing catalyst carrying out container. This prevent catalyst as the distal end of downstream process fluid stream internally baffle single pass reactors is mobile and prevents piece-rate system Fouling.The inorganization catalyst of free form structure makes it possible to that they are effectively placed directly within process fluid flowing path In, include the mobile window of internal flow baffle.The embodiment of production of butanol system is urged including wherein heterogeneous butylene hydration Agent is in the case where such position, i.e., the described position makes the process fluid for the mobile window for flowing through downstream damper non-with this Homogeneous butylene hydration catalyst contact, and the embodiment of production of butanol system includes wherein close to downstream flow window The case where reaction of butylene and water is mixed in each baffle chamber.The position of catalyst can be such so that flow through upstream The process fluid of the mobile window of baffle is contacted with heterogeneous butylene hydration catalyst.Other catalyst modes, including such as grid, The structured form of matrix and sheet and " amorphous " form make (such as shape can be cured, thermoplastic and other ductility) Inside the direction for obtaining the internal flow baffle that can catalyst be installed, adheres to, is coated with or is sprayed on inner wall and restriction baffle chamber On surface.The embodiment of production of butanol system includes that wherein catalyst is placed on the inner wall for limiting baffle chamber, and butanol The embodiment of production technology includes the feelings for the reaction for being wherein mixed butylene and water along the position of inner wall in each baffle chamber Condition.For each baffle chamber, upstream baffle in face of downstream side and downstream damper in face of upstream side inwardly baffle chamber. The embodiment of production of butanol system includes the side for the inwardly baffle chamber that catalyst is wherein placed in internal flow baffle On.
External movement driver
Production of butanol system is included in the device outside interior panelling single pass reactors, is not changing production of butanol technique Other operating parameters (including temperature, mass flowrate and pressure) in the case of cause process fluid unstable state flowing.Pass through The unstable state flowing for causing process fluid in process fluid is directly transferred the motion to using external movement driver.It can be with 2 hertz to 5 hertz of reciprocating frequence and 20 millimeters to 40 millimeters of past complex amplitude operate external movement driver.
External movement driver include electricity, motor machine, waterpower, pneumatic, gas injection, compressed gas, chemistry it is anti- It answers and any other system or device, assigns or be transferred in process fluid for that will move.
In production of butanol technique, by interfering its momentum, outside fortune in fluid flow through internal baffle single pass reactors Dynamic driver causes the unstable state of process fluid to be flowed.It wears and send to distal end, outside fortune from the proximal end of reactor with process fluid Dynamic driver physically acts on the process fluid.The part contacted using device and process fluid, external movement driving Device will move (including vibrate, is reciprocal, variation and asynchronous fluid motion) and be conveyed to process fluid.Connected devices are in inside Movement in fluid line generates the unstable state flowing of process fluid.
In the case where not causing unstable state, production of butanol technique can be protected effectively in interior panelling single pass reactors Hold " stable state " state.Lower state is a kind of such state, wherein the fluid properties in system at arbitrary point not with when Between and change.Oil, petrochemical industry and chemical industry operation field it is to be appreciated by one skilled in the art that " steady-state operation " includes from time to time Some smaller technique changes, but usually service condition, feed and productivity all will not significant changes.
By interfering the fluid momentum of process fluid flowing, the movement that is applied by external movement driver is by steady-flow shape State becomes unstable state state.Unstable due to fluid momentum, unstable state state generates cascading, influence other techniques and Working condition includes the total output of heat transfer, reaction efficiency and system.At the time of unstable state is happened at introducing astable operation, And later as effect (for the function of time) decrease continues for some time.It interacts in not other unstable state In the case of, by addition maintaining stable service condition, the new steady s tate condition similar with initial stable state can be obtained.To Process fluid apply repeatedly, periodic or continuous astable operation lead to that there are continuous unstable state states.
Compared with the fixed position in interior panelling single pass reactors, the unstable state flow regime of caused process fluid Change the relative motion (for example, accelerate, slow down) of process fluid.The initiation of unstable state state is not interfered with through reactor Overall volume flow in unit interval or mass flow, because the introducing of feed and the transmission of crude product can influence the total of technique Body volume flow rate or mass flowrate.
