CN110526807B - Continuous reaction device and method for preparing aldehyde through hydroformylation reaction - Google Patents
Continuous reaction device and method for preparing aldehyde through hydroformylation reaction Download PDFInfo
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- CN110526807B CN110526807B CN201810516609.2A CN201810516609A CN110526807B CN 110526807 B CN110526807 B CN 110526807B CN 201810516609 A CN201810516609 A CN 201810516609A CN 110526807 B CN110526807 B CN 110526807B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- C07—ORGANIC CHEMISTRY
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- 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
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- 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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Abstract
The application discloses a continuous reaction device for preparing aldehyde by hydroformylation reaction, which comprises a reaction unit, a separation unit and a circulation unit; the circulation unit is positioned between the reaction unit and the separation unit; the reaction unit is connected with the separation unit; the catalyst is circulated between the reaction unit and the separation unit by a circulation unit. The application also discloses a method for preparing aldehyde by adopting the reaction device, the catalyst can be uninterruptedly and continuously recycled without being separated by external equipment, continuous aldehyde production can be realized, reaction heat can be quickly removed, hydroformylation reaction can be favorably carried out, the raw material conversion rate is high, the yield of target products is high, and the product normal-to-iso ratio is high.
Description
Technical Field
The application relates to a continuous reaction device for preparing aldehyde through hydroformylation reaction and a method for preparing aldehyde by adopting the continuous reaction device, belonging to the fields of chemical engineering and chemical synthesis.
Background
Hydroformylation of olefins with synthesis gas (CO and H)2) The reaction process of generating aldehyde or alcohol with one molecule more than the original olefin under the action of transition metal complex catalyst. The aldehydes, alcohols, and derivatives thereof thus produced are used in large amounts as plasticizers, fabric additives, surfactants, solvents, perfumes, and the like. This type of reaction was first discovered in 1938 by o.roland (o.roelen) in fischer-tropsch synthesis in german luer chemical company, leading to propionaldehyde and ethylene dione from synthesis gas and ethylene, and was soon applied to the process of propylene to butanol and octanol. However, the homogeneous phase complex catalysis process is always limited due to the complex processes of product separation and catalyst separation, and the research on water-organic two-phase catalysis systems and supported catalysis systems has been advanced in recent years.
At present, over ten methods for industrially producing a hydroformylation process are available, and most of the methods take aldehyde and alcohol as main products. Representative examples are German luer chemical company, Basff company, Mitsubishi chemical company, Shell company, UCC, RCH/RP, and the like. A process for producing 2-ethylhexanol and a byproduct butanol and octanol by using propylene as a raw material from German Ruhr chemical company uses a cobalt-based catalyst, and the reaction conditions are that the temperature is 100-160 ℃ and the pressure is 20-30 MPa. In order to keep the activity and the higher conversion rate of the catalyst, the process must adopt higher synthesis gas pressure and higher temperature, the positive-to-differential ratio of the obtained product is lower, the side reactions are more, the energy consumption of the whole process is high, and the catalyst recovery and regeneration process is complicated. The Pasteur process is similar to that of German luer, with higher reaction temperatures being used to increase the rate of formylation, but with a concomitant increase in side reactions. The Mitsubishi chemical company improves the process, adopts automatic control and lower temperature (100-150 ℃) to ensure that the temperature in the reaction kettle is uniform, takes the production of butyraldehyde by propylene as an example, the selectivity can reach 85-88 percent, and the normal-to-iso ratio is 4: 1; the defects are that the reaction pressure is still very high (15-30 MPa), and the catalyst separation effect is complex. The catalyst coordinated by trialkyl phosphine and cobalt carbonyl is used by Shell company, so that the stability is high, the operation pressure is low (2.0-5.0 MPa), the hydrogenation activity is high, and the normal alcohol content in the product is high; however, the hydroformylation reaction activity of the modified cobalt-phosphine catalyst is much lower than that of the traditional cobalt carbonyl, only 1/5-1/6 of the cobalt carbonyl is needed, and alkane byproducts are greatly increased and can reach 10-15%. The UCC process is developed by United states of America combined carbonization company, British David electric company and Zhuangxinwan Feng company, a system which adopts a large amount of excess triphenylphosphine as ligand and triphenylphosphine carbonyl rhodium hydride as catalyst is adopted, so that the reaction can be carried out under a mild condition, the operation pressure is greatly reduced, the defects are that the price of rhodium is high, the catalyst is poisoned and inactivated, and the process is only limited to a device which uses low-carbon olefin as raw material and uses ethylene and propylene to produce propionaldehyde and butyraldehyde. The RCH/RP process has the core advantages that a special reaction kettle is adopted, when reaction products leave the reaction kettle, the separation process of the catalyst is completed, and the catalyst is always remained in the reaction kettle, but the RCH/RP process has the defects of high reaction temperature and reaction pressure, large water circulation and high energy consumption.
