CN111170839B - Method for preparing nonanal by adopting loop reactor and Venturi ejector for preparing nonanal - Google Patents
Method for preparing nonanal by adopting loop reactor and Venturi ejector for preparing nonanal Download PDFInfo
- Publication number
- CN111170839B CN111170839B CN202010056904.1A CN202010056904A CN111170839B CN 111170839 B CN111170839 B CN 111170839B CN 202010056904 A CN202010056904 A CN 202010056904A CN 111170839 B CN111170839 B CN 111170839B
- Authority
- CN
- China
- Prior art keywords
- reaction
- octene
- nonanal
- venturi ejector
- loop reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
- B05B7/02—Spray pistols; Apparatus for discharge
- B05B7/04—Spray pistols; Apparatus for discharge with arrangements for mixing liquids or other fluent materials before discharge
- B05B7/0416—Spray pistols; Apparatus for discharge with arrangements for mixing liquids or other fluent materials before discharge with arrangements for mixing one gas and one liquid
- B05B7/0425—Spray pistols; Apparatus for discharge with arrangements for mixing liquids or other fluent materials before discharge with arrangements for mixing one gas and one liquid without any source of compressed gas, e.g. the air being sucked by the pressurised liquid
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
-
- 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
- B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
- B01J2540/30—Non-coordinating groups comprising sulfur
- B01J2540/32—Sulfonic acid groups or their salts
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing nonanal by using a loop reactor. The method prepares n-nonanal by the hydroformylation reaction of octene; the preparation method of n-nonanal uses 1-octene, hydrogen and carbon monoxide as raw materials, and triphenylphosphine sodium tri-meta-sulfonate and rhodium chloride as catalysts to carry out octene hydroformylation reaction. The water/oil/gas three-phase reaction interface is added through the loop reactor, the mass transfer rate among the reaction raw material 1-octene, the synthetic gas (hydrogen and carbon monoxide) and the catalyst water solution is increased, so that the conversion rate of the hydroformylation reaction is improved, and the conversion rate of octene is further improved and the selectivity of n-nonanal in the product is improved by optimizing the design parameters and relevant process parameters of a venturi ejector which is a core part of the loop reactor.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a method for preparing nonanal by performing hydroformylation reaction by adopting novel reactor equipment, namely a loop reactor.
Background
Nonanal is widely applied to essence formulas, is often used as top note of aldehyde essence base, is used for modulating the fragrance types of roses, neroli, lily of the valley, peonies, irises, sunflower leaves, sweet oranges, lemons, jasmine, tuberose, radix sileris and the like, and is industrially mainly prepared by a nonanol dehydrogenation method. The process has the problems of high production cost, complex process, low product yield, serious environmental pollution and the like.
Olefin molecules with syngas (CO + H) 2 ) Under certain temperature, pressure and catalysis, aldehyde with one more carbon can be obtained through hydroformylation. The homogeneous rhodium-based complex catalyst can carry out propylene hydroformylation reaction under the conditions of 85-90 ℃ and 1.8MPa, and the process is called LPO low-pressure rhodium method. In the low pressure rhodium process, the reaction product is miscible with the catalyst and the product is separated by distillation. Too high a temperature in the distillation stage leads to decomposition of the rhodium complex catalystDeactivated and there was some amount of catalyst loss. Thus, a liquid/liquid two-phase (RCH/RP) process has been proposed, i.e., a water-oil two-phase reaction is carried out by using a water-soluble catalyst, and after the reaction is finished, the reaction is kept still, a water phase containing the catalyst and an organic phase containing a product can be automatically layered, the water phase containing the catalyst can be recycled, the production cost is reduced, and the method is successfully applied to the industrial production of n-butyraldehyde.
In the water-soluble rhodium complex catalytic system, the hydroformylation reaction occurs at the interface between two phases, so the mass transfer speed between olefin and the catalyst aqueous solution becomes the catalytic reaction speed control factor. Although the water/oil two-phase catalytic system has obtained great achievement in the hydroformylation of low-carbon olefins represented by propylene, when the system is popularized to the hydroformylation reaction of high-carbon olefins, the water solubility of the high-carbon olefins is extremely low, so that the mass transfer rate of the reaction in a water phase is slow, the reaction is limited, and the industrial application prospect is poor.
