CN110526807A - A kind of hydroformylation reaction prepares the continuous reaction apparatus and method of aldehyde - Google Patents
A kind of hydroformylation reaction prepares the continuous reaction apparatus and method of aldehyde Download PDFInfo
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- CN110526807A CN110526807A CN201810516609.2A CN201810516609A CN110526807A CN 110526807 A CN110526807 A CN 110526807A CN 201810516609 A CN201810516609 A CN 201810516609A CN 110526807 A CN110526807 A CN 110526807A
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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
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
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- 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
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- 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
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
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- 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
- Y02P20/584—Recycling of catalysts
Abstract
This application discloses the continuous reaction apparatus that a kind of hydroformylation reaction prepares aldehyde, the reaction unit includes reaction member, separative unit, cycling element；The cycling element is between the reaction member and separative unit；The reaction member is connect with the separative unit；Catalyst is recycled between the reaction member and the separative unit by cycling element.Disclosed herein as well is the methods for preparing aldehyde using the reaction unit; catalyst can be separated without external equipment can continual continuous recycling; it can be realized continuous production aldehyde; and reaction heat can be quickly moved out; be conducive to the progress of hydroformylation reaction; feed stock conversion is high, and target product yield is high, and product is just different than high.
Description
Technical field
The continuous reaction apparatus of aldehyde is prepared this application involves a kind of hydroformylation reaction and the side of aldehyde is prepared using the device
Method belongs to chemical and the field of chemical synthesis.
Background technique
Hydroformylation reaction is alkene and synthesis gas (CO and H2) generate under transition metal complex catalysts effect than former
The aldehyde of alkene bull point or the reaction process of alcohol.Thus aldehyde, alcohol and its derivative produced is widely used as plasticizer, knits
Object additive, surfactant, solvent and fragrance etc..This kind of reaction is by O. rowland (O.Roelen) earliest in 1938 Nian De
Rule chemical company, state is engaged in be found in F- T synthesis, obtains propionic aldehyde and second diketone by synthesis gas and ethylene, and apply quickly
In the technique of propylene octyl alconyl.However homogeneous complex catalysis technique because product separate, catalyst separation process complexity always by
To limitation, the research of aqueous biphasic catalyst system and supported catalyst system is in progress in recent years.
The anti-method of industrial production hydroformylation process has ten several at present, and most of using aldehyde, alcohol as major product.Tool
It is representational to have German Rule chemical company, BASF AG, chemical conversion company, Mitsubishi, Shell Co. Ltd, UCC, RCH/RP etc..Moral
The propylene of Rule chemical company, state is that raw material produces 2- base second hexanol by-product octyl alconyl technique, using cobalt-base catalyst, reacts item
Part is 100~160 degree of temperature, 20~30MPa.To keep catalyst activity and higher conversion ratio, which must be using very
High synthesis atmospheric pressure and higher temperature, and products obtained therefrom is just different relatively low, side reaction is more, and integrated artistic energy consumption is high, urges
Agent recycling and regenerative process are complicated.The technical process of BASF AG is similar to German Rule, uses higher reaction
Temperature is to improve the speed of formylation reaction, but side reaction increases more therewith.Chemical conversion company, Mitsubishi changes technical process
Into using automatic control and lower temperature (100~150 degree) makes reactor temperature uniform, is with production of propylene butyraldehyde
Example, selectively can achieve 85~88%, just different to compare 4:1；Shortcoming is reaction pressure still very high (15~30MPa), is urged
Agent separating effect is complicated.The catalyst for using trialkyl phosphine and carbonyl cobalt to be coordinated of Shell Co. Ltd, stability is high, operation
Pressure is low (2.0~5.0MPa), and hydrogenation activity is high, and n-alkanol content is high in product；But the hydrogen formyl of modified cobalt phosphine catalyst
Change reactivity ratio's traditional oxo cobalt and want much lower, only 1/5 to the 1/6 of carbonyl cobalt, while alkane by-product greatly increases, it can
Up to 10~15%.UCC technique by American Association Carbide and the electric corporation Dai Wei, Britain and the rich company's joint development of Zhuan Xinwan,
Using excessive triphenylphosphine as ligand, triphenyl phasphine carbonyl hydrogenation Rh is the system of catalyst, and reaction can be made relatively mild
Under conditions of carry out, operating pressure substantially reduces, the disadvantage is that rhodium is expensive, and catalyst poisoning inactivates, and this technique only limits
In low-carbon alkene as raw material, ethylene, production of propylene propionic aldehyde, butyraldehyde device.The Core Superiority of RCH/RP technique be using
The separation process of catalyst has been completed when reaction product leaves reaction kettle in a kind of special reaction kettle, and catalyst stays always
In reaction kettle, but disadvantage is that reaction temperature and reaction pressure are higher, has a large amount of water to recycle, energy consumption is high.
