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WO2022198873A1 - 一种辛醇的产生系统及方法 - Google Patents

一种辛醇的产生系统及方法 Download PDF

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Publication number
WO2022198873A1
WO2022198873A1 PCT/CN2021/109750 CN2021109750W WO2022198873A1 WO 2022198873 A1 WO2022198873 A1 WO 2022198873A1 CN 2021109750 W CN2021109750 W CN 2021109750W WO 2022198873 A1 WO2022198873 A1 WO 2022198873A1
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WO
WIPO (PCT)
Prior art keywords
micro
butyraldehyde
reactor
octanol
bubbles
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PCT/CN2021/109750
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English (en)
French (fr)
Inventor
张志炳
周政
李磊
张锋
孟为民
王宝荣
杨高东
罗华勋
杨国强
田洪舟
曹宇
Original Assignee
南京延长反应技术研究院有限公司
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Publication of WO2022198873A1 publication Critical patent/WO2022198873A1/zh

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/20—Mixing gases with liquids
    • 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
    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • 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
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration

Definitions

  • the invention relates to the field of propylene hydroxylation reaction preparation, in particular to a system and method for producing octanol.
  • Octanol is an important raw material for the synthesis of fine chemical products. At present, the output of octanol in my country is huge, accounting for about 21% of the world's total.
  • Octanol uses synthesis gas and propylene as raw materials, and generates n-isobutyraldehyde through formylation reaction, and then obtains n-isobutanol can also be condensed with two molecules of n-butyraldehyde to form unsaturated bonds to obtain octanol.
  • Octanol has the typical characteristics of alcoholic organics, and all have special odor. It is a colorless, transparent, flammable liquid with moderate toxicity and can form an azeotrope with water.
  • the main production methods of octanol include fermentation method, acetaldehyde condensation method and propylene oxo method.
  • propylene oxo method has developed rapidly with remarkable advantages in the world and is the main method for producing butanol and octanol.
  • butyraldehyde take synthesis gas and propylene as raw materials, take carbonyl rhodium, triphenylphosphine complex or other industrially used similar substances as catalysts, react to produce mixed butyraldehyde, separate the catalyst and further Rectifying and separating to obtain butyraldehyde mixture;
  • the butyraldehyde mixture enters the butyraldehyde hydrogenation system to generate butanol, and then removes light heavy components through rectification, and separates isomers to obtain n-butanol and isobutanol;
  • n-butyraldehyde enters the condensation system for carbonyl condensation to produce octenal, and then hydrogenation and rectification are added to remove light and heavy components to finally produce octanol.
  • CH3CH2CH2CH C( C2H5 ) CHO + 2H2 ⁇ CH3CH2CH2CH ( CH2CH3 ) CH2OH
  • Chinese Patent Publication No.: CN103012089A discloses a method for oxo synthesis of propylene, comprising sending propylene, stripped synthesis gas and hydroformylation catalyst solution into a first oxo butyraldehyde condensation unit for contact reaction, and the butyraldehyde condensation unit
  • the foam component containing the hydroformylation catalyst is sent to the first separator for separation, a part of the obtained gas phase component is returned, and the other part is sent to the second oxo butyraldehyde for condensation with the synthesis gas and the hydroformylation catalyst solution.
  • propylene, synthesis gas and the catalyst are only contacted by the first oxo butyraldehyde condensation unit, and the gas phase components enter the first oxo to form large bubbles.
  • the bubble volume is too large, it cannot be combined with the liquid phase.
  • the sub-catalysts are fully contacted, which reduces the reaction efficiency of the system.
  • the reaction rate of the synthesis gas, propylene and the catalyst is reduced, resulting in a reduction in the utilization rate of propylene and synthesis gas, causing waste of raw materials to a large extent, and increasing the production cost of octanol, which is not in line with the existing circular economy. requirements.
  • the method does not take into account the problems of small phase boundary area, serious droplet condensation and low reaction efficiency in the direct reaction between lye and n-butyraldehyde solution.
  • the hydrogenation reaction in the method utilizes a fixed-bed reactor. Since it is a strong exothermic reaction, a large amount of heat needs to be removed in the process, and the reaction energy consumption is large and the efficiency is low.
  • the first object of the present invention is to provide a system for producing octanol, which pre-disperses n-butyraldehyde into macro-bubbles by using a first pre-disperser, and then disperses and breaks it into micro-bubbles through a micro-interface generator,
  • the mass transfer area of the phase boundary between n-butyraldehyde and lye is increased, which is beneficial to improve the reaction efficiency; by setting the first pre-disperser, it is beneficial to improve the generation rate of micro-bubbles;
  • the air bubbles are evenly distributed.
  • the second object of the present invention is to provide a reaction method for producing octanol using the above-mentioned production system.
  • the reaction method is easy to operate, has high butyraldehyde conversion rate and high product quality, is beneficial to reduce energy consumption, and achieves higher efficiency than existing processes. good response.
  • the invention provides an octanol production system, comprising: a carbonyl reactor and a butyraldehyde separation device; the carbonyl reactor is connected with the butyraldehyde separation device; the butyraldehyde separation device is provided with an n-butyraldehyde outlet , the n-butyraldehyde outlet is connected with a condensation reactor, a first reboiler and a first pre-disperser are arranged between the condensation reactor and the butyraldehyde separation device, and the gas phase outlet of the first reboiler and the liquid phase outlet are both passed into the first predispersor; the n-butyraldehyde separated by the butyraldehyde separation device flows out from the n-butyraldehyde outlet, and passes through the first reboiler and the first reboiler.
  • a pre-disperser is dispersed into n-butyraldehyde bubbles
  • a micro-interface generator is arranged in the condensation reactor, and the micro-interface generator is connected with the first pre-disperser to further disperse the n-butyraldehyde bubbles into micro-level micro-bubbles;
  • the condensation reactor A rotating shaft is arranged longitudinally inside, and the rotating shaft penetrates the bottom of the condensation reactor and is connected with a motor; the part of the rotating shaft located in the condensation reactor is provided with a plurality of stirring paddles; the top of the rotating shaft is connected with distribution disk; the distribution disk is arranged at the outlet of the micro-interface generator;
  • the distribution disk is conical; a plurality of guide holes are evenly distributed on the distribution disk to evenly distribute the micro-bubbles generated by the micro-interface generator;
  • the material outlet of the condensation reactor is connected with a hydrogenation reactor, a second reboiler and an external microbubble generator are arranged between the hydrogenation reactor and the condensation reactor, and the condensation reactor generates
  • the octenal is divided into a gas-phase stream and a liquid-phase stream through the second reboiler, and the gas-phase stream and the liquid-phase stream are all passed into the external micro-bubble generator, and in the external-type micro-bubble generator. After being dispersed into micron-sized octenal microbubbles, flow into the hydrogenation reactor;
  • the hydrogenation reactor is provided with a built-in micro-bubble generator, and the built-in micro-interface generator is connected with the hydrogen cylinder; a second pre-disperser is arranged between the hydrogen cylinder and the built-in micro-interface generator , the second pre-disperser is located outside the hydrogenation reactor; after the hydrogen is dispersed into hydrogen bubbles by the second pre-dispersor, it is again dispersed into micron-scale hydrogen micro-bubbles inside the built-in micro-interface generator.
  • the present invention provides a system for producing octanol, which uses a first pre-disperser to pre-disperse n-butyraldehyde into large bubbles and then disperses and breaks it by a micro-interface generator.
  • the formation of microbubbles increases the mass transfer area of the phase boundary between n-butyraldehyde and lye, which is beneficial to improve the reaction efficiency; the use of the first pre-disperser is beneficial to increase the generation rate of microbubbles.