Disclosure of Invention
According to one aspect of the application, a continuous reaction device for preparing aldehyde by hydroformylation is provided, wherein a catalyst in the reaction device can be continuously recycled without being separated by external equipment, continuous aldehyde production can be realized, reaction heat can be quickly removed, and the hydroformylation reaction is favorably carried out.
The reaction device comprises a reaction unit, a separation unit and a circulation unit;
the circulation unit is positioned between the reaction unit and the separation unit;
the reaction unit is connected with the separation unit;
the catalyst is circulated between the reaction unit and the separation unit by the circulation unit.
Optionally, the reaction unit comprises a discharge port;
the discharge hole is connected with the feed inlet I of the separation unit.
Optionally, the discharge port is located at an upper portion of the reaction unit.
Optionally, the separation unit comprises a catalyst outlet;
the catalyst outlet is connected to the circulation unit.
Optionally, the catalyst outlet is located at the bottom of the circulation unit.
Optionally, the separation unit comprises a catalyst feed inlet II;
the catalyst feed inlet II is positioned at the upper part of the catalyst outlet.
Optionally, the reaction unit comprises a feed inlet III;
the feed inlet III is connected with the circulating unit.
Optionally, the feed port III is connected to the circulation unit via a feed mixer.
Optionally, the reaction raw material and the catalyst enter the feed inlet III through the feed mixer.
Optionally, the reaction raw materials comprise CO and H2And an olefin.
Optionally, the separation unit comprises a product withdrawal port.
Optionally, the product withdrawal port is an oil phase withdrawal port.
Optionally, the separation unit comprises a purge gas outlet.
Optionally, the separation unit comprises a condensate inlet;
the cooled liquid in the purge gas condenser enters the separation unit through the condensate inlet.
Optionally, the cooled gas in the purge gas condenser is processed through a purge gas flare cabinet.
Optionally, the reaction unit is a reactor;
the separation unit is an oil-water separator;
the circulating unit is a circulating pump.
Optionally, the reactor is a gas-liquid three-phase reactor;
the reactor is a tubular reactor;
the operating medium of the shell in the tubular reactor is cooling liquid;
the water phase in the oil-water separator is a catalyst water solution, and the oil phase comprises a reaction product aldehyde;
the circulating pump is selected from any one of a centrifugal pump, a plunger pump, a screw pump and a diaphragm pump.
Optionally, the apparatus comprises: a reactor, an oil-water separator and a circulating pump;
the reactor is a gas-liquid three-phase reactor;
the reactor is a tubular reactor;
the operating medium of the shell in the tubular reactor is cooling liquid;
the reactor comprises a feed inlet III and a discharge outlet;
the oil-water separator comprises an oil phase extraction outlet, a purge gas outlet, a feed inlet I, a catalyst feed inlet II, a catalyst outlet and a condensate inlet;
the position of the catalyst feed inlet II is higher than the catalyst outlet;
the purge gas outlet is connected with a purge gas condenser;
the cooled liquid in the purge gas condenser enters the separation unit through the condensate inlet; the gas cooled in the purge gas condenser is treated by a purge gas fire-removing cabinet;
the feed inlet I is a reaction mixture feed inlet, and the discharge outlet is a reaction mixture discharge outlet;
the discharge hole is connected with the feed inlet I;
the catalyst outlet is connected with the circulating pump;
the feed inlet III is connected with the circulating pump through a feed mixer;
the CO and H2And olefins are mixed by the feedMixing in the reactor, and entering the reactor through the feed inlet III.