Summary of the invention
According to the one aspect of the application, the continuous reaction apparatus that a kind of hydroformylation reaction prepares aldehyde is provided, this is anti-
Answer in device catalyst can be separated without external equipment can continual continuous recycling, can be realized continuous life
Aldehyde is produced, and reaction heat can be quickly moved out, is conducive to the progress of hydroformylation reaction.
The reaction unit includes reaction member, separative unit, cycling element；
The cycling element is between the reaction member and separative unit；
The reaction member is connect with the separative unit；
Catalyst is recycled between the reaction member and the separative unit by the cycling element.
Optionally, the reaction member includes discharge port；
The discharge port is connect with the feed inlet I of the separative unit.
Optionally, the discharge port is located at the top of the reaction member.
Optionally, the separative unit includes catalyst outlet；
The catalyst outlet is connect with the cycling element.
Optionally, the catalyst outlet is located at the bottom of the cycling element.
Optionally, the separative unit includes catalyst feeds II；
The catalyst feeds II is located at the top of the catalyst outlet.
Optionally, the reaction member includes feed inlet III；
The feed inlet III is connect with the cycling element.
Optionally, the feed inlet III is connect with the cycling element by entry mixers.
Optionally, reaction raw materials and catalyst enter the feed inlet III by the entry mixers.
Optionally, the reaction raw materials include CO, H2And alkene.
Optionally, the separative unit includes product extraction mouth.
Optionally, the product extraction mouth is that oil mutually produces mouth.
Optionally, the separative unit includes periodic off-gases outlet.
Optionally, the separative unit includes condensate liquid import；
Cooling liquid enters the separative unit by the condensate liquid import in the periodic off-gases condenser.
Optionally, gas cooling in the periodic off-gases condenser is handled by periodic off-gases reducing internal heat cabinet.
Optionally, the reaction member is reactor；
The separative unit is oil water separator；
The cycling element is circulating pump.
Optionally, the reactor is solution-air-liquid phase reactor；
The reactor is shell and tube reactor；
The operation medium of shell is coolant liquid in the shell and tube reactor；
Water phase is catalyst aqueous solution in the oil water separator, and oil mutually includes reaction product aldehyde；
Any one of the circulating pump in centrifugal pump, plunger pump, screw pump and diaphragm pump.
Optionally, described device includes: reactor, oil water separator and circulating pump；
The reactor is solution-air-liquid phase reactor；
The reactor is shell and tube reactor；
The operation medium of shell is coolant liquid in the shell and tube reactor；
The reactor includes feed inlet III and discharge port；
The oil water separator includes that oil mutually produces mouth, periodic off-gases outlet, feed inlet I, catalyst feeds II, catalyst
Outlet and condensate liquid import；
The position of the catalyst feeds II is higher than the catalyst outlet；
The periodic off-gases outlet is connect with periodic off-gases condenser；
Cooling liquid enters the separative unit by the condensate liquid import in the periodic off-gases condenser；It is described to speed
Cooling gas is handled by periodic off-gases reducing internal heat cabinet in deflation condenser；
The feed inlet I is reaction mixture feed mouth, and the discharge port is reaction mixture discharge port；
The discharge port is connect with the feed inlet I；
The catalyst outlet is connect with the circulating pump；
The feed inlet III is connect by entry mixers with the circulating pump；
Described CO, H2It is mixed with alkene by the entry mixers, enters the reaction by the feed inlet III
Device.
Optionally, described device prepares aldehyde for alpha-olefin hydroformylation reaction.