During unstable state is flowed, the instantaneous generation and disappearance of fluid vortex and adverse current can occur in process fluid.Class Be similar to flow with the relevant random direction of turbulent flow, in the flowing of typical laminar-type, under the fluidised form of low reynolds number it can also happen that Unstable state is flowed.Only within transient period, by making mobile a part of process fluid by interior panelling single pass reactors It is flowed in a manner of unpredictable and unstable state, the unstable state flowing of process fluid promotes mixing, reaction and heat in baffle chamber It transmits.
External movement driver is connected to the device that effectively can directly assign movement inside process fluid.Work as technique When fluid still usually proximally flow to distal end by internal flow pipeline, the operation of piston-like operator causes flow of process fluid Dynamic springing up and retreating.The device of the septiform contacted with process fluid fluid is expanded relative to incompressible process fluid It opens and shrinks, and the similar volume in direct replacement internal flow pipeline, this generates the shakinesses of required process fluid flowing It is fixed.
The embodiment of production of butanol system includes with the oscillator head that reciprocating frequence is 2 hertz (Hertz) to 5 hertz Oscillator assembly.In such an implementation, external movement driver can be by under 2 hertz to 5 hertz of frequency Oscillation effectively causes the unstable state in process fluid flowing, and in an alternate embodiment, external movement driver is at about 3 hertz Hereby lower oscillation.The embodiment of production of butanol system includes shaking with the oscillator head for being 20 millimeters to 40 millimeters toward complex amplitude Swing device assembly.In such an implementation, external movement driver can pass through shaking under 20 millimeters to 40 millimeters of amplitude The unstable state in effectively causing process fluid to flow is swung, in an alternate embodiment, external movement driver is with about 30 millis The amplitude oscillatory of rice.
The embodiment of production of butanol system includes more than one external movement driver, wherein each external movement drives Device is all connected to the device that effectively can directly assign momentum in process fluid.The embodiment of production of butanol technique includes Run simultaneously the first and second external movement drivers.Another embodiment of production of butanol technique includes unsynchronized revolution One and the second external movement driver.
Temperature control system
Temperature adjusting fluid is transported to the outside of interior panelling single pass reactors by temperature control system, to keep butylene water Close the suitable temperature of reaction.Include heat exchange for keeping the example of the temperature control system of temperature in interior panelling single pass reactors Device, cooling jacket and air blower.The example of useful temperature adjusting fluid includes water, ethylene glycol and air.Commonly temperature Adjust the forced convertion of fluid.
Piece-rate system
Production of butanol system includes the separation that can effectively detach mixed butyl alcohol, mixed butene and water from crude product System.
Production of butanol system can effectively by mixed butene from crude product Selective Separation, to generate without butylene The mixed butene of crude product and recycling.The mixed butene of recycling can be used for the recycling of production of butanol system, and as reaction Object feed is introduced into interior panelling single pass reactors.The recycling of unreacted mixed butene improves the process efficiency of butylene.
Production of butanol system can also effectively by water from crude product Selective Separation, to generate water-free thick production Object.The water of recycling can be used for the recycling by production of butanol system, and introduce interior panelling list as reactant feed Journey reactor.Water can also be used as system and remove a part for object to handle.
The embodiment of production of butanol system can effectively independently select butylene hydration catalyst from crude product Property separation.Centrifugal force is introduced into crude product by cyclone separation system so that heavier liquid and solid is detached with lighter product. Cyclone separation system can be used in particular for solid heterogeneous catalyst, because when applying angular momentum, solid can be effectively easy Ground is detached with remaining liquid.Cascade filtration can also effectively complete similar task, and solid is removed from crude product, is made It obtains buildup of solids and is detached from from filter surfaces under its own gravity.Heat effectively can be introduced into thick production by vaporizer Object so that crude product part forms steam.Evaporator (including thin film evaporator) can effectively by the product of high-boiling and Solid is detached with the part that can effectively reach steam-like in crude product under lower operating pressure.The hydration of recycling is urged Agent and any other solid or very heavy liquid can effectively send out production of butanol system for recycling or handling.
