WO2019223032A1

WO2019223032A1 - Continuous reaction apparatus and method for using hydroformylation reaction to prepare aldehyde

Info

Publication number: WO2019223032A1
Application number: PCT/CN2018/090837
Authority: WO
Inventors: 安丽华
Original assignee: An Lihua
Priority date: 2018-05-25
Filing date: 2018-06-12
Publication date: 2019-11-28
Also published as: CN110526807B; CN110526807A

Abstract

A continuous reaction apparatus for using hydroformylation reaction to prepare aldehyde, and a method for using the reaction apparatus for preparing aldehyde. Said reaction apparatus comprises a reaction unit, a separation unit, and a recycling unit. Said recycling unit is arranged between the reaction unit and the separation unit. The reaction unit is connected to the separation unit, and a catalyst circulates between the reaction unit and the separation unit through the recycling unit.

Description

Continuous reaction device and method for preparing aldehyde by hydroformylation reaction

Technical field

The present application relates to a continuous reaction device for preparing an aldehyde by a hydroformylation reaction and a method for preparing an aldehyde by using the device, and belongs to the fields of chemical engineering and chemical synthesis.

Background technique

The hydroformylation reaction is a reaction process in which an olefin and synthesis gas (CO and H ₂ ) generate one molecule more aldehyde or alcohol than the original olefin under the action of a transition metal complex catalyst. The aldehydes, alcohols, and derivatives derived therefrom are used in large quantities as plasticizers, fabric additives, surfactants, solvents, and perfumes. This type of reaction was first discovered by O. Roelen in Fischer-Tropsch synthesis at the German Ruhr Chemical Company in 1938. Propionaldehyde and ethylenedione were obtained from syngas and ethylene, and soon applied to propylene Process for producing butanol. However, the homogeneous complex catalytic process has been limited due to the complexity of product separation and catalyst separation. In recent years, research on water-organic two-phase catalytic systems and supported catalytic systems has made progress.

At present, there are dozens of methods for the industrial production of hydroformylation, and most of them mainly use aldehydes and alcohols. Representatives include German Ruhr Chemical Company, BASF, Mitsubishi Chemical Corporation, Shell, UCC, RCH / RP and so on. German Luer Chemical Company's propylene as raw material for the production of 2-ylethylhexanol as a by-product of butanol, using a cobalt-based catalyst, the reaction conditions are 100 to 160 degrees, 20 to 30 MPa. In order to maintain catalyst activity and high conversion rate, the process must use high syngas pressure and high temperature, and the resulting product has low orthonormality, many side reactions, high overall energy consumption, and catalyst recovery and regeneration. The process is complicated. BASF's process is similar to that of Ruhr, Germany. It uses a higher reaction temperature to increase the speed of the formylation reaction, but the side reactions increase more. Mitsubishi Chemical Co., Ltd. has improved the process. It uses automatic control and a lower temperature (100 to 150 degrees) to make the temperature in the reactor uniform. Taking propylene for butyraldehyde as an example, the selectivity can reach 85 to 88%. The ratio is 4: 1; the disadvantage is that the reaction pressure is still high (15-30 MPa), and the catalyst separation effect is complicated. Shell company uses trialkylphosphine and cobalt carbonyl coordination catalyst, high stability, low operating pressure (2.0 ~ 5.0MPa), high hydrogenation activity, high normal alcohol content in the product; but modified cobalt phosphine The hydroformylation activity of the catalyst is much lower than that of traditional cobalt carbonyl, which is only 1/5 to 1/6 of cobalt carbonyl. At the same time, the by-products of alkane increase greatly, which can reach 10 to 15%. The UCC process was jointly developed by United Carbonation Corporation of the United States, David Electric Co., Ltd. and Johnson Matthey Corporation. A large amount of excess triphenylphosphine was used as the ligand and triphenylphosphine carbonyl rhodium hydride was used as the catalyst system to make the reaction mild The operation pressure is greatly reduced. The disadvantages are that rhodium is expensive and the catalyst is poisoned and deactivated. This process is limited to low-carbon olefins as raw materials and ethylene and propylene to produce propionaldehyde and butyraldehyde. The core advantage of the RCH / RP process is the use of a special reactor. When the reaction product leaves the reactor, the catalyst separation process has been completed. The catalyst remains in the reactor, but the disadvantage is that the reaction temperature and reaction pressure are relatively low. High, there are a large number of water cycles, and large energy consumption.