Alternatively, the apparatus is used for the hydroformylation of alpha-olefins to produce aldehydes.
According to another aspect of the present application, there is provided a method for preparing an aldehyde by a hydroformylation reaction, wherein the raw materials of the method comprise an olefin, CO and hydrogen, and an aqueous solution containing rhodium and a ligand thereof is used as a catalyst aqueous solution, and the aldehyde is prepared by using any one of the continuous reaction devices for preparing an aldehyde by a hydroformylation reaction.
Optionally, the method comprises at least:
(a) adding the catalyst aqueous solution into a separation unit, starting a circulation unit, and circulating the catalyst aqueous solution between the reactor and the oil-water separator through the circulation unit;
(b) introducing reaction raw materials into a reaction unit;
(c) and materials obtained by the reaction in the reaction unit pass through a separation unit to be subjected to phase separation and catalyst circulation.
Optionally, the method comprises at least the following steps:
1) adding a catalyst aqueous solution serving as a water phase into an oil-water separator, starting a circulating pump, and establishing circulation between a reactor and the oil-water separator;
2) after the circulation is stable, continuously introducing olefin, carbon monoxide and hydrogen, mixing in a feed mixer, introducing the mixture serving as an organic phase into a reaction mixture feed inlet at the bottom of the reactor, performing hydroformylation reaction under the action of a catalyst, discharging the reaction mixture from a discharge outlet at the top of the reactor, and introducing the reaction mixture into an oil-water separator;
3) the reaction mixture is separated in an oil-water separator, the water phase contains catalyst water solution and returns to the reactor for continuous use through a circulating pump, and the oil phase contains product aldehyde and unreacted raw materials and is continuously extracted.
Optionally, the aqueous catalyst solution in step 1) is an aqueous solution of a water-soluble phosphine ligand containing rhodium; the rhodium content in the catalyst aqueous solution is 200-300 ppm, and the concentration of the water-soluble phosphine ligand is 4.8-7.2%.
The volume ratio of each feed in the method is as follows:
an aqueous phase, namely an organic phase is 3-5: 1; h2:CO＝1～2:1。
Optionally, the volume ratio of each feed in the process is:
an aqueous phase, namely an organic phase is 3-5: 1; h2:CO＝1.05:1。
Optionally, the reaction temperature in the step 2) is 30-220 ℃, and the reaction pressure is 0.5-5.0 MPa.
Optionally, the reaction temperature is 50-180 ℃, and the reaction pressure is 0.6-4.8 MPa.
In the present application, multiphase refers to two or more phases (or fluid phases) that are immiscible or only partially miscible with each other, such as, but not limited to, liquid phases (inorganic liquid, organic liquid), gas phases, solid phases, and the like.
As a specific embodiment, the reactor herein comprises a shell-side barrel and a tube bundle;
the tube bundle is positioned in the shell pass cylinder, and the inner space of the tube bundle is not communicated with the inner space of the shell pass cylinder;
the two ends of the tube bundle are respectively provided with a feed inlet and a discharge outlet, and the feed inlet and the discharge outlet are communicated with the outside of the shell pass cylinder;
the shell pass cylinder is provided with a baffle plate.
Optionally, the shell pass cylinder is provided with a cooling liquid inlet, a cooling liquid outlet and 2-50 baffle plates;
wherein, the cooling liquid inlet and the cooling liquid outlet are arranged on the outer wall of the shell pass cylinder.
Optionally, the baffle plates are horizontally arranged on the inner wall of the shell pass cylinder, the baffle plates are arranged in parallel, and the distance between the baffle plates is 10-1000 mm.
In the application, through circulating flow's coolant liquid can realize fast removing heat in the shell side barrel, and then improves the selectivity of reaction product aldehyde.