According to the another aspect of the application, a kind of method that hydroformylation reaction prepares aldehyde is provided, which is characterized in that institute
The raw material for stating method includes alkene, CO and hydrogen, using the aqueous solution of rhodium-containing and its ligand as catalyst aqueous solution, using above-mentioned
One hydroformylation reaction prepares the continuous reaction apparatus of aldehyde, and aldehyde is prepared.
Optionally, the method includes at least:
(a) catalyst aqueous solution is added to separative unit, opens cycling element, catalyst aqueous solution passes through cycling element
It is recycled between reactor and oil water separator；
(b) reaction raw materials are passed into reaction member；
(c) material reacted in the reaction member passes through separative unit, is mutually separated and catalyst circulation.
Optionally, the method at least includes the following steps:
1) it is added catalyst aqueous solution as water phase in oil water separator, starts circulating pump, establish reactor and grease
Circulation between separator；
2) after the stable circulation, alkene, carbon monoxide and hydrogen, and the conduct after entry mixers mixing are continuously passed through
Organic phase is passed through the reaction mixture feed mouth of reactor bottom, and hydroformylation reaction occurs under the action of catalyst, and reaction is mixed
It closes object to be discharged by reactor head discharge port, into oil water separator；
3) reaction mixture separates in oil water separator, and water phase includes catalyst aqueous solution, is pumped back to reaction through circulation
Device continues to use, and oil mutually includes product aldehyde and unreacted raw material, continuous extraction.
Optionally, catalyst aqueous solution described in step 1) is the aqueous solution of the water-soluble phosphine ligand containing rhodium；It is described to urge
The content of rhodium is 200~300ppm in agent aqueous solution, and water-soluble phosphine ligand concentration is 4.8%~7.2%.
The volume ratio respectively fed in the method are as follows:
Water phase: organic phase=3~5:1；H2: CO=1~2:1.
Optionally, the volume ratio respectively fed in the method are as follows:
Water phase: organic phase=3~5:1；H2: CO=1.05:1.
Optionally, reaction temperature described in step 2) is 30~220 DEG C, and reaction pressure is 0.5~5.0MPa.
Optionally, the reaction temperature is 50~180 DEG C, and reaction pressure is 0.6~4.8MPa.
In the application, multiphase refers to mutually non-miscible or only partially miscible two or more phases (or stream phase), such as but not
It is limited to liquid phase (inorganic liquid phase, organic liquid phase), gas phase, solid phase etc..
As a kind of specific embodiment, reactor described herein includes shell-side cylinder and tube bank；
The tube bank is located inside the shell-side cylinder, and the inside of the inner space of the tube bank and the shell-side cylinder
Space is not connected；
The both ends of the tube bank are respectively provided with inlet port and outlet port, the feed inlet and the discharge port and the shell side
It is communicated outside cylinder；
The shell-side cylinder is equipped with baffle plate.
Optionally, the shell-side cylinder is equipped with cooling liquid inlet, cooling liquid outlet and 2-50 block baffle plate；
Wherein, the cooling liquid inlet and cooling liquid outlet are arranged on the outer wall of the shell-side cylinder.
Optionally, the baffle plate is horizontally disposed on the inner wall of the shell-side cylinder, and each baffle plate is arranged in parallel, respectively
The spacing of baffle plate is 10-1000mm.
It in the application, may be implemented quickly to reduce phlegm and internal heat by the coolant liquid circulated in the shell-side cylinder, and then improve
The selectivity of reaction product aldehyde.
In a preferred embodiment of the present invention, the shell-side cylinder outer wall is equipped with cooling liquid inlet, coolant liquid
Outlet and 2-50 block baffle plate, such as 2 pieces, 5 pieces, 10 pieces, 20 pieces, 25 pieces, 30 pieces, 35 pieces, 40 pieces, 45 pieces, 50 pieces and with
Any point value in upper each point value in the range of any two composition.
In the application, the effect of the baffle plate is to increase cooling liquid speed, strengthens and moves the thermal efficiency.Between each baffle plate
Away from what is formed for any two in 10-1000mm, such as 10mm, 100mm, 200mm, 500mm, 1000mm, and the above point value
Any point value in range.Spacing between each baffle plate can be equal or differs, under preferable case, between each baffle plate
Spacing it is equal.