At present, the effects of homogeneous reaction and two-phase separation are achieved mainly by methods of fluorine two-phase, organic liquid/liquid two-phase, temperature control phase separation or ionic liquid and the like based on the characteristics of high-temperature mixing and dissolving and low-temperature phase separation, and the hydroformylation conversion effect of high-carbon olefin is improved. The improved methods mostly add organic solvent of specific structural molecules or rhodium catalyst using specific ligand into the reaction system. For practical industrial production, high-cost solvents are reduced or not used as much as possible, the catalyst is recycled to reduce the production cost, and the amplification effect of the process method is fully considered, so the improved method has poor industrial application prospect and still stays in the research stage.
And finally, the rhodium catalyst is transferred from the catalyst solution in the reaction process in order to realize homogeneous reaction due to methods such as fluorine two-phase, organic liquid/liquid two-phase, temperature-controlled phase separation or ionic liquid, so that catalyst loss occurs to a certain degree when the two phases are separated.
Disclosure of Invention
The invention provides a novel preparation process of n-nonanal, which increases a water/oil/gas three-phase reaction interface through a loop reactor, increases the mass transfer rate among reaction raw materials 1-octene, synthesis gas (hydrogen and carbon monoxide) and a catalyst aqueous solution, thereby improving the conversion rate of hydroformylation reaction, and further improves the conversion rate of octene and the selectivity of n-nonanal in a product by optimizing the design parameters and related process parameters of a venturi ejector, which is a core part of the loop reactor.
In order to achieve the above object, the present invention provides a method for preparing nonanal using a loop reactor, which comprises preparing n-nonanal by hydroformylation of octene; the preparation method of n-nonanal comprises the steps of carrying out octene hydroformylation reaction by using 1-octene, hydrogen and carbon monoxide as raw materials and triphenylphosphine sodium tri-meta-sulfonate and rhodium chloride as catalysts; and controlling the linear velocity of liquid at the nozzle of the Venturi ejector to be 70-120 m/s in the reaction process; at the initial stage of hydroformylation reaction, adding a catalyst aqueous phase solution formed by dissolving triphenylphosphine sodium tri-meta-sulfonate and rhodium chloride in water and organic phase 1-octene into a reaction kettle of the loop reactor; the volume ratio of the catalyst aqueous phase solution to the 1-octene is (0.5-3): 1, the molar ratio of triphenylphosphine sodium tri-meta-sulfonate to rhodium chloride is (20-80): 5363 and the molar ratio of 1,1-octene to rhodium in the aqueous solution of the catalyst is (1000-3000): 1.
the inner diameter of the opening of the venturi ejector inlet section in the loop reactor adopted by the method is as follows: nozzle bore diameter: the inner diameter of the closed air chamber: length of mixed section: the ratio of the length of the diffusion section is 38: (1.5-4.5): (2-7): (20 to 70): (500-1500), the opening angle of the diffusion section is 10-40 degrees.
Preferably, the volume of the catalyst aqueous phase solution is greater than the volume of 1-octene and less than 3 times the volume of 1-octene.
Optimally, the volume ratio of the catalyst aqueous phase solution to the 1-octene is 1.3:1, the molar ratio of triphenylphosphine sodium tri-meta-sulfonate to rhodium chloride is 50: 5363 and the molar ratio of 1,1-octene to rhodium in the aqueous catalyst solution is 2000:1.
preferably, the venturi ejector inducer opening internal diameter: nozzle bore diameter: the inner diameter of the closed air chamber: length of mixed section: the ratio of the length of the diffusion section is 38:2.5:3.8:40:1000, the opening angle of the diffusion section is 21 degrees; the linear velocity of the liquid at the nozzle of the venturi ejector during the reaction was controlled to 85m/s.
Meanwhile, in the hydroformylation reaction process of the octylene, the pressure of a reaction system is controlled to be 1.5MPa to 2.5MPa, and the reaction temperature is controlled to be 80 ℃ to 130 ℃. Preferably, the pressure of the reaction system is controlled to be 2.0MPa, and the reaction temperature is controlled to be 110 +/-1 ℃.
And when the initial state of the octene hydroformylation reaction is controlled, the liquid level in the reaction kettle of the loop reactor is 75% +/-2% of the height of the whole reaction kettle.
Further, the bottom end of the Venturi ejector extends into the lower end of the interior of the reaction kettle, and the extending position of the bottommost end of the Venturi ejector is 10% +/-3% of the height of the whole reaction kettle.