In a preferred embodiment of the present invention, the shell-side cylinder is provided with a cooling liquid inlet, a cooling liquid outlet and 2-50 baffles, for example, 2, 5, 10, 20, 25, 30, 35, 40, 45, 50 and any two of the above components.
In the application, the baffle plate has the function of increasing the flow velocity of the cooling liquid and enhancing the heat transfer efficiency. The baffles may be spaced apart by 10-1000mm, for example 10mm, 100mm, 200mm, 500mm, 1000mm, and any point in the range consisting of any two of the above points. The baffles may be equally spaced or unequally spaced, preferably equally spaced.
Optionally, the baffle plate is provided with small holes, the aperture of each small hole is 1-100mm, the arrangement mode is regular triangle, square or the combination of the regular triangle and the square, and the aperture ratio is 0.1% -20%.
In a preferred embodiment of the present invention, the apertures of the baffle have a diameter of 1-100mm, such as 1mm, 10mm, 20mm, 50mm, 100mm and any two of the above ranges, and are arranged in a regular triangle, square or any combination thereof, and have an aperture ratio of 0.1% -20%.
Optionally, the tube bundle has a diameter of 5-500mm and a length of 500-10000 mm.
Optionally, a distributor is arranged in the tube bundle, and the distributor comprises a distributor main tube, distributor branch tubes and distribution caps.
The tube bundle comprises 1-1000 reaction tubes, and the arrangement mode of each reaction tube in the tube bundle is at least one of regular triangle, square and single row.
In a preferred embodiment of the invention, the tube bundle comprises 1 to 1000 reaction tubes, for example 1, 10, 100, 500, 1000, and others in the range of any two of the above.
Optionally, dispersing assemblies are arranged in the reaction tubes, and the number of the dispersing assemblies in each reaction tube is 1-1000;
the specific surface area of the dispersion component is 100-1000m2/m3The porosity is between 0.01 and 0.1; length is 10-1000 mm.
In a preferred embodiment of the invention, the tube bundle is provided with a number of dispersing elements in the tube bundle of 1-1000 per reaction tube, such as 1, 10, 100, 500, 1000, and others in the range of any two of the above.
In the present application, the combined use of the tube bundle and the dispersion assembly enables the maximum possible uniform dispersion of the reactants, improves the disadvantages of conventional reactors and enables the increase of the conversion and the selectivity of the product aldehyde.
The beneficial effects that this application can produce include:
1) according to the continuous reaction system and the method for preparing the aldehyde by the hydroformylation reaction of the alpha-olefin, the catalyst can be continuously recycled without being separated by external equipment.
2) The continuous reaction system and the method for preparing the aldehyde through the alpha-olefin hydroformylation reaction can realize continuous production of the aldehyde, can quickly remove reaction heat, and are beneficial to the hydroformylation reaction.
3) The continuous reaction system and the method for preparing the aldehyde through the alpha-olefin hydroformylation reaction have the advantages of high raw material conversion rate, high target product yield and high product normal-to-iso ratio.
Drawings
FIG. 1 is a schematic diagram of a continuous reaction system for the hydroformylation of an alpha-olefin to produce an aldehyde in one embodiment of the present application.
List of parts and reference numerals:
1-reactor 2-oil-water separator 3-purge gas condenser
4-circulating pump 5-feeding mixer 6-catalyst feeding port
7-inlet 8-outlet 9-inlet for reaction mixture
10-purge gas outlet 11-condensate inlet 12-oil phase extraction outlet
13-catalyst outlet
Detailed Description
The present application is described in detail below with reference to examples and figures, which are intended to more clearly illustrate the reaction systems and methods of the present application, and not to limit the present application.
In the examples of the present application, the conversion of α -olefin and the selectivity of the product aldehyde were calculated on the basis of carbon mole number as follows:
FIG. 1 is a schematic diagram of a continuous reaction system for the hydroformylation of an alpha-olefin to produce an aldehyde in one embodiment of the present application.
The application provides a continuous reaction system for preparing aldehyde by alpha-olefin hydroformylation, which comprises a reactor 1, an oil-water separator 2, a purge gas condenser 3, a circulating pump 4 and a feeding mixer 5 which are connected with each other.