  • the outlet of the micro-interface generator of the present invention is also provided with a distribution disc, which can promote the redistribution of micro-bubbles in the condensation reactor; in addition, the distribution disc of the present invention is connected with a rotating shaft, and the rotating shaft drives the distribution The disc rotates, which can further promote the uniform distribution of the micro-bubbles; the stirring paddle set on the rotating shaft is also to promote the uniform distribution of the micro-bubbles, thereby improving the reaction efficiency.
  • the present invention improves the application effect of the micro-interface generator by combining the first pre-disperser, the micro-interface generator, the distribution disc and the stirring paddle.
  • a built-in micro-bubble generator is arranged in the hydrogenation reactor to disperse and break the hydrogen gas into micro-bubbles, and the external micro-bubble generator disperses and breaks octenal into micro-bubbles, thereby improving octenal and octenal.
  • the phase boundary contact area of hydrogen increases the conversion rate and reaction rate.
  • both the first pre-dispersor and the second pre-dispersor are provided with multiple layers of dispersion layers, and the dispersion layers are formed by stacking a plurality of circular granules with different diameters.
  • the granular material can be made of acid-resistant and corrosion-resistant materials.
  • the circular granular bodies between the two adjacent layers cooperate with each other to form multiple gaps of the same size. The gas passes through the gaps to form bubbles, which improves the mass transfer on the gas surface. area.
  • the side wall of the condensation reactor is provided with a liquid injector for injecting alkali liquid
  • the liquid injector comprises a semicircular injector main body and a spray head uniformly arranged on the semicircular surface of the injector main body ; the liquid injector is located below the micro-interface generator along the vertical direction; the liquid injector is connected with an alkali liquid storage tank.
  • two bubble distributors with opposite outlets are arranged inside the hydrogenation reactor, the bubble distributor located above is connected to the built-in micro-bubble generator, and the bubble distributor located below is connected to the built-in micro-bubble generator.
  • An external microbubble generator is connected.
  • the bubble distributor can make the bubbles evenly distributed, and the outlet can relatively make the octenal bubbles and the hydrogen bubbles hedged, which further promotes the even distribution of the bubbles.
  • the bubble distributor includes a distributor body and a plurality of nozzles; the plurality of nozzles are obliquely arranged on the distributor body to uniformly disperse the micro-bubbles.
  • the nozzle can redistribute the micro-bubbles, preventing a large number of micro-bubbles from gathering together, and the micro-bubbles enter the main body of the distributor and are sprayed in different directions through the nozzle.
  • a solvent inlet is arranged at the bottom of the carbonyl reactor; a propylene inlet and a synthesis gas inlet are arranged on the side wall of the carbonyl reactor in sequence; two micro-interfaces with opposite outlets are arranged in the carbonyl reactor to generate
  • the micro-interface generator located above is connected to the propylene inlet, and the micro-interface generator located below is connected to the synthesis gas inlet.
  • a bubble distributor is arranged at the outlet of the two micro-interface generators.
  • a catalyst injector is further arranged on the side wall of the carbonyl reactor, and the catalyst injector is arranged vertically between the two micro-interface generators.
  • the catalyst injector has the same structure as the liquid injector.
  • the carbonyl reactor of the invention is provided with two micro-interface generators to disperse and crush propylene and synthesis gas respectively.
  • propylene and synthesis gas are dispersed and crushed into micro-level micro-bubbles by the micro-interface generator respectively, and then carbonylation is carried out.
  • the reaction increases the mass transfer area of the phase boundary between propylene and synthesis gas; the outlets of the two micro-interface generators are opposed to each other, which can play a hedging effect to achieve uniform distribution of micro-bubbles.
  • the micro-interface generator located in the upper part is connected with the propylene inlet
  • the micro-interface generator located in the lower part is connected with the synthesis gas inlet
  • the synthesis gas is relatively the gas source. It needs to be synthesized in advance, and the raw materials are all flammable and explosive gases, so in order to improve its safety, try to set the position of its air inlet as low as possible. Therefore, the micro-interface generator for crushing propylene is set in the upper part, and the micro-interface generator for crushing syngas is set in the lower part. This arrangement also fully considers safety, reaction efficiency and other factors. After the micro-interface generator is sufficiently broken and dispersed, it will pass through the gas distributor located on the upper part of the micro-interface generator with a higher probability to achieve a more uniform distribution.
  • the present invention uses a first pre-disperser to pre-disperse n-butyraldehyde into large bubbles, and then disperses and breaks it into micro-bubbles through a micro-interface generator, thereby improving the efficiency of n-butyraldehyde and lye.
  • the phase boundary mass transfer area of the lye; the use of the first pre-disperser is beneficial to improve the generation rate of microbubbles.
  • the outlet of the micro-interface generator of the present invention is also provided with a distribution disc, which can promote the redistribution of micro-bubbles in the condensation reactor; in addition, the distribution disc of the present invention is connected with a rotating shaft, and the rotating shaft drives the distribution The disc rotates, which can further promote the uniform distribution of the micro-bubbles; the stirring paddle set on the rotating shaft is also to promote the uniform distribution of the micro-bubbles, thereby improving the reaction efficiency. It can be seen that the present invention improves the application effect of the micro-interface generator by combining the first pre-disperser, the micro-interface generator and the distribution disc.
  • a built-in micro-bubble generator is arranged in the hydrogenation reactor to disperse and break the hydrogen gas into micro-bubbles, and the external micro-bubble generator disperses and breaks octenal into micro-bubbles, thereby improving octenal and octenal.
  • the phase boundary contact area of hydrogen improves the conversion rate and reaction rate, and at the same time, by combining the second pre-disperser with the built-in microbubble generator, the generation efficiency of hydrogen microbubbles is improved.
  • micro-interface generator used in the present invention has been embodied in the inventor's prior patents, such as application numbers CN201610641119.6, CN201610641251.7, CN201710766435.0, CN106187660, CN105903425A, Patents of CN109437390A, CN205833127U and CN207581700U.
  • application numbers CN201610641119.6, CN201610641251.7, CN201710766435.0, CN106187660, CN105903425A, Patents of CN109437390A, CN205833127U and CN207581700U In the previous patent CN201610641119.6, the specific product structure and working principle of the micro-bubble generator (that is, the micro-interface generator) were introduced in detail.
  • the body is provided with an inlet communicating with the cavity, the opposite first and second ends of the cavity are open, wherein the cross-sectional area of the cavity is from the middle of the cavity to the first and second ends of the cavity.
  • the second end is reduced; the secondary crushing piece is arranged at at least one of the first end and the second end of the cavity, a part of the secondary crushing piece is arranged in the cavity, and both ends of the secondary crushing piece and the cavity are open
  • An annular channel is formed between the through holes of the micro-bubble generator.
  • the micro-bubble generator also includes an air inlet pipe and a liquid inlet pipe.” From the specific structure disclosed in the application document, we can know that its specific working principle is: the liquid enters the micron tangentially through the liquid inlet pipe. In the bubble generator, ultra-high-speed rotation and cutting of the gas make the gas bubbles break into micro-bubbles at the micron level, thereby increasing the mass transfer area between the liquid phase and the gas phase, and the micro-bubble generator in this patent belongs to the pneumatic micro-interface generation. device.
  • the previous patent 201610641251.7 records that the primary bubble breaker has a circulating liquid inlet, a circulating gas inlet and a gas-liquid mixture outlet, and the secondary bubble breaker communicates the feed port with the gas-liquid mixture outlet, indicating that the bubble breaker is both It needs to be mixed with gas and liquid.
  • the primary bubble breaker mainly uses circulating liquid as power, so in fact, the primary bubble breaker belongs to the hydraulic micro-interface generator, and the secondary bubble breaker is a gas-liquid breaker. The mixture is simultaneously fed into the elliptical rotating ball for rotation, so that the bubbles are broken during the rotation, so the secondary bubble breaker is actually a gas-liquid linkage type micro-interface generator.