The invention also provides a Venturi ejector for preparing nonanal by adopting the method, and the Venturi ejector comprises an inlet section, a nozzle, a mixing section and a diffusion section which are communicated in sequence; the inlet section and the nozzle are of a reducing pipe type; the periphery of the inlet section and the nozzle is provided with a tapered annular air chamber which is communicated with the mixing section; the diffusion section is a gradually expanding pipe type; the side surface of the gas chamber is provided with a gas circulating pipe and is connected with the top of the reaction kettle; the inner diameter of the opening of the venturi ejector inlet section is as follows: nozzle bore diameter: the inner diameter of the closed air chamber: length of mixed section: the ratio of the length of the diffusion section is 38:2.5:3.8:40:1000, the opening angle of the diffuser section is 21 °.
Compared with the prior art, the invention has the following advantages:
1. the loop reactor is used as key process equipment for preparing nonanal by means of octene hydroformylation, micron-sized bubbles generated by the Venturi ejector are dispersed to a liquid phase, local high gas-liquid mass transfer rate can be effectively caused, and meanwhile, interface contact between a catalyst water phase and a reactant oil phase is increased through high-speed ejection at the nozzle of the Venturi ejector, so that the catalytic reaction rate is further improved.
Meanwhile, the research of the invention finds that the volume ratio of the catalyst water phase to the organic phase of the raw material octene in the reaction kettle influences the mass transfer rate between olefin and the catalyst water solution due to the influence on the mixed interface of the water phase and the oil phase, and is a key factor influencing the hydroformylation reaction. On the basis, the invention provides the optimal volume ratio of the aqueous phase catalyst solution to the organic phase octene, when the volume of the aqueous phase is larger than that of the organic phase, the catalytic reaction rate can be obviously increased, but when the optimal volume ratio is 1.3, the catalytic reaction rate is inhibited along with the increase of the volume of the aqueous phase.
The other key factor influencing the hydroformylation reaction of the octenes is that the structure design of a loop reactor serving as reaction equipment, particularly a venturi ejector serving as a key component, plays a critical role in controlling the linear velocity of liquid at a nozzle and generated micron-sized bubbles, and further influences the speed of a multiphase reaction. By optimizing the structural design of the Venturi ejector, the gas-liquid mass transfer process is promoted, and the conversion rate of the octenes and the molar ratio (normal-iso ratio) of n-nonanal to isononanal in the product are improved.
2. The invention still takes a water/oil two-phase catalytic system as a basis, does not use organic solvents with specific molecular structures, such as fluorine organic solvents or surfactants, ionic liquids and the like, and saves the production cost.
3. The invention uses rhodium chloride and commercialized TPPTS as catalyst, the catalyst cost is lower, and because the liquid reaction system exists in water/oil two phases all the time in the whole process, homogeneous reaction is not introduced, the loss rate of the content of noble metal rhodium in the currently used improved method is reduced, and the catalyst cost is further reduced.
Drawings
FIG. 1 is a schematic diagram of a loop reactor for hydroformylation of 1-octene to produce n-nonanal according to the present invention;
FIG. 2 is a schematic structural view of a venturi ejector in embodiment 1 of the present invention.
In the figure, 1-a reaction kettle, 2-a Venturi ejector, 3-a heat exchanger and 4-a circulating pump; 21-inlet section, 22-mixing section, 23-diffusion section, 24-nozzle, 25-gas circulation pipe, 26-gas chamber.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments.
As shown in figure 1, the nonanal production of the invention employs a loop reactor for the hydroformylation of 1-octene. The loop reactor comprises a reaction kettle 1, a circulating pump 4, a heat exchanger 3 and a Venturi ejector 2.
When the reactor works, the circulating pump is started. The reaction liquid circulates in the loop at a large flow rate, the venturi ejector 2 ejects at a high speed, and negative pressure is formed at the working nozzle, so that gas is sucked into the venturi ejector. One side of the top of the reaction kettle 1 is provided with a branch pipe which is connected with an air inlet and can form air circuit circulation locally. The Venturi ejector forms tiny bubbles with large specific surface area, so that gas-liquid contact is increased, and the reaction speed is accelerated. The lower end of the Venturi ejector is positioned below the liquid level, and the gas-liquid mixed material and the liquid in the reaction kettle are impacted, so that the effect of promoting dispersion and mixing is achieved, and the reaction is promoted to further proceed. The material enters the heat exchanger 3 from the bottom end of the reaction kettle through the circulating pump 4 and enters the Venturi ejector 2 from the top end of the reaction kettle 1. The heat exchanger 3 removes or provides heat released or absorbed during the reaction and controls the reaction temperature to fluctuate by + -1 deg.C. And (3) gradually reducing the reactants and gradually increasing the products along with the reaction, and discharging the products from the bottom end of the reaction kettle after the reaction is completely finished.