Summary of the Invention

According to an aspect of the present application, a continuous reaction device for preparing aldehyde by hydroformylation reaction is provided. The catalyst in the reaction device can be used continuously without interruption without being separated by external equipment. It can quickly remove the heat of reaction, which is conducive to the progress of the hydroformylation reaction.

The reaction device includes a reaction unit, a separation unit, and a circulation unit;

The circulation unit is located between the reaction unit and the separation unit;

The reaction unit is connected to the separation unit;

The catalyst is circulated between the reaction unit and the separation unit through the circulation unit.

Optionally, the reaction unit includes a discharge port;

The outlet is connected to the inlet I of the separation unit.

Optionally, the discharge port is located at an upper part of the reaction unit.

Optionally, the separation unit includes 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 includes a catalyst feed port II;

The catalyst feed port II is located above the catalyst outlet.

Optionally, the reaction unit includes a feed port III;

The feed port III is connected to the circulation unit.

Optionally, the feed port III is connected to the circulation unit through a feed mixer.

Optionally, the reaction feedstock and catalyst enter the feed port III through the feed mixer.

Optionally, the reaction feedstock includes CO, H ₂ and olefins.

Optionally, the separation unit includes a product extraction port.

Optionally, the product extraction port is an oil phase extraction port.

Optionally, the separation unit includes a purge gas outlet.

Optionally, the separation unit includes 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 by a purge gas defire cabinet.

Optionally, the reaction unit is a reactor;

The separation unit is an oil-water separator;

The circulation unit is a circulation pump.

Optionally, the reactor is a gas-liquid-liquid three-phase reactor;

The reactor is a tubular reactor;

The operating medium of the shell in the tubular reactor is a cooling liquid;

The water phase in the oil-water separator is an aqueous catalyst solution, and the oil phase includes a reaction product aldehyde;

The circulation pump is selected from any one of a centrifugal pump, a plunger pump, a screw pump, and a diaphragm pump.

Optionally, the device includes: a reactor, an oil-water separator, and a circulation pump;

The reactor is a gas-liquid-liquid three-phase reactor;

The reactor is a tubular reactor;

The operating medium of the shell in the tubular reactor is a cooling liquid;

The reactor includes a feed port III and a discharge port;

The oil-water separator includes an oil phase production 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 port II is higher than the catalyst outlet;

The purge gas outlet is connected to the purge gas condenser;

The liquid cooled in the purge gas condenser enters the separation unit through the condensate inlet; the gas cooled in the purge gas condenser is processed by the purge gas to the fire cabinet;

The feed port I is a reaction mixture feed port, and the discharge port is a reaction mixture discharge port;

The outlet is connected to the inlet I;

The catalyst outlet is connected to the circulation pump;

The feed port III is connected to the circulation pump through a feed mixer;

The CO, H ₂ and olefin are mixed through the feed mixer and enter the reactor through the feed port III.

Optionally, the device is used for α-olefin hydroformylation to produce aldehydes.

According to another aspect of the present application, a method for preparing an aldehyde by a hydroformylation reaction is provided, characterized in that the raw materials of the method include olefin, CO, and hydrogen, and an aqueous solution containing rhodium and its ligand is used as a catalyst aqueous solution, A continuous reaction device for preparing an aldehyde by using any of the above hydroformylation reactions is used to prepare an aldehyde.

Optionally, the method includes at least:

(a) adding the catalyst aqueous solution to the separation unit, turning on the circulation unit, and the catalyst aqueous solution is circulated between the reactor and the oil-water separator through the circulation unit;

(b) passing the reaction raw materials to the reaction unit;

(c) The material obtained by the reaction in the reaction unit passes through a separation unit to perform phase separation and catalyst recycling.