  • micro-interface generator used in the present invention is not limited to the above several forms.
  • specific structure of the bubble breaker described in the prior patent is only one of the forms that the micro-interface generator of the present invention can take.
  • previous patent 201710766435.0 recorded that "the principle of the bubble breaker is to achieve high-speed jets to achieve gas collision", and also stated that it can be used in micro-interface enhanced reactors to verify the relationship between the bubble breaker and the micro-interface generator.
  • the top of the bubble breaker is the liquid phase inlet, and the side is the gas phase inlet.
  • the liquid phase entering from the top provides the entrainment power, so as to achieve the effect of crushing into ultra-fine bubbles, which can also be seen in the accompanying drawings.
  • the bubble breaker has a conical structure, and the diameter of the upper part is larger than that of the lower part, so that the liquid phase can provide better entrainment power.
  • micro-interface generator Since the micro-interface generator was just developed in the early stage of the previous patent application, it was named as micro-bubble generator (CN201610641119.6), bubble breaker (201710766435.0), etc., and later changed its name to micro-interface generator with continuous technological improvement.
  • the micro-interface generator and micro-interface generator in the present invention are equivalent to the previous micro-bubble generator, bubble breaker, etc., but the names are different. To sum up, the micro-interface generator of the present invention belongs to the prior art.
  • a rectification column is connected to the material outlet of the hydrogenation reactor; the octanol produced by the hydrogenation reactor is rectified and discharged by the rectification column.
  • the hydrogenation reactor is a slurry bed reactor.
  • the carbonyl reactor is connected with a catalyst circulation device for supplementing the catalyst.
  • a demister is arranged between the carbonyl reactor and the butyraldehyde separation device, and the product of the carbonyl reactor flows into the butyraldehyde separation device after being defoamed by the demister.
  • the present invention also provides a reaction method using the above-mentioned production system, comprising the steps of:
  • n-butyraldehyde After the n-butyraldehyde is broken by the micro-interface, it is subjected to a condensation reaction with the lye to generate octenal, and the octenal and hydrogen are respectively subjected to micro-interface fragmentation, and the crude octanol product is obtained after the hydrogenation reaction, and the crude octanol product is obtained.
  • the product octanol is obtained after rectification and purification.
  • the reaction temperature for the synthesis of the hydroxyl group is 80-95° C., and the pressure is 0.8-1.3 MPa; the catalyst is a rhodium catalyst.
  • the reaction temperature in the condensation reactor is 65-75° C.
  • the reaction pressure is 0.23-0.28 MPa.
  • reaction temperature in the hydrogenation reactor is 60-78° C.
  • reaction pressure is 0.50-0.80 MPa.
  • the hydrogenation reaction catalyst is a metal such as nickel, chromium, and an oxide catalyst triphenylphosphine solution or other industry-approved auxiliaries of the same type to participate in the reaction.
  • the octanol product obtained by the reaction method of the invention has good quality, high yield and high conversion rate of butyraldehyde.
  • the preparation method itself has low reaction temperature, greatly reduced pressure and significantly reduced cost.
  • Fig. 1 is the structural representation of the production system of octanol provided by the embodiment of the present invention 1;
  • FIG. 2 is the structural representation inside the condensation reactor provided by the embodiment of the present invention 1;
  • FIG. 4 is a schematic structural diagram of a first predisperser provided in Embodiment 1 of the present invention.
  • FIG. 5 is a schematic structural diagram of the catalyst injector provided in Example 1 of the present invention.
  • 80-condensation reactor 801-micro interface generator
  • the terms “installed”, “connected” and “connected” should be understood in a broad sense, unless otherwise expressly specified and limited, for example, it may be a fixed connection or a detachable connection Connection, or integral connection; can be mechanical connection, can also be electrical connection; can be directly connected, can also be indirectly connected through an intermediate medium, can be internal communication between two elements.
  • installed should be understood in a broad sense, unless otherwise expressly specified and limited, for example, it may be a fixed connection or a detachable connection Connection, or integral connection; can be mechanical connection, can also be electrical connection; can be directly connected, can also be indirectly connected through an intermediate medium, can be internal communication between two elements.
  • this embodiment provides an octanol production system, including: a carbonyl reactor 10 and a butyraldehyde separation device 30; the carbonyl reactor 10 is connected to the butyraldehyde separation device 30; the carbonyl reactor 10 A demister 20 is arranged between the device and the butyraldehyde separation device 30 , and the product of the carbonyl reactor 10 flows into the butyraldehyde separation device 30 after being defoamed by the demister 20 .
  • the bottom of the carbonyl reactor 10 is provided with a solvent inlet 103; the side wall of the carbonyl reactor 10 is provided with a propylene inlet 101 and a synthesis gas inlet 102 in sequence; two micro-interface generators with opposite outlets are arranged in the carbonyl reactor 10 105 , the upper micro-interface generator 105 is connected to the propylene inlet 101 , and the lower micro-interface generator 105 is connected to the syngas inlet 102 .
  • a bubble distributor 106 is provided at the outlet of the two micro-interface generators 105 .
  • a catalyst injector 104 is also arranged on the side wall of the carbonyl reactor 10 , and the catalyst injector 104 is arranged between the two micro-interface generators 105 in the vertical direction.
  • the butyraldehyde separation device 30 is provided with an n-butyraldehyde outlet 302 and a mixed butyraldehyde outlet 301, and the n-butyraldehyde outlet 302 is connected with a condensation reactor 80, and a condensation reactor 80 is provided between the butyraldehyde separation device 30
  • a first reboiler 40 and a first predispersor 50 and the gas phase outlet and the liquid phase outlet of the first reboiler 40 are both passed into the first predisperser 50;
  • the n-butyraldehyde separated by the butyraldehyde separation device 30 It flows out from the n-butyraldehyde outlet 302, is dispersed into n-butyraldehyde bubbles through the first reboiler 40 and the first pre-dispersor 50, and then passes into the condensation reactor 80.
  • a micro-interface generator 801 is arranged in the condensation reactor 80, and the micro-interface generator 801 is connected with the first pre-disperser 50 to further disperse the n-butyraldehyde bubbles into micro-bubbles of micron level;
  • the condensation reactor A rotating shaft 803 is longitudinally arranged inside the 80, and the rotating shaft 803 penetrates the bottom of the condensation reactor 80 and is connected with a motor 140; the part of the rotating shaft 803 located in the condensation reactor 80 is provided with a plurality of stirring paddles 804;
  • the disc 805; the distribution disc 805 is arranged at the outlet of the micro-interface generator 801;
  • the distribution disk 805 is tapered; the distribution disk 805 is evenly distributed with a plurality of guide holes to evenly distribute the micro-bubbles generated by the micro-interface generator 801;
  • the side wall of the condensation reactor 80 is provided with a liquid injector 802 for injecting alkali liquid.
  • the liquid injector 802 includes a semicircular injector body 1041 and a The spray head 1042; the liquid sprayer 802 is located below the micro-interface generator 801 in the vertical direction; the liquid sprayer 802 is connected with the lye storage tank 90.
  • the catalyst injector 104 has the same structure as the liquid injector 802 .
  • a hydrogenation reactor 120 is connected to the material outlet of the condensation reactor 80, and a second reboiler 100 and an external microbubble generator 110 are arranged between the hydrogenation reactor 120 and the condensation reactor 80.
  • Octenal is divided into gas-phase stream and liquid-phase stream through the second reboiler 100, and both the gas-phase stream and the liquid-phase stream are passed into the external micro-bubble generator 110, and are dispersed into micron-level in the external micro-bubble generator 110.
  • the octenal microbubbles then flow into the hydrogenation reactor 120 .