Optionally, the baffle plate is equipped with aperture, and the aperture of the aperture is 1-100mm, and arrangement mode is positive triangle
Shape, square or both any combination, percent opening 0.1%-20%.
In a preferred embodiment of the present invention, the aperture of aperture is 1-100mm, such as 1mm on the baffle plate,
10mm, 20mm, 50mm, 100mm and more than any two composition in each point value range in other point values, arrangement mode
For equilateral triangle, square or both any combination, percent opening 0.1%-20%.
Optionally, the diameter of the tube bank is 5-500mm, length 500-10000mm.
Optionally, distributor is equipped in the tube bank, the distributor includes distributor supervisor, distributor branch pipes and distribution
Cap.
The tube bank includes 1-1000 root reaction tube, in the tube bank arrangement mode of each reaction tube be selected from equilateral triangle,
It is at least one of square and single-row.
In a preferred embodiment of the present invention, it is described tube bank include 1-1000 root reaction tube, such as 1,10,
Other point values in the range of any two composition in 100,500,1000, and above each point value.
Optionally, dispersed components thereof is equipped in the reaction tube, the quantity of dispersed components thereof is 1-1000 in every reaction tube；
The specific surface area of the dispersed components thereof is 100-1000m2/m3, voidage is between 0.01-0.1；Length is in 10-
Between 1000mm.
In a preferred embodiment of the present invention, dispersed components thereof, dispersion in every reaction tube are equipped in the tube bank
The quantity of component is 1-1000, such as 1,10,100,500,1000, and any two in above each point value
Other point values in the range of a composition.
In the application, the connected applications of the tube bank and the dispersed components thereof can farthest realize the equal of reactant
Even dispersion improves the defect of traditional reactor and can be improved the selectivity of conversion ratio and product aldehyde.
The beneficial effect that the application can generate includes:
1) a kind of alpha-olefin hydroformylation reaction provided herein prepares the continuous reaction system and method for aldehyde, catalysis
Agent can be separated without external equipment can continual continuous recycling.
2) a kind of alpha-olefin hydroformylation reaction provided herein prepares the continuous reaction system and method for aldehyde, can
It realizes continuous production aldehyde, and reaction heat can be quickly moved out, be conducive to the progress of hydroformylation reaction.
3) a kind of alpha-olefin hydroformylation reaction provided herein prepares the continuous reaction system and method for aldehyde, has
Feed stock conversion is high, and target product yield is high, and product is just different than high advantage.
Detailed description of the invention
Fig. 1 is the continuous reaction system signal that alpha-olefin hydroformylation reaction prepares aldehyde in a kind of embodiment of the application
Figure.
Component and reference signs list:
1- reactor 2- oil water separator 3- periodic off-gases condenser
4- circulating pump 5- entry mixers 6- catalyst feeds
7- feed inlet 8- discharge port 9- reaction mixture feed mouth
10- periodic off-gases export 11- condensate liquid import 12- oil mutually extraction mouth
13- catalyst outlet
Specific embodiment
The application is described in detail below with reference to embodiment and attached drawing, attached drawing, embodiment and related description are intended to more clearly visible right
The reaction system and method for the application is illustrated, rather than limits the application.
In embodiments herein, the conversion ratio of alpha-olefin and the selectivity of product aldehyde are all based on carbon molal quantity and are counted
It calculates, calculation method is as follows:
Fig. 1 is the continuous reaction system signal that alpha-olefin hydroformylation reaction prepares aldehyde in a kind of embodiment of the application
Figure.
This application provides the continuous reaction system that a kind of alpha-olefin hydroformylation reaction prepares aldehyde, the reaction system packets
Include reactor 1 interconnected, oil water separator 2, periodic off-gases condenser 3, circulating pump 4, entry mixers 5.