Optionally, the method includes at least the following steps:

1) Add the catalyst aqueous solution as the water phase to the oil-water separator, start the circulation pump, and establish the circulation between the reactor and the oil-water separator;

2) After the cycle is stabilized, olefin, carbon monoxide and hydrogen are continuously introduced, and after mixing in the feed mixer, the organic phase is passed to the reaction mixture feed port at the bottom of the reactor, and the hydroformylation reaction occurs under the action of the catalyst. The reaction mixture is discharged from the outlet at the top of the reactor and enters the oil-water separator;

3) The reaction mixture is separated in an oil-water separator. The water phase contains the catalyst aqueous solution and is returned to the reactor through the circulation pump for continued use. The oil phase contains the product aldehyde and unreacted raw materials and is continuously produced.

Optionally, the catalyst aqueous 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:

Water phase: organic phase = 3 to 5: 1; H ₂ : CO = 1 to 2: 1.

Optionally, the volume ratio of each feed in the method is:

Water phase: organic phase = 3 to 5: 1; H ₂ : CO = 1.05: 1.

Optionally, the reaction temperature in step 2) is 30-220 ° C, and the reaction pressure is 0.5-5.0 MPa.

Optionally, the reaction temperature is 50 to 180 ° C, and the reaction pressure is 0.6 to 4.8 MPa.

In this application, multiphase refers to two or more phases (or liquid phases) that are immiscible or only partially miscible with each other, such as, but not limited to, liquid phase (inorganic liquid phase, organic liquid phase), gas phase, and solid phase. .

As a specific implementation manner, the reactor described in this application includes a shell-side cylinder and a tube bundle;

The tube bundle is located inside the shell-side barrel, and the internal space of the tube bundle and the internal space of the shell-side barrel are not connected with each other;

The two ends of the tube bundle respectively have a feeding port and a feeding port, and the feeding port and the feeding port are in communication with the outside of the shell-side cylinder;

The shell-side cylinder is provided with a baffle.

Optionally, the shell-side cylinder is provided with a coolant inlet, a coolant outlet, and 2-50 baffles;

Wherein, the cooling liquid inlet and the cooling liquid outlet are disposed on an outer wall of the shell-side cylinder.

Optionally, the baffles are horizontally arranged on the inner wall of the shell-side cylinder, and the baffles are arranged in parallel, and the distance between the baffles is 10-1000 mm.

In the present application, the cooling fluid circulating in the shell-side cylinder can quickly remove heat, thereby improving the selectivity of the reaction product aldehyde.

In a preferred embodiment of the present invention, the outer wall of the shell-side cylinder is provided with a coolant inlet, a coolant outlet, and 2-50 baffles, such as 2, 5, 10, 20, 25 Block, 30 block, 35 block, 40 block, 45 block, 50 block, and any point value in the range consisting of any two of the above point values.

In the present application, the role of the baffle is to increase the cooling fluid flow rate and enhance the heat transfer efficiency. The distance between each baffle is 10-1000mm, such as 10mm, 100mm, 200mm, 500mm, 1000mm, and any point value in a range consisting of any two of the above point values. The spacing between the baffles may be equal or different. Preferably, the spacing between the baffles is equal.

Optionally, a small hole is provided on the baffle plate, the hole diameter of the small hole is 1-100mm, the arrangement is regular triangle, square or any combination of the two, and the opening ratio is 0.1% -20%.

In a preferred embodiment of the present invention, the hole diameter of the small hole on the baffle plate is 1-100 mm, for example, 1 mm, 10 mm, 20 mm, 50 mm, 100 mm, and any two of the above points. For other points, the arrangement is regular triangle, square or any combination of the two, and the opening rate is 0.1% -20%.

Optionally, the tube bundle has a diameter of 5-500 mm and a length of 500-10000 mm.

Optionally, a sparger is provided in the tube bundle, and the sparger includes a sparger main pipe, a sparger branch pipe, and a distribution cap.

The tube bundle includes 1-1000 reaction tubes, and the arrangement of the reaction tubes in the tube bundle is selected from at least one of a regular triangle, a square, and a single row.

In a preferred embodiment of the present invention, the tube bundle includes 1-1000 reaction tubes, for example, 1, 10, 100, 500, 1000, and a range of any two of the above points. Other point values in.