  • the hydrogenation reactor 120 is provided with a built-in micro-bubble generator 1201, and the built-in micro-interface generator 801 is connected to the hydrogen cylinder 60; a second pre-disperser 70 is arranged between the hydrogen cylinder 60 and the built-in micro-interface generator 801, and the second The pre-disperser 70 is located outside the hydrogenation reactor 120 ; the hydrogen is dispersed into hydrogen bubbles by the second pre-dispersor 70 and then dispersed into micron-scale hydrogen micro-bubbles inside the built-in micro-interface generator 801 .
  • the octenal microbubbles react with the hydrogen microbubbles, and the reaction product enters the rectifying tower 130 for rectification.
  • both the first pre-dispersor 50 and the second pre-dispersor 70 are provided with a multi-layer dispersion layer 501 , and the dispersion layer 501 is formed by stacking a plurality of circular granular bodies with different diameters.
  • the granular material can be made of acid-resistant and corrosion-resistant materials.
  • the circular granular bodies between two adjacent layers cooperate with each other to form a plurality of gaps of the same size, and the gas passes through the gaps to form bubbles.
  • the hydrogenation reactor 120 is provided with two bubble distributors 106 with opposite outlets.
  • the bubble distributor 106 located above is connected to the built-in micro-bubble generator 1201, and the bubble distributor 106 located below is connected to the external micro-bubble generator 1201.
  • a bubble generator 110 is connected.
  • the bubble distributor 106 can make the bubbles evenly distributed, and the outlet can relatively create a hedge between the octenal bubbles and the hydrogen bubbles, which further promotes the even distribution of the bubbles.
  • the bubble distributor 106 includes a distributor main body 1061 and a plurality of nozzles 1062; the plurality of nozzles 1062 are obliquely arranged on the distributor main body 1061 to uniformly disperse the micro-bubbles.
  • the nozzle 1062 can redistribute the micro-bubbles, preventing a large number of micro-bubbles from gathering together, and the micro-bubbles enter the distributor body 1061 and are sprayed in different directions through the nozzle 1062.
  • the hydrogenation reactor 120 is a slurry bed reactor.
  • the carbonyl reactor 10 is connected with a catalyst circulation device 150 for supplementing the catalyst.
  • the catalyst circulation device 150 can also promote the recycling of the catalyst and save the cost.
  • the solvent in the carbonyl reactor 10 is n-butyraldehyde
  • the solvent in the hydrogenation reactor 120 is octanol
  • the solvent in the condensation reactor 80 is octanol.
  • the propylene gas and the synthesis gas are passed into the carbonyl reactor 10, the reaction temperature in the carbonyl reactor 10 is set to 80° C., the reaction pressure is set to 0.8MPa, and the micro-interface generator 105 breaks the propylene and the synthesis gas into pieces.
  • the micro-bubbles are formed into micro-sized bubbles, and the micro-bubbles are released into the carbonyl reactor 10, so that the materials are fully contacted and the oxo reaction is carried out.
  • the oxo reaction product is transported to the butyraldehyde separation device 30, and the n-butyraldehyde enters the micro-interface generator 801 through the first pre-disperser 50, and the micro-interface generator 801 smashes the n-butyraldehyde into micron-scale micro-bubbles, and It is released into the condensation reactor 80, so that the n-butyraldehyde and the alkali liquid are fully contacted to carry out the condensation reaction.
  • the reaction temperature in the condensation reactor 80 was set to 60° C., and the reaction pressure was set to 0.18 MPa.