Entrained fluids from crude product for selectively extracting butanol.Crude product includes a certain amount of water, therefore and water Unmixing organic compound can be used for extracting, which is easily separated from water and compared with water, mixes fourth Alcohol has better compatibility to the organic compound.Compared with mixed butyl alcohol, under normal pressure with lower distillation boiling point Entrained fluids are also useful, because it can effectively relatively scientifically detach entrainer from mixed butyl alcohol.Useful The example of entrainer fluid includes pentane, hexane, hexene, hexamethylene, benzene,toluene,xylene and its mixture.
The introducing of poor entrainer fluid (it is unmixing with the water in crude product) causes crude product to be divided into two-phase：Including entrainment The water phase of the organic phase and poor butanol rich in butanol of agent.Butanol extraction column can be effectively by water phase and entrainer phase point From.Figure 1A -1B show butanol extraction column 184, produce the water phase (being transmitted as output water 112) of poor butanol；And it is rich in The entrainer and butanol mixture of butanol, are transmitted to butanol knockout tower 186.Other refining system techniques will be enriched in the folder of butanol Band agent liquid turns are at refined mixed butyl alcohol and poor entrainer fluid.
Mixed butyl alcohol can be effectively directly separated by osmotic evaporation film from crude product.Butanol including osmotic evaporation film Production technology selectively pervaporation mixed butyl alcohol, without selectively pervaporation water.Pervaporation object is gaseous Mixed butyl alcohol can effectively be condensed and distill and form refined mixed butyl alcohol.Retentate is the liquid for including most of water Body, it includes a part of mixed butyl alcohols.The retentate of this refining system cannot be only used for recycling to withdraw required butanol, It may further be used to retain water to reuse.
Support device
Embodiment includes many other standard components or equipment make it possible to effectively to run described device, technique, Method and system.The example of this standard device known to persons of ordinary skill in the art includes：Heat exchanger, pump, air blower, again Boil device, steam generator, condensation process device, film, single-stage and compound compressor, separation and fractionation apparatus, valve, switch, control Device and pressure, temperature, level and flow sensor.
Can be controlled by the computer of human intervention, pre-programmed and response system or combination thereof come carry out technique or Operation, control and the implementation of some or all of method step.
Run production of butanol system
Under the service condition of interior panelling single pass reactors, butylene hydration catalyst can be effectively in process fluid Mixed butene is selectively converted to mixed butyl alcohol.The embodiment of production of butanol technique includes operation production of butanol system, So that the temperature of process fluid maintains in the range of about 80 DEG C to about 150 DEG C in interior panelling single pass reactors.Production of butanol The embodiment of technique includes operation production of butanol system so that the temperature of process fluid maintains in interior panelling single pass reactors In the range of about 100 DEG C to about 120 DEG C.The embodiment of production of butanol technique includes operation production of butanol system so that interior The pressure of process fluid maintains in the range of about 5 bars to about 70 bars in portion's baffle single pass reactors.
By a part of component of mixed butyl alcohol or mixed butyl alcohol maintain liquid or Supercritical Conditions or both Under combined situation, the mixing in interior panelling single pass reactors can be enhanced.The embodiment of production of butanol technique includes operation Production of butanol system so that maintaining the temperature and pressure of process fluid in interior panelling single pass reactors makes at mixed butene In the range of liquid.The embodiment of production of butanol technique includes operation production of butanol system so that by interior panelling one way The temperature and pressure of process fluid maintains in the range for keeping mixed butene in a supercritical state in reactor.
Compared with the fixed volume reactor assembly of standard, the improvement mixing being happened in interior panelling single pass reactors is permitted Perhaps higher material production capacity.The embodiment of production of butanol technique includes operation production of butanol system so that keeps off inside In the range of the residence time of process fluid maintains about 0.1 hour to about 0.2 hour in plate single pass reactors.Less stop Time ensures higher air speed, 1- butylene is exposed at a temperature of isomerization may be caused to generate more useless 2- butylene Possibility minimize.
Example
The example of specific embodiment is conducive to more fully understand production of butanol system and technique.These examples not Ying Yiren Where formula limits or limits the scope of the present invention.
Embodiment 1-4 and comparative example 1-4
It vibrates baffle reactor (OBR) and handles five kinds of embodiment mixtures (1-4).Autoclave reactor handles five kinds and compares Example mixture (1-4).Each embodiment has similar water：1- butene molar ratios value and similar catalyst：1- fourths The comparative example of alkene relativeness.For example, embodiment 1 is compareed with comparative example 1, and embodiment 2 is compareed with comparative example 2, etc..Table 1 shows The composition of embodiment 1-4 and comparative example 1-4 are gone out.1- butylene, water and the total volume of introducing are all in terms of milliliter (mL).Molar ratio is Numerical value without unit.