In the application, circulation is connected and is formed by circulating pump 4 between reactor 1 and oil water separator 2, in application, can
The first feeding catalyst aqueous solution into oil water separator 2 drives catalyst aqueous solution in reactor 1 and grease point with circulating pump 4
From circulation is formed between device 2, reach after stablizing, then into reaction raw materials, starts hydroformylation reaction, continuous feed, discharging, reaction
Mixture separates in oil water separator 2, and water phase is catalyst aqueous solution, is recycled, and oil mutually includes product aldehyde.
In the preferred embodiment of the application, the reactor is solution-air-liquid phase reactor, including cylinder；
There is solution-air-liquid dispersion inner member in cylinder；Production aldehyde suitable for 50~180 DEG C of temperature, under the conditions of 0.5~5.0MPa of pressure
Hydroformylation reaction；
In the preferred embodiment of the application, the reactor is solution-air-liquid phase reactor, reactor packet
Include shell-side cylinder, end socket and tube bank；Device (connected and formed with branch pipe and distribution cap by distribution supervisor) is distributed in tube bank；It is suitable for
50~180 DEG C of temperature, the hydroformylation reaction of the production aldehyde under the conditions of 0.5~5.0MPa of pressure.
In the preferred embodiment of the application, the first reactor includes shell-side cylinder and tube side, wherein institute
The operation medium II for stating shell-side cylinder is coolant liquid, and coolant liquid can be one of water, salt water or glycol water, institute
The operation medium III for stating tube bank includes material solution, catalyst aqueous solution, CO and H2Gaseous mixture and reaction product aldehyde.
The cooling of reactor shell-side cylinder is realized by coolant liquid and quickly removes reaction heat, and then improves the choosing of product aldehyde
Selecting property.
In the preferred embodiment of the application, the shell-side cylinder be equipped with cooling liquid inlet, cooling liquid outlet and
2-50 block baffle plate 20, for example, 2 pieces, 5 pieces, 10 pieces, 20 pieces, 25 pieces, 30 pieces, 35 pieces, 40 pieces, 45 pieces, 50 pieces and more than it is each
Any point value in range that any two form in point value.The effect of baffle plate is to increase cooling liquid speed, strengthens and move heat
Efficiency.
In the preferred embodiment of the application, the cooling liquid inlet and cooling liquid outlet are arranged in reactor 2
On the outer wall of shell-side cylinder；The lower part of shell-side cylinder is arranged in the import of coolant liquid, and coolant liquid enters shell-side cylinder by import, and
It is flowed in shell-side cylinder, has the function that cooling reaction system, finally from the cooling liquid outlet that shell-side cylinder top is arranged in
Place's outflow.
In the preferred embodiment of the application, the baffle plate is horizontally disposed at the reactor shell-side cylinder
Inner wall on, baffle plate is arranged in parallel, and the spacing of each baffle plate is 10-1000mm, such as 10mm, 100mm, 200mm, 500mm,
Any point value in range that any two form in 1000mm, and the above point value.Spacing between each baffle plate can phase
Deng that can not also wait, under preferable case, the spacing between each baffle plate is equal.
In the preferred embodiment of the application, the baffle plate is equipped with aperture, and the aperture of the aperture is 1-
100mm, such as 1mm, 10mm, 20mm, 50mm, 100mm and more than any two composition in each point value range in its
His point value, arrangement mode are equilateral triangle, square or both any combination, percent opening 0.1%-20%.
In the preferred embodiment of the application, material is introduced and is restrained by the end socket feed inlet；The end socket goes out
Material mouth draws tube bank discharging.
In the preferred embodiment of the application, it is described tube bank include 1-1000 root reaction tube, such as 1,10,
Other point values in the range of any two composition in 100,500,1000, and above each point value, the tube bank
Diameter be 5-500mm, length 500-10000mm, the arrangement mode of each reaction tube is selected from equilateral triangle, just in the tube bank
It is at least one of rectangular and single-row.
In the preferred embodiment of the application, it is equipped with dispersed components thereof in the reaction tube, divides in every reactor tank
The quantity for dissipating component is 1-1000, such as any in 1,10,100,500,1000, and above each point value
Other point values in the range of two compositions；The specific surface area of the dispersed components thereof is 100-1000m2/m3, voidage is in 0.01-
0.1；Length is in 10-1000mm.