  • the condensation reaction product is dispersed and broken by the external micro-bubble generator 110 and then enters the hydrogenation reactor 120.
  • the reaction temperature in the hydrogenation reactor 120 is set to 60°C and the reaction pressure is set to 0.50MPa.
  • the hydrogenation reaction product is rectified by the rectification tower 130 to obtain octanol.
  • the conversion rate of propylene is 98.5%
  • the conversion rate of butyraldehyde is 97.2%
  • the synthesis efficiency of the process is increased by 4.3%.
  • the production system of this embodiment is the same as that of Embodiment 1, except that in this embodiment, the reaction temperature in the carbonyl reactor 10 is set to 88°C, and the reaction pressure is set to 1.1MPa; the reaction temperature in the condensation reactor 80110 is set to 65°C °C, the reaction pressure is set to 0.21 MPa; the reaction temperature in the hydrogenation reactor 120 is set to 70 °C, and the reaction pressure is set to 0.70 MPa.
  • the conversion rate of propylene is 99.0%
  • the conversion rate of butyraldehyde is 98.5%
  • the synthesis efficiency of the process is increased by 4.5%.
  • the production system of this embodiment is the same as that of Embodiment 1, except that in this embodiment, the reaction temperature in the carbonyl reactor 10 is set to 95° C., and the reaction pressure is set to 1.3 MPa; the reaction temperature in the condensation reactor 80 is set to 70° C. °C, the reaction pressure is set to 0.25 MPa; the reaction temperature in the hydrogenation reactor 120 is set to 78 °C, and the reaction pressure is set to 0.80 MPa.
  • the production system of the present invention has high material conversion rate, low energy consumption, low cost, high safety, low required reaction temperature and pressure, and side reactions. It is worthy of widespread application.

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Abstract

一种辛醇的产生系统，包括：羰基反应器（10）和丁醛分离装置（30）；羰基反应器（10）与丁醛分离装置（30）相连；丁醛分离装置（30）上设置有正丁醛出口（302），正丁醛出口（302）连接有缩合反应器（80），缩合反应器（80）与丁醛分离装置（30）间设置有第一再沸器（40）和第一预分散器（50），第一再沸器（40）的气相出口和液相出口均通入第一预分散器（50）中；丁醛分离装置（30）分离出的正丁醛从正丁醛出口（302）中流出，经第一再沸器（40）和第一预分散器（50）分散成正丁醛气泡后通入缩合反应器（80）中；缩合反应器（80）中设置有微界面发生器（801），微界面发生器（801）与第一预分散器（50）相连以将正丁醛气泡进一步分散成微米级别的微气泡。

Description

一种辛醇的产生系统及方法 技术领域
本发明涉及丙烯羟基化反应制备领域，具体而言，涉及一种辛醇的产生系统及方法。
背景技术
辛醇是合成精细化工产品的重要原料，目前我国辛醇产量巨大，约占世界总量的21％，辛醇以合成气和丙烯为原料，经过甲酰化反应生成正异丁醛，进而得到正异丁醇，亦可两分子正丁醛缩合生再加成不饱和键得到辛醇。辛醇具有醇类有机物的典型特征，均具有特殊气味，为无色透明、易燃液体，有中等毒性，与水能够形成共沸物。主要用于生产增塑剂、溶剂、脱水剂、消泡剂、分散剂、浮选剂、石油添加剂及合成香料等。由于其广泛的用途，辛醇的产量和用量也逐年提高。
辛醇的主要生产方法有发酵法、乙醛缩合法和丙烯羰基合成法，其中，丙烯羰基合成法在世界范围内以显著地优势而迅速发展，是生产丁醇和辛醇的主要方法。
丙烯羰基合成法制备辛醇的步骤如下：
(1)丁醛的生成：以合成气和丙烯为原料，以羰基铑、三苯基膦络合物或其它工业上使用的同类型物质为催化剂，反应生产生成混合丁醛，分离催化剂后进一步精馏分离得到丁醛混合物；
(2)丁醇的生成：丁醛混合物进入丁醛加氢系统，产生丁醇，再经过精馏脱除轻重组分、异构物分离得到正丁醇和异丁醇；
(3)辛醇的生成：以正丁醛进入缩合系统进行羰基缩合，生产辛烯醛，再加氢、精馏脱除轻重组分，最终生产辛醇。
丙烯羰基合成法制备辛醇的主要方程式如下：
(1)丙烯氢甲酰化生成正丁醛(n-Bal)：
CH 3CH＝CH 2+CO+H 2→CH 3CH 2CH 2CHO
(2)丙烯氢甲酰化生成异丁醛(i-Bal)：
CH 3CH＝CH 2+CO+H 2→CH 3CH 2(CHO)CH 3
(3)混合丁醛加氢生成异丁醇和正丁醇：
CH 3CH 2CH 2CHO+H 2→CH 3CH 2CH 2CH 2OH
CH 3CH 2(CHO)CH 3+H 2→CH 3CH(CH 3)CH 2OH
(4)正丁醛缩合反应生成2-乙基-3-丙基丙烯醛(EPA):
2CH 3CH 2CH 3CHO→CH 3CH 2CH 2CH＝C(C 2H 5)CHO+H 2O
(5)2-乙基-3-丙基丙烯醛加氢生成辛醇：
CH 3CH 2CH 2CH＝C(C 2H 5)CHO+2H 2→CH 3CH 2CH 2CH(CH 2CH 3)CH 2OH
中国专利公开号：CN103012089A公开了一种丙烯羰基合成的方法，包括将丙烯和气提合成气以及氢甲酰化催化剂溶液送入第一羰基合成丁醛缩合单元中接触反应，将该丁醛缩合单元中的含有氢甲酰化催化剂的泡沫组分送入第一分离器分离，得到的气相组分的一部分返回，另一部分与合成气和氢甲酰化催化剂溶液送入第二羰基合成丁醛缩合单元中接触反应，并将该丁醛缩合单元中的含有氢甲酰化催化剂的泡沫组分送入第二分离器分离；将至少部分的第一、第二羰基合成丁醛缩合单元釜底的液相和合成气一起送入气提塔中气提，塔底得到液相组分，塔顶得到所述气提合成气；将气提塔塔底液相组分送入分离塔中分离，塔顶采出丁醛粗产品，塔底采出催化剂溶液。该方法能够有效地提高丙烯的利用率，减少尾气中丙烯的含量。由此可见，所述方法存在以下问题：
第一，所述方法中仅通过第一羰基合成丁醛缩合单元使丙烯、合成气与催化剂接触，气相组分进入第一羰基合成形成大气泡，然而由于气泡体积过大，无法与液相组分催化剂充分接触，降低了系统的反应效率。
第二，所述方法中合成气与丙烯与催化剂反应速率降低，导致丙烯和合成气利用率降低，很大程度上造成原料的浪费，增加了辛醇的生产成本，不符合 现有的循环经济的要求。