In this application, connect and form the circulation through circulating pump 4 between reactor 1 and the oil water separator 2, during the application, can be earlier to feeding catalyst aqueous solution in the oil water separator 2, form the circulation with circulating pump 4 drive catalyst aqueous solution between reactor 1 and oil water separator 2, reach stable back, the reaction raw materials that advances again, begin the hydroformylation reaction, continuous feeding, the ejection of compact, reaction mixture separates in oil water separator 2, the aqueous phase is catalyst aqueous solution, recycle, the oil phase includes product aldehyde.
In a preferred embodiment of the present application, the reactor is a gas-liquid three-phase reactor comprising a barrel; the cylinder is internally provided with a gas-liquid dispersion inner member; the method is suitable for hydroformylation reaction for producing aldehyde under the conditions of 50-180 ℃ and 0.5-5.0 MPa of pressure;
in a preferred embodiment of the present application, the reactor is a gas-liquid three-phase reactor, which comprises a shell-side cylinder, a head and a tube bundle; a distributor (formed by connecting a main distribution pipe, branch pipes and distribution caps) is arranged in the pipe bundle; the method is suitable for hydroformylation reaction for producing aldehyde under the conditions of 50-180 ℃ and 0.5-5.0 MPa of pressure.
In a preferred embodiment of the present application, the first reactor comprises a shell-side cylinder and a tube-side, wherein the operation medium II of the shell-side cylinder is a cooling liquid, the cooling liquid can be one of water, brine or ethylene glycol aqueous solution, and the operation medium III of the tube bundle comprises a raw material solution, a catalyst aqueous solution, CO and H2Mixed gas and reaction product aldehyde.
The shell-side cylinder of the reactor is cooled, and reaction heat is quickly removed through cooling liquid, so that the selectivity of the product aldehyde is improved.
In a preferred embodiment of the present application, the shell-side cylinder is provided with a coolant inlet, a coolant outlet, and 2-50 baffles 20, e.g., 2, 5, 10, 20, 25, 30, 35, 40, 45, 50, and any two of the above points in a range. The baffle plate has the function of increasing the flow velocity of the cooling liquid and enhancing the heat transfer efficiency.
In a preferred embodiment of the present application, the coolant inlet and the coolant outlet are provided on the outer wall of the shell-side cylinder of the reactor 2; the inlet of the cooling liquid is arranged at the lower part of the shell pass cylinder, the cooling liquid enters the shell pass cylinder from the inlet and flows in the shell pass cylinder to achieve the effect of cooling the reaction system, and finally flows out from the cooling liquid outlet arranged at the upper part of the shell pass cylinder.
In a preferred embodiment of the present application, the baffles are horizontally disposed on the inner wall of the shell-side cylinder of the reactor, the baffles are disposed in parallel, and the distance between the baffles is 10-1000mm, such as 10mm, 100mm, 200mm, 500mm, 1000mm, and any point in the range consisting of any two of the above points. The baffles may be equally spaced or unequally spaced, preferably equally spaced.
In a preferred embodiment of the present application, the baffle plate is provided with small holes, the diameter of the small holes is 1-100mm, such as 1mm, 10mm, 20mm, 50mm, 100mm and other point values in the range of any two of the above point values, the arrangement mode is regular triangle, square or any combination of the two, and the aperture ratio is 0.1% -20%.
In a preferred embodiment of the present application, the head feed inlet introduces material into the tube bundle; and the discharge hole of the end socket leads out the discharged material of the tube bundle.
In a preferred embodiment of the present application, the tube bundle comprises 1-1000 reaction tubes, such as 1, 10, 100, 500, 1000, and others in the range of any two of the above, the tube bundle has a diameter of 5-500mm and a length of 500-10000mm, and the reaction tubes within the tube bundle are arranged in at least one selected from the group consisting of regular triangles, squares, and single rows.
In a preferred embodiment of the present application, the reactor tubes are provided with dispersing elements, and the number of dispersing elements in each reactor tube is 1-1000, such as 1, 10, 100, 500, 1000, and other points in the range of any two of the above points; the specific surface area of the dispersion component is 100-1000m2/m3The porosity is 0.01-0.1; the length is 10-1000 mm.