The connected applications of tube bank and dispersed components thereof can farthest realize the evenly dispersed of reactant, and it is anti-to improve tradition
It answers the defect of kettle and can be improved the selectivity of process efficiency and product aldehyde.
In the preferred embodiment of the application, circulating pump 4 is equipped between the reactor 1 and oil water separator 2,
The circulating pump 4 can drive response mixture recycled between reactor 1 and oil water separator 2.
In the preferred embodiment of the application, the circulating pump 4 be selected from centrifugal pump, plunger pump, screw pump and every
Any one in membrane pump.
In the preferred embodiment of the application, the system also includes mixer 5, the setting of mixer 5 exists
Between reactor feed mouth 7 and the outlet of circulating pump 4, reaction raw materials are sufficiently pre-mixed.
Embodiment 1
Using process shown in FIG. 1, process conditions are as follows:
Catalyst aqueous solution is formed using the proportion of example 1 in publication CN101462932A.
Reaction temperature: 80 DEG C, reaction pressure is 2.5MPa (A)；
Reactor feed pig's tongue part:
Catalyst aqueous solution feed rate: 10m3/ hour；
Ethylene feed flow: 25Nm3/ hour；
CO+H2Feed rate: 50Nm3/ hour；
CO:H2=1:1 (molar ratio)；
Discharge result at discharge port 3:
Conversion of ethylene: 98%；
Propionic aldehyde yield: 98%.
The present embodiment selectively realizes vinyl group hydroformylation with the high propionic aldehyde of 98% high conversion of ethylene and 98%
Reaction prepares the production process of propionic aldehyde.
Embodiment 2
Using process shown in FIG. 1, process conditions are as follows:
Catalyst aqueous solution is formed using the proportion of example 5 in publication CN101462932A.
Reaction temperature: 110 DEG C, reaction pressure is 2.5MPa (A)；
Reactor feed pig's tongue part:
Catalyst aqueous solution feed rate: 10m3/ hour；
Propylene feed flow: 50kg/ hours；
CO+H2Feed rate: 50Nm3/ hour；
CO:H2=1:1 (molar ratio)；
Discharge result at discharge port 3:
Propylene conversion: 98%；
N-butanal yield: 97%；
N-butanal: isobutylaldehyde=40:1 (molar ratio).
The present embodiment selectively realizes propylene hydrocarbon hydrogen formyl with the high n-butanal of 98% high propylene conversion and 97%
Change the production process that reaction prepares n-butanal.
Embodiment 3
Using process shown in FIG. 1, process conditions are as follows:
Catalyst aqueous solution is formed using the proportion of example 10 in publication CN101462932A.
Reaction temperature: 120 DEG C, reaction pressure is 3.0MPa (A)；
Reactor feed pig's tongue part:
Catalyst aqueous solution feed rate: 10m3/ hour；
1- butene feed flow: 60kg/ hours；
CO+H2Feed rate: 50Nm3/ hour；
CO:H2=1:1 (molar ratio)；
Discharge result at discharge port 3:
1- butene conversion: 97%；
Valeraldehyde yield: 97%；
Valeraldehyde: isopentyl aldehyde=60:1 (molar ratio).
The present embodiment selectively realizes 1- butylene hydrocarbon hydrogen with 97% high 1- butene conversion and 97% high valeraldehyde
Formylation reaction prepares the production process of valeraldehyde.
Embodiment 4
Using process shown in FIG. 1, process conditions are as follows:
Catalyst aqueous solution is formed using the proportion of embodiment 32 in publication CN106000470.
Reaction temperature: 80 DEG C, reaction pressure is 2.0MPa (A)；
Reactor feed pig's tongue part:
Catalyst aqueous solution feed rate: 10m3/ hour；
1- octene feed rate: 100kg/ hours；
CO+H2Feed rate: 50Nm3/ hour；
CO:H2=1:1 (molar ratio)；
Discharge result at discharge port 3:
1- octene conversion: 97.2%；
N-nonyl aldehyde yield: 95%；
N-nonyl aldehyde: isononyl aldehyde=50:1 (molar ratio).