第三，所述方法未考虑碱液与正丁醛溶液直接反应中，相界面积小，液滴凝并现象严重，反应效率低等问题。
第四，所述方法中加氢反应利用固定床反应器，由于其为强放热反应，过程中需移出大量的热，且反应能耗大效率低。
有鉴于此，特提出本发明。
发明内容
本发明的第一目的在于提供一种辛醇的产生系统，该产生系统通过使用第一预分散器将正丁醛预分散为大气泡后再通过微界面发生器将其分散破碎成微气泡，提高了正丁醛与碱液的相界传质面积，有利于提高反应效率；通过设置第一预分散器，有利于提高微气泡的生成速率；通过在出口设置分布圆盘能够促进产生的微气泡均匀分布。
本发明的第二目的在于提供一种采用上述产生系统进行制辛醇的反应方法，该反应方法操作简便，丁醛转化率高，产品品质高，有利于减少能耗，达到比现有工艺更佳的反应效果。
为了实现本发明的上述目的，特采用以下技术方案：
本发明提供了一种辛醇的产生系统，包括：羰基反应器和丁醛分离装置；所述羰基反应器与所述丁醛分离装置相连；所述丁醛分离装置上设置有正丁醛出口，所述正丁醛出口连接有缩合反应器，所述缩合反应器与所述丁醛分离装置间设置有第一再沸器和第一预分散器，所述第一再沸器的气相出口和液相出口均通入所述第一预分散器中；所述丁醛分离装置分离出的正丁醛从所述正丁醛出口中流出，经所述第一再沸器和所述第一预分散器分散成正丁醛气泡后通入所述缩合反应器中；
所述缩合反应器内设置有微界面发生器，所述微界面发生器与所述第一预 分散器相连以将所述正丁醛气泡进一步分散成微米级别的微气泡；所述缩合反应器内部纵向设置有旋转轴，所述旋转轴穿透所述缩合反应器底部连接有电机；所述旋转轴位于所述缩合反应器内的部分设置有多个搅拌桨；所述旋转轴顶部连接有分布圆盘；所述分布圆盘设置在所述微界面发生器的出口处；
所述分布圆盘呈锥形；所述分布圆盘上均匀分布有多个导向孔以将所述微界面发生器产生的微气泡均匀分布；
所述缩合反应器的物料出口连接有加氢反应器，所述加氢反应器与所述缩合反应器之间设置有第二再沸器和外置式微气泡发生器，所述缩合反应器产生的辛烯醛经所述第二再沸器分为气相物流和液相物流，气相物流和液相物流均通入所述外置式微气泡发生器中，在所述外置式微气泡发生器中分散成微米级的辛烯醛微气泡后流入所述加氢反应器中；
所述加氢反应器内设置有内置式微气泡发生器，所述内置式微界面发生器与所述氢气瓶相连；所述氢气瓶与所述内置式微界面发生器之间设置有第二预分散器，所述第二预分散器位于所述加氢反应器外侧；氢气经所述第二预分散器分散为氢气泡后在所述内置式微界面发生器内部再次分散为微米级别的氢气微气泡。
现有技术中，碱液与正丁醛溶液直接反应中，相界面积小，液滴凝并现象严重，反应效率低。且后续生成的辛烯醛加氢反应过程中，也存在接触面积小，反应效率低的问题，这些都严重影响了生成的辛醇的产率。
为解决上述技术问题，本发明提供了一种辛醇的产生系统，该微界面产生系统通过使用第一预分散器将正丁醛预分散为大气泡后再通过微界面发生器将其分散破碎成微气泡，提高了正丁醛与碱液的相界传质面积，有利于提高反应效率；第一预分散器的使用则有利于提高微气泡的生成速率。本发明的微界面发生器的出口处还设置有分布圆盘，分布圆盘能够促进微气泡在缩合反应器内的再分布；另外，本发明的分布圆盘连接有旋转轴，旋转轴带动分布圆盘旋转，这样能够进一步促进微气泡的均匀分布；旋转轴上设置的搅拌桨也是为了 促进微气泡均匀分布，进而提高反应效率。
可见，本发明通过将第一预分散器、微界面发生器、分布圆盘和搅拌桨相结合，提高了微界面发生器的应用效果。
另外，本发明通过在加氢反应器内设置内置式微气泡发生器，将氢气分散破碎成微气泡，并通过外置式微气泡发生器将辛烯醛分散破碎成微气泡，提高了辛烯醛和氢气的相界接触面积，提高了转化率和反应速率。
优选的，所述第一预分散器与所述第二预分散器内部均设置有多层分散层，所述分散层由多个不同直径的圆形散粒体堆砌而成。散粒体材质可选择由耐酸耐腐蚀的材料制成，相邻两层之间的圆形散粒体相互配合形成多个相同大小的间隙，气体经过间隙形成气泡，提高了气体表面的传质面积。
优选的，所述缩合反应器侧壁设置有用于喷射碱液的液体喷射器，所述液体喷射器包括呈半圆形的喷射器主体和均匀布置在所述喷射器主体半圆面上的喷射头；所述液体喷射器沿竖直方向位于所述微界面发生器的下方；所述液体喷射器连接有碱液储罐。将碱液通过液体喷射器喷射，能够提高与正丁醛的接触面积，提高了正丁醛的转化率。
优选的，所述加氢反应器内部设置有两个出口相对的气泡分布器，位于上方的所述气泡分布器与所述内置式微气泡发生器相连，位于下方的所述气泡分布器与所述外置式微气泡发生器相连。气泡分布器能够使气泡均匀分布，出口相对能够使辛烯醛气泡与氢气气泡间产生对冲，进一步促进气泡分布均匀。
优选的，所述气泡分布器包括分布器主体和多个喷嘴；多个所述喷嘴倾斜布置在所述分布器主体上以将微气泡均匀分散。喷嘴能够对微气泡起到再分布的作用，防止大量的微气泡聚集在一起，微气泡进入分布器主体中，通过喷嘴喷射到不同的方向。
优选的，所述羰基反应器的底部设置有溶剂进口；所述羰基反应器的侧壁上依次设置有丙烯进口和合成气进口；所述羰基反应器内设置有两个出口相对的微界面生成器，位于上方的所述微界面生成器与所述丙烯进口相连，位于下 方的所述微界面生成器与所述合成气进口相连。两个微界面生成器的出口处均设置有气泡分布器。
优选的，所述羰基反应器的侧壁上还设置有催化剂喷射器，所述催化剂喷射器沿竖直方向设置在两个所述微界面生成器之间。所述催化剂喷射器与所述液体喷射器结构相同。
本发明的羰基反应器内设置有两个微界面生成器分别对丙烯和合成气进行分散破碎，反应时，丙烯和合成气分别经微界面生成器分散破碎为微米级别的微气泡后进行羰基化反应，提高了丙烯和合成气的相界传质面积；将两个微界面生成器的出口相对，能够起到对冲效果，以实现微气泡的均匀分布。
需要注意的是，本发明在对微界面生成器进行排布时，位于上部的微界面生成器与丙烯进口连接，位于下部的微界面生成器与合成气进口连接，合成气相对来说气源需要预先合成，而且原料均属于易燃易爆气体，所以为了提高其安全性，尽量将其进气口设置的位置比较低一些，同时鉴于其进入羰基反应器内部后更容易朝着反应器顶部流动，所以用于破碎丙烯的微界面生成器设置在上部，破碎合成气的微界面生成器设置在下部，这样的排布方式也是充分考虑了安全性、反应效率等多方面的因素，合成气通过微界面生成器充分破碎分散后，也会更加大概率的通过位于微界面生成器上部的气体分布器以实现更为均匀的分布。
为提高正丁醛与碱液的反应效率，本发明使用第一预分散器将正丁醛预分散为大气泡后再通过微界面发生器将其分散破碎成微气泡，提高了正丁醛与碱液的相界传质面积；第一预分散器的使用则有利于提高微气泡的生成速率。
本发明的微界面发生器的出口处还设置有分布圆盘，分布圆盘能够促进微气泡在缩合反应器内的再分布；另外，本发明的分布圆盘连接有旋转轴，旋转轴带动分布圆盘旋转，这样能够进一步促进微气泡的均匀分布；旋转轴上设置的搅拌桨也是为了促进微气泡均匀分布，进而提高反应效率。可见，本发明通过将第一预分散器、微界面发生器和分布圆盘结合，提高了微界面发生器的应 用效果。
另外，本发明通过在加氢反应器内设置内置式微气泡发生器，将氢气分散破碎成微气泡，并通过外置式微气泡发生器将辛烯醛分散破碎成微气泡，提高了辛烯醛和氢气的相界接触面积，提高了转化率和反应速率，同时通过将第二预分散器与内置式微气泡发生器结合使用，提高了氢气微气泡的生成效率。
本领域所属技术人员可以理解的是，本发明所采用的微界面发生器在本发明人在先专利中已有体现，如申请号CN201610641119.6、CN201610641251.7、CN201710766435.0、CN106187660、CN105903425A、CN109437390A、CN205833127U及CN207581700U的专利。在先专利CN201610641119.6中详细介绍了微米气泡发生器(即微界面发生器)的具体产品结构和工作原理，该申请文件中记载了“微米气泡发生器包括本体和二次破碎件、本体内具有空腔，本体上设有与空腔连通的进口，空腔的相对的第一端和第二端均敞开，其中空腔的横截面积从空腔的中部向空腔的第一端和第二端减小；二次破碎件设在空腔的第一端和第二端中的至少一个处，二次破碎件的一部分设在空腔内，二次破碎件与空腔两端敞开的通孔之间形成一个环形通道。微米气泡发生器还包括进气管和进液管。”从该申请文件中公开的具体结构可以知晓其具体工作原理为：液体通过进液管切向进入微米气泡发生器内，超高速旋转并切割气体，使气体气泡破碎成微米级别的微气泡，从而提高液相与气相之间的传质面积，而且该专利中的微米气泡发生器属于气动式微界面发生器。