The combined application of the tube bundle and the dispersion assembly can realize the uniform dispersion of reactants to the maximum extent, improve the defects of the traditional reaction kettle and improve the process efficiency and the selectivity of the product aldehyde.
In a preferred embodiment of the present application, a circulation pump 4 is provided between the reactor 1 and the oil-water separator 2, and the circulation pump 4 is capable of driving the reaction mixture to circulate between the reactor 1 and the oil-water separator 2.
In a preferred embodiment of the present application, the circulation pump 4 is selected from any one of a centrifugal pump, a plunger pump, a screw pump, and a diaphragm pump.
In a preferred embodiment of the present application, the system further comprises a mixer 5, the mixer 5 being arranged between the reactor feed opening 7 and the outlet of the circulation pump 4 for thoroughly premixing the reaction raw materials.
Example 1
The process shown in FIG. 1 is adopted, and the process conditions are as follows:
the catalyst aqueous solution adopts the proportioning composition of example 1 in the published patent No. CN 101462932A.
Reaction temperature: the reaction pressure is 2.5MPa (A) at 80 ℃;
reactor feed inlet conditions:
catalyst aqueous solution feed flow rate: 10m3Hour/hour;
ethylene feed flow rate: 25Nm3Hour/hour;
CO+H2feeding flow rate: 50Nm3Hour/hour;
CO:H21:1 (molar ratio);
discharging results at the discharging port 3:
ethylene conversion: 98 percent;
propionaldehyde yield: 98 percent.
This example realizes the production of propanal by hydroformylation of ethylene hydrocarbon with high conversion of ethylene of 98% and high selectivity to propanal of 98%.
Example 2
The process shown in FIG. 1 is adopted, and the process conditions are as follows:
the catalyst aqueous solution adopts the proportioning composition of example 5 in the published patent No. CN 101462932A.
Reaction temperature: the reaction pressure is 2.5MPa (A) at 110 ℃;
reactor feed inlet conditions:
catalyst aqueous solution feed flow rate: 10m3Hour/hour;
propylene feed flow rate: 50 kg/hour;
CO+H2feeding flow rate: 50Nm3Hour/hour;
CO:H21:1 (molar ratio);
discharging results at the discharging port 3:
conversion of propylene: 98 percent;
yield of n-butyraldehyde: 97 percent;
n-butyraldehyde: isobutyraldehyde is 40:1 (molar ratio).
This example realizes the production of n-butyraldehyde by hydroformylation of propylene hydrocarbon with high propylene conversion of 98% and high selectivity to n-butyraldehyde of 97%.
Example 3
The process shown in FIG. 1 is adopted, and the process conditions are as follows:
the aqueous catalyst solution was prepared according to the formulation of example 10 of published patent No. CN 101462932A.
Reaction temperature: the reaction pressure is 3.0MPa (A) at 120 ℃;
reactor feed inlet conditions:
catalyst aqueous solution feed flow rate: 10m3Hour/hour;
1-butene feed flow: 60 kg/hour;
CO+H2feeding flow rate: 50Nm3Hour/hour;
CO:H21:1 (molar ratio);
discharging results at the discharging port 3:
1-butene conversion: 97 percent;
n-valeraldehyde yield: 97 percent;
n-valeraldehyde: isovaleraldehyde is 60:1 (molar ratio).
This example realizes the production of n-valeraldehyde by hydroformylation of 1-butene hydrocarbon with 97% high 1-butene conversion and 97% high n-valeraldehyde selectivity.
Example 4
The process shown in FIG. 1 is adopted, and the process conditions are as follows:
the aqueous solution of the catalyst adopts the proportioning composition of the example 32 in the published patent No. CN 106000470.
Reaction temperature: the reaction pressure is 2.0MPa (A) at 80 ℃;
reactor feed inlet conditions:
catalyst aqueous solution feed flow rate: 10m3Hour/hour;
1-octene feed flow: 100 kg/hour;
CO+H2feeding flow rate: 50Nm3Hour/hour;
CO:H21:1 (molar ratio);
discharging results at the discharging port 3:
1-octene conversion: 97.2 percent;
yield of n-nonanal: 95 percent;
n-nonanal: isononanal is 50:1 (molar ratio).