For the technique of each embodiment and comparative example, by the butylene hydration catalyst for each embodiment or the amount of comparative example (D008；County, Hebei Province, China KaiRui Chemical Co., Ltd.s) and water be introduced into specified type of reactor (OBR；Autoclave) in. A certain amount of 1- butylene is introduced specified type of reactor for respective experiment under nitrogen pressure.It is sealed in reactor Afterwards, reactor is heated to operating temperature (100-110 DEG C).For the experiment in autoclave reactor, heating mantle remains entire Operating temperature in experiment.For the experiment in OBR, hot silicone oil bath maintains operating temperature.Reaction time in autoclave and OBR It is 1 hour.In the technique of embodiment, OBR reactors are under 3 hertz of (Hz) frequencies and 30 millimeters of amplitude by embodiment group Object mixing is closed, while autoclave stirs each comparative example composition under the speed of 200 revs/min (RPM).Two kinds of reactors are all Composition is mixed to form the homogeneous mixture of unmixing reactant.After 1 hour, all types of reactors stops altogether It is mixed, it is cooled to room temperature and gives off unreacted 1- butylene.Analysis is carried out to the product liquid of each embodiment and comparative example to help In the transformation efficiency of the amount and 1- butylene that determine 2- butanol.
Table 1 shows that under similar process conditions (that is, temperature, time, feed composition), the embodiment in OBR is fed The handling result of comparative example feed composition in composition and autoclave reactor.For all four operations, with autoclave The material of processing is compared, the amount (weight %) of the material of OBR processing and conversion mole % all highers of 1- butylene.
From table 1 it follows that the operation result relative to comparative example autoclave, whole OBR test runs results all have There are higher 1- butene conversions.
Fig. 6 shows in graphical form for oscillation baffle reactor (embodiment) and autoclave reactor (comparative example), The water of introducing：1- butene molar ratios are relative to butylene to the relationship of mole % conversion ratios of butanol.Fig. 6 reacts the introducing of table 3 The molar ratio data of device are drawn relative to the relationship of identified 1- butene conversions data.For every group information (embodiment and Comparative example) data, be quasi- using second order polynomial using Microsoft Excel 2010 (State of Washington, Redmond) The curve of conjunction.
Fig. 6 also shows the water of mole the % conversion ratios and introducing of 1- butylene：Second order between 1- butene molar ratios is multinomial Formula relationship.For OBR, identified second order relationship fitting is good, and with the R for being more than 0.992Value.OBR is tested and is transported The second order polynomial of row result provides in equation 1：
MCRC4=/BtOH=-0.002173* (MRH2O:C4=)2+0.061323*MRH2O:C4=+ 0.14264 (equation 1),
Wherein MCRC4=/BtOHIt is molar yield (by mole % in terms of) of the 1- butylene to butanol, MRH2O:C4=It is the mixed of introducing Close the molar ratio of water and 1- butylene in object.Equation 1 is determined by the molar ratio range from about 1 to about 21.