另外，在先专利201610641251.7中有记载一次气泡破碎器具有循环液进口、循环气进口和气液混合物出口，二次气泡破碎器则是将进料口与气液混合物出口连通，说明气泡破碎器都是需要气液混合进入，另外从后面的附图中可知，一次气泡破碎器主要是利用循环液作为动力，所以其实一次气泡破碎器属于液动式微界面发生器，二次气泡破碎器是将气液混合物同时通入到椭圆形的旋转球中进行旋转，从而在旋转的过程中实现气泡破碎，所以二次气泡破碎器实际上是属于气液联动式微界面发生器。其实，无论是液动式微界面发生器， 还是气液联动式微界面发生器，都属于微界面发生器的一种具体形式，然而本发明所采用的微界面发生器并不局限于上述几种形式，在先专利中所记载的气泡破碎器的具体结构只是本发明微界面发生器可采用的其中一种形式而已。此外，在先专利201710766435.0中记载到“气泡破碎器的原理就是高速射流以达到气体相互碰撞”，并且也阐述了其可以用于微界面强化反应器，验证本身气泡破碎器与微界面发生器之间的关联性；而且在先专利CN106187660中对于气泡破碎器的具体结构也有相关的记载，具体见说明书中第[0031]-[0041]段，以及附图部分，其对气泡破碎器S-2的具体工作原理有详细的阐述，气泡破碎器顶部是液相进口，侧面是气相进口，通过从顶部进来的液相提供卷吸动力，从而达到粉碎成超细气泡的效果，附图中也可见气泡破碎器呈锥形的结构，上部的直径比下部的直径要大，也是为了液相能够更好的提供卷吸动力。
由于在先专利申请的初期，微界面发生器才刚研发出来，所以早期命名为微米气泡发生器(CN201610641119.6)、气泡破碎器(201710766435.0)等，随着不断技术改进，后期更名为微界面发生器，现在本发明中的微界面发生器和微界面生成器相当于之前的微米气泡发生器、气泡破碎器等，只是名称不一样。综上所述，本发明的微界面发生器属于现有技术。
优选的，所述加氢反应器的物料出口处连接有精馏塔；所述加氢反应器产生的辛醇经所述精馏塔精馏后排出。
优选的，所述加氢反应器为浆态床反应器。
优选的，所述羰基反应器上连接有用于补充催化剂的催化剂循环装置。
优选的，所述羰基反应器与所述丁醛分离装置之间设置有除沫器，所述羰基反应器的产物经所述除沫器除沫后流入所述丁醛分离装置中。
本发明还提供了一种采用上述产生系统的反应方法，包括如下步骤：
将丙烯和合成气与催化剂混合，进行羟基合成反应，再经过除沫后得到粗产品，粗产品经分离得到正丁醛；
正丁醛经微界面破碎后，与碱液进行缩合反应生成辛烯醛，辛烯醛与氢气 分别进行微界面破碎后，经加氢反应后得到辛醇粗产品，将所述辛醇粗产品精馏纯化后得到产物辛醇。
优选的，所述羟基合成反应温度为80-95℃，压力为0.8-1.3MPa；所述催化剂为铑催化剂。
优选的，所述缩合反应器内的反应温度为65-75℃，反应压强为0.23-0.28MPa。
进一步地，所述加氢反应器内的反应温度为60-78℃，反应压强为0.50-0.80MPa。
进一步地，所述加氢反应催化剂为镍，铬等金属及氧化物催化剂三苯基膦溶液或其它行业内认可的同类型助剂参与反应。
采用本发明的反应方法得到的辛醇产品品质好、收率高，丁醛转化率高。且该制备方法本身反应温度低、压力大幅度下降，成本显著降低。
与现有技术相比，本发明的有益效果在于：
(1)本发明的产生系统通过使用第一预分散器将正丁醛预分散为大气泡后再通过微界面发生器将其分散破碎成微气泡，提高了正丁醛与碱液的相界传质面积，有利于提高反应效率；
(2)通过设置第一预分散器，有利于提高微气泡的生成速率；
(3)通过在微界面发生器出口设置分布圆盘能够促进产生的微气泡均匀分布。
附图说明
通过阅读下文优选实施方式的详细描述，各种其他的优点和益处对于本领域普通技术人员将变得清楚明了。附图仅用于示出优选实施方式的目的，而并不认为是对本发明的限制。而且在整个附图中，用相同的参考符号表示相同的部件。在附图中：
图1为本发明实施例1提供的辛醇的产生系统的结构示意图；
[根据细则91更正 17.08.2021]　
图2为本发明实施例1提供的缩合反应器内部的结构示意图；
图3为本发明实施例1提供的气泡分布器的结构示意图；
图4为本发明实施例1提供的第一预分散器的结构示意图；
图5为本发明实施例1提供的催化剂喷射器的结构示意图。
附图说明：
10-羰基反应器；                      101-丙烯进口；
102-合成气进口；                     103-溶剂进口；
104-催化剂喷射器；                   1041-喷射器主体；
1042-喷射头；                        105-微界面生成器；
106-气泡分布器；                     1061-分布器主体；
1062-喷嘴；                          20-除沫器；
30-丁醛分离装置；                    301-混合丁醛出口；
302-正丁醛出口；                     40-第一再沸器；
50-第一预分散器；                    501-分散层；
60-氢气瓶；                          70-第二预分散器；
80-缩合反应器；                      801-微界面发生器；
802-液体喷射器；                     803-旋转轴；
804-搅拌桨；                         805-分布圆盘；
90-碱液储罐；                        100-第二再沸器；
110-外置式微气泡发生器；             120-加氢反应器；
1201-内置式微气泡发生器；            130-精馏塔；
140-电机；                           150-催化剂循环装置。
具体实施方式
下面将结合附图和具体实施方式对本发明的技术方案进行清楚、完整地描述，但是本领域技术人员将会理解，下列所描述的实施例是本发明一部分实施例，而不是全部的实施例，仅用于说明本发明，而不应视为限制本发明的范围。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
在本发明的描述中，需要说明的是，术语“中心”、“上”、“下”、“左”、“右”、“竖直”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。此外，术语“第一”、“第二”、“第三”仅用于描述目的，而不能理解为指示或暗示相对重要性。
在本发明的描述中，需要说明的是，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以具体情况理解上述术语在本发明中的具体含义。
为了更加清晰的对本发明中的技术方案进行阐述，下面以具体实施例的形式进行说明。
实施例1
如图1-5所示，本实施例提供了一种辛醇的产生系统，包括：羰基反应器10和丁醛分离装置30；羰基反应器10与丁醛分离装置30相连；羰基反应器 10与丁醛分离装置30之间设置有除沫器20，羰基反应器10的产物经除沫器20除沫后流入丁醛分离装置30中。
其中，羰基反应器10的底部设置有溶剂进口103；羰基反应器10的侧壁上依次设置有丙烯进口101和合成气进口102；羰基反应器10内设置有两个出口相对的微界面生成器105，位于上方的微界面生成器105与丙烯进口101相连，位于下方的微界面生成器105与合成气进口102相连。两个微界面生成器105的出口处均设置有气泡分布器106。
羰基反应器10的侧壁上还设置有催化剂喷射器104，催化剂喷射器104沿竖直方向设置在两个微界面生成器105之间。
在本实施例中，丁醛分离装置30上设置有正丁醛出口302和混合丁醛出口301，正丁醛出口302连接有缩合反应器80，缩合反应器80与丁醛分离装置30间设置有第一再沸器40和第一预分散器50，第一再沸器40的气相出口和液相出口均通入第一预分散器50中；丁醛分离装置30分离出的正丁醛从正丁醛出口302中流出，经第一再沸器40和第一预分散器50分散成正丁醛气泡后通入缩合反应器80中。
如图2所示，缩合反应器80内设置有微界面发生器801，微界面发生器801与第一预分散器50相连以将正丁醛气泡进一步分散成微米级别的微气泡；缩合反应器80内部纵向设置有旋转轴803，旋转轴803穿透缩合反应器80底部连接有电机140；旋转轴803位于缩合反应器80内的部分设置有多个搅拌桨804；旋转轴803顶部连接有分布圆盘805；分布圆盘805设置在微界面发生器801的出口处；
其中，分布圆盘805呈锥形；分布圆盘805上均匀分布有多个导向孔以将微界面发生器801产生的微气泡均匀分布；