Optionally, a dispersion component is provided in the reaction tube, and the number of dispersion components in each reaction tube is 1-1000;

The specific surface area of the dispersion component is 100-1000 m ² / m ³ , the porosity is between 0.01-0.1, and the length is between 10-1000 mm.

In a preferred embodiment of the present invention, the tube bundle is provided with dispersing components, and the number of dispersing components in each reaction tube is 1-1000, such as 1, 10, 100, 500, 1000, and Any other point value in the range consisting of any two of the above point values.

In this application, the combined application of the tube bundle and the dispersing component can achieve uniform dispersion of the reactants to the greatest extent, improve the defects of the traditional reactor, and improve the conversion rate and selectivity of the product aldehyde.

The beneficial effects that this application can produce include:

1) A continuous reaction system and method for preparing an aldehyde by hydroformylation of an α-olefin provided by the present application. The catalyst can be used continuously without interruption without being separated by external equipment.

2) A continuous reaction system and method for preparing an aldehyde by hydroformylation of an α-olefin provided by the present application, which can realize continuous production of aldehyde, and can quickly remove the reaction heat, which is beneficial to the progress of the hydroformylation reaction.

3) A continuous reaction system and method for preparing an aldehyde by hydroformylation of an α-olefin provided by the present application has the advantages of high raw material conversion, high target product yield, and high product singularity ratio.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of a continuous reaction system for preparing an aldehyde by hydroformylation of an α-olefin in an embodiment of the present application.

List of parts and references:

1-reactor 2-oil-water separator 3-purge gas condenser

4-circulating pump 5-feed mixer 6-catalyst inlet

7-feed port 8-discharge port 9-reaction mixture feed port

10- Chi gas outlet 11- Condensate inlet 12- Oil phase production outlet

13- Catalyst outlet

Detailed ways

The following describes the application in detail with reference to the examples and drawings. The drawings, examples and related descriptions are intended to explain the reaction system and method of the application more clearly, without limiting the application.

In the examples of the present application, the conversion rate of the α-olefin and the selectivity of the product aldehyde are calculated based on the number of moles of carbon. The calculation method is as follows:

The application provides a continuous reaction system for preparing an aldehyde by hydroformylation of an α-olefin. The reaction system includes an interconnected reactor 1, an oil-water separator 2, a purge gas condenser 3, a circulation pump 4, an inlet料混器 5。 Mixer 5.

In the present application, the reactor 1 and the oil-water separator 2 are connected through a circulation pump 4 to form a cycle. In application, the catalyst aqueous solution may be fed into the oil-water separator 2 first, and the catalyst aqueous solution is driven by the circulation pump 4 in the reactor 1 A cycle is formed between the oil and water separator 2, and after reaching stability, the reaction raw materials are fed again to start the hydroformylation reaction. Continuous feeding and discharging are performed. The reaction mixture is separated in the oil-water separator 2. The aqueous phase is an aqueous catalyst solution and circulated In use, the oil phase includes the product aldehyde.

In a preferred embodiment of the present application, the reactor is a gas-liquid-liquid three-phase reactor, which includes a cylinder; there are gas-liquid-liquid internal components in the cylinder; suitable for a temperature of 50 to 180 ° C and a pressure Hydroformylation reaction to produce aldehyde under 0.5 ～ 5.0MPa condition;

In a preferred embodiment of the present application, the reactor is a gas-liquid-liquid three-phase reactor, and the reactor includes a shell-side cylinder, a head, and a tube bundle; the tube bundle has a distributor (by a distribution main pipe and branch pipes and Distribution cap connection composition); Suitable for hydroformylation reaction for producing aldehyde under the conditions of temperature of 50-180 ° C and pressure of 0.5-5.0 MPa.

In a preferred embodiment of the present application, the first reactor includes a shell-side cylinder and a tube side, wherein the operating medium II of the shell-side cylinder is a cooling liquid, and the cooling liquid may be water, brine, or ethylene glycol. One of the alcohol aqueous solutions, and the operating medium III of the tube bundle includes a raw material solution, a catalyst aqueous solution, a mixed gas of CO and H _2, and a reaction product aldehyde.