This example realizes the production of n-nonanal by hydroformylation of 1-octene hydrocarbons with a high conversion of 1-octene and a high selectivity to n-nonanal of 97.2%.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (7)
1. A method for preparing aldehyde by hydroformylation reaction is characterized in that raw materials of the method comprise olefin, CO and hydrogen, aqueous solution containing rhodium and ligand thereof is used as catalyst aqueous solution, and a continuous reaction device for preparing aldehyde by hydroformylation reaction is adopted to prepare aldehyde;
the continuous reaction device for preparing the aldehyde by the hydroformylation reaction comprises a reactor, an oil-water separator and a circulating pump;
the reactor is a gas-liquid three-phase reactor;
the reactor is a tubular reactor;
the operating medium of the shell in the tubular reactor is cooling liquid;
the reactor comprises a feed inlet III and a discharge outlet;
the oil-water separator comprises an oil phase extraction outlet, a purge gas outlet, a feed inlet I, a catalyst feed inlet II, a catalyst outlet and a condensate inlet;
the position of the catalyst feed inlet II is higher than the catalyst outlet;
the purge gas outlet is connected with a purge gas condenser;
the liquid cooled in the purge gas condenser enters the oil-water separator through the condensate inlet; the cooled gas in the purge gas condenser is treated by a purge gas torch;
the feed inlet I is a reaction mixture feed inlet, and the discharge outlet is a reaction mixture discharge outlet;
the discharge hole is connected with the feed inlet I;
the catalyst outlet is connected with the circulating pump;
the feed inlet III is connected with the circulating pump through a feed mixer;
the reaction raw materials are mixed by the feed mixer and enter the reactor through the feed inlet III;
the method comprises at least the following steps:
1) adding a catalyst aqueous solution serving as a water phase into an oil-water separator, starting a circulating pump, and establishing circulation between a reactor and the oil-water separator;
2) after the circulation is stable, continuously introducing olefin, carbon monoxide and hydrogen, mixing in a feed mixer, introducing the mixture serving as an organic phase into a reaction mixture feed inlet at the bottom of the reactor, performing hydroformylation reaction under the action of a catalyst, discharging the reaction mixture from a discharge outlet at the top of the reactor, and introducing the reaction mixture into an oil-water separator;
3) the reaction mixture is separated in an oil-water separator, the water phase contains catalyst water solution and returns to the reactor for continuous use through a circulating pump, and the oil phase contains product aldehyde and unreacted raw materials and is continuously extracted.
2. The method of claim 1, wherein the aqueous phase in the oil-water separator is an aqueous catalyst solution and the oil phase comprises the reaction product aldehyde;
the circulating pump is selected from any one of a centrifugal pump, a plunger pump, a screw pump and a diaphragm pump.
3. According to claimThe method of claim 1, wherein the device is used forαHydroformylation of olefins to produce aldehydes.
4. The process according to claim 1, wherein the aqueous catalyst solution in step 1) is an aqueous solution of a water-soluble phosphine ligand containing rhodium; the content of rhodium in the catalyst aqueous solution is 200-300 ppm, and the concentration of the water-soluble phosphine ligand is 4.8% -7.2%;
the volume ratio of each feed in the method is as follows:
an aqueous phase, namely an organic phase = 3-5: 1; h2: CO=1~2:1。
5. The process according to claim 4, wherein the volume ratio of each feed in the process is:
an aqueous phase, namely an organic phase = 3-5: 1; h2: CO=1.05:1。
6. The method according to claim 4, wherein the reaction temperature in step 2) is 30 to 220 ℃ and the reaction pressure is 0.5 to 5.0 MPa.
7. The method according to claim 6, wherein the reaction temperature in step 2) is 50 to 180 ℃ and the reaction pressure is 0.6 to 4.8 MPa.
Priority Applications (2)
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| 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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| 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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