如图3所示，缩合反应器80侧壁设置有用于喷射碱液的液体喷射器802，液体喷射器802包括呈半圆形的喷射器主体1041和均匀布置在喷射器主体1041半圆面上的喷射头1042；液体喷射器802沿竖直方向位于微界面发生器 801的下方；液体喷射器802连接有碱液储罐90。将碱液通过液体喷射器802喷射，能够提高与正丁醛的接触面积，进而正丁醛的转化率。
在本实施例中，催化剂喷射器104与液体喷射器802结构相同。
缩合反应器80的物料出口连接有加氢反应器120，加氢反应器120与缩合反应器80之间设置有第二再沸器100和外置式微气泡发生器110，缩合反应器80产生的辛烯醛经第二再沸器100分为气相物流和液相物流，气相物流和液相物流均通入外置式微气泡发生器110中，在外置式微气泡发生器110中分散成微米级的辛烯醛微气泡后流入加氢反应器120中。
加氢反应器120内设置有内置式微气泡发生器1201，内置式微界面发生器801与氢气瓶60相连；氢气瓶60与内置式微界面发生器801之间设置有第二预分散器70，第二预分散器70位于加氢反应器120外侧；氢气经第二预分散器70分散为氢气泡后在内置式微界面发生器801内部再次分散为微米级别的氢气微气泡。辛烯醛微气泡与氢气微气泡发生反应，反应产物进入精馏塔130精馏。
如图4所示，第一预分散器50与第二预分散器70内部均设置有多层分散层501，分散层501由多个不同直径的圆形散粒体堆砌而成。散粒体材质可选择由耐酸耐腐蚀的材料制成，相邻两层之间的圆形散粒体相互配合形成多个相同大小的间隙，气体经过间隙形成气泡。
本实施例中，加氢反应器120内部设置有两个出口相对的气泡分布器106，位于上方的气泡分布器106与内置式微气泡发生器1201相连，位于下方的气泡分布器106与外置式微气泡发生器110相连。气泡分布器106能够使气泡均匀分布，出口相对能够使辛烯醛气泡与氢气气泡间产生对冲，进一步促进气泡分布均匀。
其中，气泡分布器106包括分布器主体1061和多个喷嘴1062；多个喷嘴1062倾斜布置在分布器主体1061上以将微气泡均匀分散。喷嘴1062能够对微气泡起到再分布的作用，防止大量的微气泡聚集在一起，微气泡进入分布器主 体1061中，通过喷嘴1062喷射到不同的方向。
其中，加氢反应器120为浆态床反应器。
为减少催化剂的浪费，羰基反应器10上连接有用于补充催化剂的催化剂循环装置150。催化剂循环装置150还能够促进催化剂的循环利用，节约成本。
在本实施例中，羰基反应器10内的溶剂为正丁醛，加氢反应器120内的溶剂为辛醇，缩合反应器80内的溶剂为辛醇。
具体操作时，将丙烯气和合成气通入羰基反应器10中，羰基反应器10内的反应温度设置为80℃，反应压强设置为0.8MPa，微界面生成器105将丙烯和合成气打碎成微米尺度的微气泡，并将微气泡释放到羰基反应器10内部，使得物料充分接触，并进行羰基合成反应。
将羰基合成反应产物输送至丁醛分离装置30中，正丁醛通过第一预分散器50进入微界面发生器801，微界面发生器801将正丁醛打碎成微米尺度的微气泡，并释放到缩合反应器80内部，使得正丁醛与碱液充分接触，进行缩合反应。缩合反应器80内的反应温度设置为60℃，反应压强设置为0.18MPa。
缩合反应产物通过外置式微气泡发生器110分散破碎后进入到加氢反应器120中，加氢反应器120中反应温度设置为60℃，反应压强设置为0.50MPa。加氢反应产物经精馏塔130精馏后得到辛醇。
经检测，使用所述系统及工艺后，丙烯转化率98.5％，丁醛转化率97.2％，工艺的合成效率提升4.3％。
实施例2
本实施例的产生系统与实施例1一致，区别仅在于本实施例中羰基反应器10内的反应温度设置为88℃，反应压强设置为1.1MPa；缩合反应器80110内的反应温度设置为65℃，反应压强设置为0.21MPa；加氢反应器120中反应温度设置为70℃，反应压强设置为0.70MPa。
经检测，使用所述系统及工艺后，丙烯转化率99.0％，丁醛转化率98.5％， 工艺的合成效率提升4.5％。
实施例3
本实施例的产生系统与实施例1一致，区别仅在于本实施例中羰基反应器10内的反应温度设置为95℃，反应压强设置为1.3MPa；缩合反应器80内的反应温度设置为70℃，反应压强设置为0.25MPa；加氢反应器120中反应温度设置为78℃，反应压强设置为0.80MPa。
经检测，使用所述系统及工艺后，丙烯转化率99.3％，丁醛转化率99.0％，工艺的合成效率提升5.0％。
总之，与现有技术的丙烯羰基化制辛醇的产生系统相比，本发明的产生系统物料转化率高、能耗低、成本低、安全性高、所需反应温度和压力低、副反应少，值得广泛推广应用。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (10)

  1. 一种辛醇的产生系统，其特征在于，包括：羰基反应器和丁醛分离装置；所述羰基反应器与所述丁醛分离装置相连；所述丁醛分离装置上设置有正丁醛出口，所述正丁醛出口连接有缩合反应器，所述缩合反应器与所述丁醛分离装置间设置有第一再沸器和第一预分散器，所述第一再沸器的气相出口和液相出口均通入所述第一预分散器中；所述丁醛分离装置分离出的正丁醛从所述正丁醛出口中流出，经所述第一再沸器和所述第一预分散器分散成正丁醛气泡后通入所述缩合反应器中；
    所述缩合反应器内设置有微界面发生器，所述微界面发生器与所述第一预分散器相连以将所述正丁醛气泡进一步分散成微米级别的微气泡；所述缩合反应器内部纵向设置有旋转轴，所述旋转轴穿透所述缩合反应器底部连接有电机；所述旋转轴位于所述缩合反应器内的部分设置有多个搅拌桨；所述旋转轴顶部连接有分布圆盘；所述分布圆盘设置在所述微界面发生器的出口处；
    所述分布圆盘呈锥形；所述分布圆盘上均匀分布有多个导向孔以将所述微界面发生器产生的微气泡均匀分布；
    所述缩合反应器的物料出口连接有加氢反应器，所述加氢反应器与所述缩合反应器之间设置有第二再沸器和外置式微气泡发生器，所述缩合反应器产生的辛烯醛经所述第二再沸器分为气相物流和液相物流，气相物流和液相物流均通入所述外置式微气泡发生器中，在所述外置式微气泡发生器中分散成微米级的辛烯醛微气泡后流入所述加氢反应器中；
    所述加氢反应器内设置有内置式微气泡发生器，所述内置式微界面发生器与所述氢气瓶相连；所述氢气瓶与所述内置式微界面发生器之间设置有第二预分散器，所述第二预分散器位于所述加氢反应器外侧；氢气经所述第二预分散器分散为氢气泡后在所述内置式微界面发生器内部再次分散为微米级别的氢气微气泡。
  2. 根据权利要求1所述的辛醇的产生系统，其特征在于，所述第一预分 散器与所述第二预分散器内部均设置有多层分散层，所述分散层由多个不同直径的圆形散粒体堆砌而成。
  3. 根据权利要求1所述的辛醇的产生系统，其特征在于，所述缩合反应器侧壁设置有用于喷射碱液的液体喷射器，所述液体喷射器包括呈半圆形的喷射器主体和均匀布置在所述喷射器主体半圆面上的喷射头；所述液体喷射器沿竖直方向位于所述微界面发生器的下方；所述液体喷射器连接有碱液储罐。
  4. 根据权利要求1所述的辛醇的产生系统，其特征在于，所述加氢反应器内部设置有两个出口相对的气泡分布器，位于上方的所述气泡分布器与所述内置式微气泡发生器相连，位于下方的所述气泡分布器与所述外置式微气泡发生器相连。
  5. 根据权利要求4所述的辛醇的产生系统，其特征在于，所述气泡分布器包括分布器主体和多个喷嘴；多个所述喷嘴倾斜布置在所述分布器主体上以将微气泡均匀分散。
  6. 根据权利要求1所述的辛醇的产生系统，其特征在于，所述羰基反应器的侧壁上依次设置有丙烯进口和合成气进口；所述羰基反应器内设置有两个出口相对的微界面生成器，位于上方的所述微界面生成器与所述丙烯进口相连，位于下方的所述微界面生成器与所述合成气进口相连。
  7. 根据权利要求6所述的辛醇的产生系统，其特征在于，所述羰基反应器的底部设置有溶剂进口；所述羰基反应器的侧壁上还设置有催化剂喷射器，所述催化剂喷射器沿竖直方向设置在两个所述微界面生成器之间。
  8. 根据权利要求6所述的辛醇的产生系统，其特征在于，所述羰基反应器、所述缩合反应器、所述加氢反应器以及所述第二加氢反应器上均连接有用于补充催化剂的催化剂循环装置。
  9. 采用权利要求1-8任一项所述的辛醇的产生系统制备辛醇的方法，其特征在于，包括如下步骤：
    将丙烯和合成气与催化剂混合，进行羟基合成反应，再经过除沫后得到粗 产品，粗产品经分离得到正丁醛；
    正丁醛经微界面破碎后，与碱液进行缩合反应生成辛烯醛，辛烯醛与氢气分别进行微界面破碎后，经加氢反应后得到辛醇粗产品，将所述辛醇粗产品精馏纯化后得到产物辛醇。
  10. 根据权利要求9所述的方法，其特征在于，所述羟基合成反应温度为80-95℃，压力为0.8-1.3MPa；优选的，所述催化剂为铑催化剂；优选的，所述加氢反应器内的反应温度为60-78℃，反应压强为0.50-0.80MPa。
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