The present embodiment selectively realizes 1- octene hydrocarbon with 97.2% high 1- octene conversion and 95% high n-nonyl aldehyde
Hydroformylation reaction prepares the production process of n-nonyl aldehyde.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (10)
1. the continuous reaction apparatus that a kind of hydroformylation reaction prepares aldehyde, which is characterized in that the reaction unit includes that reaction is single
Member, separative unit, cycling element；
The cycling element is between the reaction member and separative unit；
The reaction member is connect with the separative unit；
Catalyst is recycled between the reaction member and the separative unit by the cycling element.
2. the apparatus according to claim 1, which is characterized in that the reaction member includes discharge port；
The discharge port is connect with the feed inlet I of the separative unit；
Preferably, the discharge port is located at the top of the reaction member.
3. the apparatus according to claim 1, which is characterized in that the separative unit includes catalyst outlet；The catalysis
Agent outlet is connect with the cycling element；
Preferably, the catalyst outlet is located at the bottom of the cycling element；
It is further preferred that the separative unit includes catalyst feeds II；The catalyst feeds II is located at described urge
The top of agent outlet.
4. the apparatus according to claim 1, which is characterized in that the reaction member includes feed inlet III；
The feed inlet III is connect with the cycling element；
Preferably, the feed inlet III is connect with the cycling element by entry mixers；
It is further preferred that reaction raw materials and catalyst enter the feed inlet III by the entry mixers；
It is further preferred that the reaction raw materials include CO, H2And alkene.
5. the apparatus according to claim 1, which is characterized in that the separative unit includes product extraction mouth；
Preferably, the product extraction mouth is that oil mutually produces mouth；
Preferably, the separative unit includes periodic off-gases outlet；
It is further preferred that the separative unit includes condensate liquid import；Cooling liquid passes through in the periodic off-gases condenser
The condensate liquid import enters the separative unit；
It is further preferred that gas cooling in the periodic off-gases condenser is handled by periodic off-gases reducing internal heat cabinet.
6. the apparatus according to claim 1, which is characterized in that the reaction member is reactor；
The separative unit is oil water separator；
The cycling element is circulating pump；
Preferably, the reactor is solution-air-liquid phase reactor；
The reactor is shell and tube reactor；
The operation medium of shell is coolant liquid in the shell and tube reactor；
Water phase is catalyst aqueous solution in the oil water separator, and oil mutually includes reaction product aldehyde；
Any one of the circulating pump in centrifugal pump, plunger pump, screw pump and diaphragm pump.
7. the apparatus according to claim 1, which is characterized in that described device includes: reactor, oil water separator and circulation
Pump；
The reactor is solution-air-liquid phase reactor；
The reactor is shell and tube reactor；
The operation medium of shell is coolant liquid in the shell and tube reactor；
The reactor includes feed inlet III and discharge port；
The oil water separator includes that oil mutually produces mouth, periodic off-gases outlet, feed inlet I, catalyst feeds II, catalyst outlet
With condensate liquid import；
The position of the catalyst feeds II is higher than the catalyst outlet；
The periodic off-gases outlet is connect with periodic off-gases condenser；
Cooling liquid enters the separative unit by the condensate liquid import in the periodic off-gases condenser；The periodic off-gases
Cooling gas is handled by periodic off-gases reducing internal heat cabinet in condenser；
The feed inlet I is reaction mixture feed mouth, and the discharge port is reaction mixture discharge port；
The discharge port is connect with the feed inlet I；
The catalyst outlet is connect with the circulating pump；
The feed inlet III is connect by entry mixers with the circulating pump；
Described CO, H2It is mixed with alkene by the entry mixers, enters the reactor by the feed inlet III；
Preferably, described device prepares aldehyde for alpha-olefin hydroformylation reaction.
8. a kind of method that hydroformylation reaction prepares aldehyde, which is characterized in that the raw material of the method includes alkene, CO and hydrogen
Gas, using the aqueous solution of rhodium-containing and its ligand as catalyst aqueous solution, using hydrogen first described in any one of claim 1 to 7
Acylation reaction prepares the continuous reaction apparatus of aldehyde, and aldehyde is prepared.