The reactor shell-side cylinder is cooled, and the heat of reaction is quickly removed by the cooling liquid, thereby improving the selectivity of the product aldehyde.

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, such as 2, 5, 10, 20, and 25. , 30 blocks, 35 blocks, 40 blocks, 45 blocks, 50 blocks, and any point value in the range of any two points. The role of the baffle is to increase the flow rate of the cooling liquid and strengthen the heat transfer efficiency.

In a preferred embodiment of the present application, the cooling liquid inlet and the cooling liquid outlet are provided on the outer wall of the shell tube of the reactor 2; the cooling liquid inlet is provided on the lower portion of the shell tube, and the cooling liquid enters from the inlet. The shell-side cylinder flows through the shell-side cylinder to cool the reaction system, and finally flows out of the cooling liquid outlet provided at the upper part of the shell-side cylinder.

In a preferred embodiment of the present application, the baffles are horizontally arranged on the inner wall of the shell shell of the reactor, the baffles are arranged in parallel, and the distance between the baffles is 10-1000 mm, for example, 10 mm. , 100mm, 200mm, 500mm, 1000mm, and any point value in a range consisting of any two of the above point values. The spacing between the baffles may be equal or different. Preferably, the spacing between the baffles is equal.

In a preferred embodiment of the present application, a small hole is provided on the baffle plate, and a hole diameter of the small hole is 1-100 mm, for example, 1 mm, 10 mm, 20 mm, 50 mm, 100 mm and any of the above points. The other point values in the two composition ranges are arranged in a regular triangle, a square, or any combination of the two, and the opening rate is 0.1% -20%.

In a preferred embodiment of the present application, the head inlet feeds material into the tube bundle; and the head outlet draws the tube bundle out.

In a preferred embodiment of the present application, the tube bundle includes 1-1000 reaction tubes, for example, 1, 10, 100, 500, 1000, and a range of any two of the above points. For other point values, the diameter of the tube bundle is 5-500 mm and the length is 500-10000 mm. The arrangement of the reaction tubes in the tube bundle is selected from at least one of a regular triangle, a square, and a single column.

In a preferred embodiment of the present application, the reaction tube is provided with dispersing components, and the number of dispersing components in each reaction tank is 1-1000, for example, 1, 10, 100, 500, 1000, And other point values in the range of any two of the above point values; the specific surface area of the dispersing component is 100-1000 m ² / m ³ , the porosity is 0.01-0.1, and the length is 10-1000 mm.

The combined application of the tube bundle and the dispersing component can maximize the uniform dispersion of the reactants, 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 can drive 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 includes a mixer 5 which is disposed between the reactor inlet 7 and the outlet of the circulation pump 4 to fully premix the reaction raw materials.

Example 1

Using the process shown in Figure 1, the process conditions are as follows:

The catalyst aqueous solution is composed of the proportion of Example 1 in published patent number CN101462932A.

Reaction temperature: 80 ° C, reaction pressure is 2.5 MPa (A);

Reactor inlet conditions:

Catalyst aqueous solution feed flow: 10m ³ / hour;

Ethylene feed flow: 25Nm ³ / hour;

CO + H ₂ feed flow: 50Nm ³ / hour;

CO: H ₂ = 1: 1 (molar ratio);

Outlet results at 3 outlets:

Ethylene conversion: 98%;

Yield of propionaldehyde: 98%.

In this embodiment, a process of preparing propionaldehyde by the hydroformylation reaction of ethylene hydrocarbon is realized with a high ethylene conversion rate of 98% and a high propionaldehyde selectivity of 98%.

Example 2

Using the process shown in Figure 1, the process conditions are as follows:

The catalyst aqueous solution is composed of the proportion of Example 5 in the published patent number CN101462932A.

Reaction temperature: 110 ° C, reaction pressure is 2.5MPa (A);

Reactor inlet conditions:

Catalyst aqueous solution feed flow: 10m ³ / hour;

Propylene feed flow: 50kg / hour;

CO + H ₂ feed flow: 50Nm ³ / hour;

CO: H ₂ = 1: 1 (molar ratio);

Outlet results at 3 outlets:

Propylene conversion: 98%;

Yield of n-butyraldehyde: 97%;

N-butyraldehyde: isobutyraldehyde = 40: 1 (molar ratio).