In addition, the value of whole molar yields of OBR test run results (embodiment 1-4) utilize between two second orders it is more Relationship between formula is fitted, and is used to evaluate molar yield of the 1- butylene to butanol.Similar to equation 1, the two Equation is shown with graph mode with dotted line " multinomial (low) " and " multinomial (height) " in figure 6.For rubbing for embodiment , than range, equation 2 and 3 contains the value of the molar yield of embodiment 1-4 for you：
EMCRC4=/BtOH≥-0.002173*(MRH2O:C4=)2+0.061323*MRH2O:C4=+ 0.045 (equation 2) and
EMCRC4=/BtOH≤-0.002173*(MRH2O:C4=)2+0.061323*MRH2O:C4=+ 0.24028 (equation 3),
Wherein EMCRC4=/BtOHIt is estimation molar yield (by mole % in terms of) of the 1- butylene to butanol, MRH2O:C4=It is to draw The molar ratio of water and 1- butylene in the mixture entered, in the range of about 1 to about 21.The embodiment packet of butanol production method Include operation production of butanol system so that molar yield (in terms of mole %) from 1- butylene to butanol by equation 2 and 3 institute really In the range of fixed estimation molar yield.The embodiment of butanol production method includes operation production of butanol system so that 1- Butylene is approximately more than the value of the estimation molar yield determined by equation 2 to the molar yield (in terms of mole %) of butanol. In addition, be similar to equation 1-3, there are two equation use in figure 6 dotted line " multinomial (in low) " and " multinomial (in It is high) " it is shown with graph mode.For the molar ratio range close to equation 1 and the embodiment between equation 2 and 3, Equation 4 and 5 contains the value of the molar yield of embodiment 1-4：
EMCRC4=/BtOH≥-0.002173*(MRH2O:C4=)2+0.061323*MRH2O:C4=+ 0.09382 (equation 4) and
EMCRC4=/BtOH≤-0.002173*(MRH2O:C4=)2+0.061323*MRH2O:C4=+ 0.19146 (equation 5),
Wherein EMCRC4=/BtOHIt is estimation molar yield (by mole % in terms of) of the 1- butylene to butanol, MRH2O:C4=It is to draw The molar ratio of water and 1- butylene in the mixture entered, in the range of about 1 to about 21.The embodiment packet of butanol production method Include operation production of butanol system so that molar yield (in terms of mole %) from 1- butylene to butanol by equation 4 and 5 institute really In the range of fixed estimation molar yield.The embodiment of butanol production method includes operation production of butanol system so that 1- Butylene is approximately more than the value of the estimation molar yield determined by equation 4 to the molar yield (in terms of mole %) of butanol.
Embodiment 5 and comparative example 5
It will carry out Processing Example mixture 5 for the OBR of embodiment 1-4.By the autoclave reactor for comparative example 1-4 To handle comparative example mixture 5.Embodiment and comparative example have similar water：1- butene molar ratios value and similar catalyst： 1- butylene volume relationships.Table 2 shows the composition of embodiment 5 and comparative example 5.1- butylene, water and the total volume of introducing are all with milli Rise (mL) meter.Molar ratio is the numerical value of no unit.
Embodiment 5 and the technique of comparative example 5 are analogous respectively to the technique of embodiment 1-4 and comparative example 1-4, and difference exists In butylene hydration catalyst be orthophosphoric acid (H3PO4) (St. Louis Sigma-Aldrich companies).
Table 2：The operation result of embodiment 5 and comparative example 5.
Table 2 shows under similar process conditions (that is, temperature, time, composition), the example composition phase in OBR For the handling result of the comparative example composition in autoclave reactor.For operation result, with autoclave treated material phase Than the amount (weight %) and 1- butencs mole % all highers of the material of OBR processing.Reforming catalyst is closed using sour water to demonstrate,prove It is real, for similar process conditions, using OBR for being hydrated 1- butylene relative to the superiority for using autoclave reactor.

Claims (20)

1. a kind of production of butanol system for refining mixed butyl alcohol by water and mixed butene production, the production of butanol system packet It includes：
Interior panelling single pass reactors, the interior panelling single pass reactors have：
Internal flow pipeline, the internal flow pipeline by inner wall and proximally and distally between working length limit, it is described Internal flow pipeline selectively accommodates and mixes the process fluid for including water, mixed butene and mixed butyl alcohol, to be formed Crude product,
Internal flow baffle is arranged along at least part of the working length of the internal flow pipeline, described Internal flow baffle is the annular and fixed inner wall, and
Baffle chamber is continuously arranged along the working length and outer diameter is limited by the inner wall and first end and second end It is limited by the internal flow baffle, wherein one of described internal flow baffle limits the of one of described baffle chamber The first end at two ends and adjacent baffle chamber；
Piece-rate system, the piece-rate system are in fluid communication with the interior panelling single pass reactors, and orient for selectively The crude product is received, and detaches the water and the mixed butene from the crude product, it is described refined mixed to produce Close butanol；With
Oscillator assembly, the oscillator assembly are connected to the proximal end of the interior panelling single pass reactors, the oscillator Component has the reciprocating oscillator head that can selectively be moved in a manner of front and back linear movement, and with the technique stream Body is connected to so that the process fluid carries out substantially sine curve along the interior panelling single pass reactors and moves.