9. according to the method described in claim 8, it is characterized in that, the method includes at least:
(a) catalyst aqueous solution is added to separative unit, opens cycling element, catalyst aqueous solution is by cycling element anti-
It answers and is recycled between device and oil water separator；
(b) reaction raw materials are passed into reaction member；
(c) material reacted in the reaction member passes through separative unit, is mutually separated and catalyst circulation；
Preferably, the method at least includes the following steps:
1) it is added catalyst aqueous solution as water phase in oil water separator, starts circulating pump, establish reactor and water-oil separating
Circulation between device；
2) after the stable circulation, it is continuously passed through alkene, carbon monoxide and hydrogen, and as organic after entry mixers mixing
It is mutually passed through the reaction mixture feed mouth of reactor bottom, hydroformylation reaction, reaction mixture occur under the action of catalyst
It is discharged by reactor head discharge port, into oil water separator；
3) reaction mixture separates in oil water separator, water phase include catalyst aqueous solution, through circulation be pumped back to reactor after
Continuous to use, oil is continuous to produce mutually comprising product aldehyde and unreacted raw material.
10. according to the method described in claim 9, it is characterized in that, catalyst aqueous solution described in step 1) is to contain rhodium
The aqueous solution of water-soluble phosphine ligand；The content of rhodium is 200~300ppm, water-soluble phosphine ligand concentration in the catalyst aqueous solution
It is 4.8%~7.2%；
The volume ratio respectively fed in the method are as follows:
Water phase: organic phase=3~5:1；H2: CO=1~2:1；
Preferably, the volume ratio respectively fed in the method are as follows:
Water phase: organic phase=3~5:1；H2: CO=1.05:1；
Preferably, reaction temperature described in step 2) is 30~220 DEG C, and reaction pressure is 0.5~5.0MPa；
It is further preferred that reaction temperature described in step 2) is 50~180 DEG C, reaction pressure is 0.6~4.8MPa.
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| CN113045391A (en) * | 2021-03-02 | 2021-06-29 | 上海簇睿低碳能源技术有限公司 | Gas-liquid dual-cycle hydroformylation continuous reaction device and process |
| CN113209931A (en) * | 2021-05-26 | 2021-08-06 | 中国海洋石油集团有限公司 | Olefin hydroformylation reaction equipment and reaction method |
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| CN101774912A (en) * | 2010-02-21 | 2010-07-14 | 南京荣欣化工有限公司 | Technology for producing acetic ester |
| CN105418394A (en) * | 2015-10-28 | 2016-03-23 | 万华化学集团股份有限公司 | Method for preparing aldehyde compound by olefin hydroformylation |
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| DE19925384A1 (en) * | 1999-06-02 | 2000-12-07 | Oxeno Olefinchemie Gmbh | Process for the catalytic implementation of multiphase reactions, especially hydroformylations |
| CN101768059A (en) * | 2008-12-19 | 2010-07-07 | 四川省达科特能源科技有限公司 | Method for continuously formylatelating monoolefine and hydrogen by adopting static mixing reactor |
| CN101462932B (en) * | 2009-01-21 | 2012-04-18 | 成都欣华源科技有限责任公司 | Method for preparing aldehyde by hydroformylation of light olefins |
| CN106000470B (en) * | 2016-06-06 | 2018-12-14 | 四川大学 | Catalyst and its preparation method and application for hydroformylation of olefin |
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| CN101774912A (en) * | 2010-02-21 | 2010-07-14 | 南京荣欣化工有限公司 | Technology for producing acetic ester |
| CN105418394A (en) * | 2015-10-28 | 2016-03-23 | 万华化学集团股份有限公司 | Method for preparing aldehyde compound by olefin hydroformylation |
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| CN113045391A (en) * | 2021-03-02 | 2021-06-29 | 上海簇睿低碳能源技术有限公司 | Gas-liquid dual-cycle hydroformylation continuous reaction device and process |
| CN113045391B (en) * | 2021-03-02 | 2023-03-28 | 上海簇睿低碳能源技术有限公司 | Gas-liquid dual-cycle hydroformylation continuous reaction device and process |
| CN113209931A (en) * | 2021-05-26 | 2021-08-06 | 中国海洋石油集团有限公司 | Olefin hydroformylation reaction equipment and reaction method |
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