In this embodiment, a production process of preparing n-butyraldehyde by a hydroformylation reaction of propylene hydrocarbons is realized with a high propylene conversion rate of 98% and a high n-butyraldehyde selectivity.

Example 3

Using the process shown in Figure 1, the process conditions are as follows:

The catalyst aqueous solution was composed of the proportion of Example 10 in Published Patent No. CN101462932A.

Reaction temperature: 120 ° C, reaction pressure is 3.0 MPa (A);

Reactor inlet conditions:

Catalyst aqueous solution feed flow: 10m ³ / hour;

1-butene feed flow: 60kg / hour;

CO + H ₂ feed flow: 50Nm ³ / hour;

CO: H ₂ = 1: 1 (molar ratio);

Outlet results at 3 outlets:

1-butene conversion: 97%;

Yield of n-valeraldehyde: 97%;

N-valeraldehyde: isovaleraldehyde = 60: 1 (molar ratio).

In this embodiment, a 1-butene hydroformylation reaction to produce n-valeraldehyde is achieved with a high 1-butene conversion of 97% and a high n-valeraldehyde selectivity of 97%.

Example 4

Using the process shown in Figure 1, the process conditions are as follows:

The catalyst aqueous solution is composed of the proportion of Example 32 in published patent number CN106000470.

Reaction temperature: 80 ° C, reaction pressure is 2.0 MPa (A);

Reactor inlet conditions:

Catalyst aqueous solution feed flow: 10m ³ / hour;

1-octene feed flow: 100kg / hour;

CO + H ₂ feed flow: 50Nm ³ / hour;

CO: H ₂ = 1: 1 (molar ratio);

Outlet results at 3 outlets:

1-octene conversion: 97.2%;

Yield of nonanal: 95%;

N-nonanal: isononanal = 50: 1 (molar ratio).

In this embodiment, a 1-octene hydroformylation reaction to produce n-nonanal is achieved with a high 1-octene conversion of 97.2% and a high n-nonanal selectivity of 95%.

The above are just a few examples of the present application, and do not limit the application in any form. Although the present application is disclosed in the preferred embodiment as above, it is not intended to limit the application. Any person skilled in the art, Without departing from the scope of the technical solution of the present application, making some changes or modifications using the technical content disclosed above is equivalent to an equivalent implementation case, and all fall within the scope of the technical solution.

Claims

A continuous reaction device for preparing an aldehyde by a hydroformylation reaction, wherein the reaction device includes a reaction unit, a separation unit, and a circulation unit;

The circulation unit is located between the reaction unit and the separation unit;

The reaction unit is connected to the separation unit;

The catalyst is circulated between the reaction unit and the separation unit through the circulation unit.
The apparatus according to claim 1, wherein the reaction unit includes a discharge port;

The outlet is connected to the inlet I of the separation unit.
The apparatus according to claim 2, wherein the discharge port is located at an upper portion of the reaction unit.
The apparatus according to claim 1, wherein the separation unit includes a catalyst outlet; the catalyst outlet is connected to the circulation unit.
The apparatus according to claim 4, wherein the catalyst outlet is located at the bottom of the circulation unit.
The apparatus according to claim 5, wherein the separation unit comprises a catalyst feed port II; the catalyst feed port II is located at an upper part of the catalyst outlet.
The apparatus according to claim 1, wherein the reaction unit includes a feed port III;

The feed port III is connected to the circulation unit.
The apparatus according to claim 7, wherein the feed port III is connected to the circulation unit through a feed mixer.
The apparatus according to claim 8, wherein the reaction raw materials and the catalyst enter the feed port III through the feed mixer.
The apparatus according to claim 9, wherein said reaction feed comprises CO, H 2 and olefins.
The apparatus according to claim 1, wherein the separation unit includes a product extraction port.
The device according to claim 11, wherein the product extraction port is an oil phase extraction port.
The device according to claim 11, wherein the separation unit includes a purge gas outlet.
The device according to claim 13, wherein the separation unit includes a condensate inlet; the liquid cooled in the purge gas condenser enters the separation unit through the condensate inlet.
The device according to claim 14, characterized in that the cooled gas in the purge gas condenser is processed by purge gas to a fire cabinet.
The apparatus according to claim 1, wherein the reaction unit is a reactor;