2. production of butanol system according to claim 1, wherein each internal flow baffle is formed by dished plate, it should Dished plate has the aperture for extending through the plate.
3. production of butanol system according to claim 2, wherein the outer diameter of the dished plate is fixed to the inner wall.
4. production of butanol system according to claim 2 is provided with the size in the aperture and the position by the plate It sets, to generate vortex in the process fluid in the baffle chamber.
5. production of butanol system according to any one of claim 1 to 4, wherein the outer diameter of the oscillator head is slidably Engage the inner wall.
6. production of butanol system according to any one of claim 1 to 5, wherein the piece-rate system and the inside stream The distal fluid of body pipeline is connected to.
7. production of butanol system according to any one of claim 1 to 6, wherein the piece-rate system fluid and the gear At least one connection of plate room.
8. production of butanol system according to any one of claim 1 to 7, wherein the baffle chamber is along the inside stream The whole operation length of body pipeline and be arranged.
9. production of butanol system according to any one of claim 1 to 8, wherein the reciprocating frequence of the oscillator head is 2 hertz to 5 hertz.
10. production of butanol system according to any one of claim 1 to 9, wherein the past complex amplitude of the oscillator head It is 20 millimeters to 40 millimeters.
11. production of butanol system according to any one of claim 1 to 10, wherein the oscillator assembly includes machinery On be connected to and selectively drive the external movement driver of the oscillator head.
12. production of butanol system according to claim 11, wherein the oscillator assembly is described including sealingly engaging The oscillator hermetic unit of interior panelling single pass reactors and process fluid oscillator component, the process fluid oscillator component The external movement driver is mechanically connected to the oscillator head.
13. a kind of method for refining mixed butyl alcohol by the combination production of water and mixed butene, the method includes：
Interior panelling single pass reactors are provided, which has：
Internal flow pipeline, the internal flow pipeline by inner wall and proximally and distally between working length limit,
Internal flow baffle is arranged along at least part of the working length of the internal flow pipeline, described Internal flow baffle is the annular and fixed inner wall, and
Baffle chamber is continuously arranged along the working length and outer diameter is limited by the inner wall and first end and second end It is limited by the internal flow baffle, wherein one of described internal flow baffle limits the of one of described baffle chamber The first end at two ends and adjacent baffle chamber；
The process fluid comprising mixed butene, water and mixed butyl alcohol is set to pass through the interior panelling single pass reactors；
By using the oscillator assembly being connect with the proximal end of the interior panelling single pass reactors, along described interior Portion's baffle single pass reactors cause substantially sine curve movement in the process fluid, in the interior panelling single pass reactors The interior mixing process fluid, to form crude product, the oscillator assembly has can be selectively with front and back linear fortune The reciprocating oscillator head that dynamic mode moves；And
Detached from the crude product in the piece-rate system being in fluid communication with the interior panelling single pass reactors water and The mixed butene, to which production refines mixed butyl alcohol.
14. according to the method for claim 13, wherein mixing the process fluid in the interior panelling reactor Step includes by pushing the process fluid by the internal flow baffle, to the technique in the baffle chamber Cause to be vortexed in fluid.
Further include that the process fluid is transferred in described 15. according to claim 13 or method of claim 14 The piece-rate system of the far-end of portion's fluid line.
16. the method according to any one of claim 13 to 15 further includes will be in the baffle chamber at least one The process fluid in person is transferred to the piece-rate system.
17. the method according to any one of claim 13 to 16 further includes being grasped with 2 hertz to 5 hertz of reciprocating frequence Make the oscillator assembly.
18. the method according to any one of claim 13 to 17 further includes the past complex amplitude with 20 millimeters to 40 millimeters Operate the oscillator assembly.
19. the method according to any one of claim 13 to 18 further includes utilizing mechanically to be connected to the oscillator The external movement driver of head drives the oscillator head.
20. further including according to the method for claim 19, using oscillator hermetic unit that the interior panelling one way is anti- Device and process fluid oscillator component is answered to sealingly engage, the process fluid oscillator component is by the external movement driver Mechanically it is connected to the oscillator head.
CN201680058988.4A 2015-10-09 2016-10-07 Utilize the alkene hydrating process of oscillation baffle reactor Pending CN108349856A (en)

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