The separation unit is an oil-water separator;

The circulation unit is a circulation pump.
The apparatus according to claim 16, wherein the reactor is a gas-liquid-liquid three-phase reactor;

The reactor is a tubular reactor;

The operating medium of the shell in the tubular reactor is a cooling liquid;

The water phase in the oil-water separator is an aqueous catalyst solution, and the oil phase includes a reaction product aldehyde;

The circulation pump is selected from any one of a centrifugal pump, a plunger pump, a screw pump, and a diaphragm pump.
The apparatus according to claim 1, wherein the apparatus comprises: a reactor, an oil-water separator, and a circulation pump;

The reactor is a gas-liquid-liquid three-phase reactor;

The reactor is a tubular reactor;

The operating medium of the shell in the tubular reactor is a cooling liquid;

The reactor includes a feed port III and a discharge port;

The oil-water separator includes an oil phase production 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 port II is higher than the catalyst outlet;

The purge gas outlet is connected to the purge gas condenser;

The liquid cooled in the purge gas condenser enters the separation unit through the condensate inlet; the gas cooled in the purge gas condenser is processed by the purge gas to the fire cabinet;

The feed port I is a reaction mixture feed port, and the discharge port is a reaction mixture discharge port;

The outlet is connected to the inlet I;

The catalyst outlet is connected to the circulation pump;

The feed port III is connected to the circulation pump through a feed mixer;

The CO, H 2 and olefin are mixed through the feed mixer and enter the reactor through the feed port III.
The device according to claim 18, wherein the device is used for the hydroformylation of an α-olefin to produce an aldehyde.
A method for preparing an aldehyde by a hydroformylation reaction, wherein the raw materials of the method include olefins, CO, and hydrogen, and an aqueous solution containing rhodium and its ligand is used as a catalyst aqueous solution. The continuous reaction device for preparing an aldehyde by the hydroformylation reaction according to the item, to obtain an aldehyde.
The method according to claim 20, wherein the method comprises at least:

(a) adding the catalyst aqueous solution to the separation unit, turning on the circulation unit, and the catalyst aqueous solution is circulated between the reactor and the oil-water separator through the circulation unit;

(b) passing the reaction raw materials to the reaction unit;

(c) The material obtained by the reaction in the reaction unit passes through a separation unit to perform phase separation and catalyst recycling.
The method according to claim 21, wherein the method comprises at least the following steps:

1) Add the catalyst aqueous solution as the water phase to the oil-water separator, start the circulation pump, and establish the circulation between the reactor and the oil-water separator;

2) After the cycle is stabilized, olefin, carbon monoxide and hydrogen are continuously introduced, and after mixing in the feed mixer, the organic phase is passed to the reaction mixture feed port at the bottom of the reactor, and the hydroformylation reaction occurs under the action of the catalyst. The reaction mixture is discharged from the outlet at the top of the reactor and enters the oil-water separator;

3) The reaction mixture is separated in an oil-water separator. The water phase contains the catalyst aqueous solution and is returned to the reactor through the circulation pump for continued use. The oil phase contains the product aldehyde and unreacted raw materials and is continuously produced.
The method according to claim 22, wherein in the step 1), the catalyst aqueous solution 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 water-soluble phosphine compound Body concentration is 4.8% to 7.2%;

The volume ratio of each feed in the method is:

Water phase: organic phase = 3 to 5: 1; H 2 : CO = 1 to 2: 1.
The method according to claim 23, wherein the volume ratio of each feed in the method is:

Water phase: organic phase = 3 to 5: 1; H 2 : CO = 1.05: 1.
The method according to claim 22, wherein the reaction temperature in step 2) is 30 to 220 ° C, and the reaction pressure is 0.5 to 5.0 MPa.
The method according to claim 25, wherein the reaction temperature in step 2) is 50 to 180 ° C, and the reaction pressure is 0.6 to 4.8 MPa.