The heat exchanger in this patent can adopt tubular heat exchanger or plate heat exchanger.
Aiming at a specific certain chemical reaction process under a certain pressure and temperature condition, the design structure size of the Venturi ejector greatly influences the effect of mutual dispersion and contact among reaction substances, thereby finally influencing the chemical production efficiency. Referring to fig. 2, the venturi ejector 2 of the present patent is specifically composed of an inlet section 21 in the shape of a convergent tube, a nozzle 24, a mixing section 22, a diffuser section 23, and a gas chamber 26. As shown in FIG. 1, a gas circulation pipe 25 is provided at the side of the gas chamber 26 and connected to the top of the reaction vessel 1 to provide a gas circulation space in a local range.
In the initial stage of hydroformylation of octene, TPPTS and RhCl are added 3 ·3H 2 Dissolving O in water to form a catalyst solution (water phase), and adding the catalyst solution (water phase) and the reaction raw material 1-octene (organic phase) into a reaction kettle of the loop reactor; catalyst waterThe volume ratio of the phase to the organic phase of the reactant is (0.5-3): 1, the molar ratio of TPPTS to Rh element is (20-80): 1, the molar ratio of the reactant 1-octene to Rh element (1000-3000): 1
An amount of rhodium chloride (RhCl) was added at room temperature 3 ·3H 2 O, beijing chemical research institute) and triphenylphosphine sodium tri-meta-sulfonate (TPPTS, shou-lite chemical limited) were dissolved in water, and added into the reaction kettle of the loop reactor through the feed inlet together with the reaction raw material 1-octene (purity 98.2%, hong zhou-yu chemical limited). Introducing synthetic gas (the volume ratio of hydrogen to carbon monoxide is 1:1 in the distribution of Nanjing special gas plant) into the reactor through an air inlet until the system pressure is 1MPa, starting a circulating pump 4 to enable liquid in the reactor to slowly flow, emptying, repeatedly replacing air in the loop reactor for 6 times, immediately introducing the synthetic gas to the reaction pressure after the temperature is raised to a preset reaction temperature (the temperature rise time is about 15 min), and adjusting the circulating pump 4 until the flow rate reaches a certain value to be recorded as the reaction start time.
At the end of the reaction, the flow rate of the circulation pump 4 is immediately reduced and rapidly cooled to room temperature (about 15 min). The gas in the kettle is vented, the liquid in the kettle is discharged, the mixture is kept still for 5 hours for layering, the upper organic phase is taken and added with the isopropanol serving as an internal standard, and quantitative analysis is carried out on the hydroformylation product of the octenes by using a WLFX 9790 gas chromatograph (chromatographic column SE54, 30m multiplied by 0.25mm multiplied by 0.33 mu m, FID detector). The column temperature is increased from 60 ℃ to 250 ℃ at a speed of 10 ℃/min, the column temperature is kept for 10min, the temperature of the vaporization chamber is 230 ℃, and the temperature of the detector is 260 ℃.
In addition to main product n-nonanal, the organic phase raw product also contains by-product isononanal and trace n-nonanol and isononanol (total nonanol selectivity is less than 2.5%), and correction factors are introduced, and the amount of the substance of the product is calculated according to the peak area ratio of the product component to the internal standard substance isopropanol, and the reaction conversion rate and selectivity are calculated. The content of the noble metal Rh in the aqueous phase catalyst solution is determined by JY38S-ICP emission spectrum.
Best mode for carrying out the invention
To a 5L loop reactor (reactor volume 5L), TPPTS and RhCl were charged 3 ·3H 2 Dissolving O in water to form catalyst solution (water phase) and 1-octene (organic phase), and controlling the reaction of the catalyst solution and the reactionThe volume ratio of the organic phase to the organic phase is 1.3:1, the molar ratio of TPPTS to Rh element is 50:1, the molar ratio of the reactant 1-octene to Rh element is 2000:1. the total volume of the materials in the reaction kettle is 4025ml, and the liquid level in the reaction kettle of the loop reactor is 75 +/-2% of the height of the whole reaction kettle.
Introducing synthetic gas (the volume ratio of hydrogen to carbon monoxide is 1:1) into the reactor to the system pressure of 1MPa, starting the circulating pump 4 to enable liquid in the reactor to slowly flow, emptying, repeatedly replacing air in the loop reactor for 6 times, raising the temperature (the temperature rise time is about 15 min) to the preset reaction temperature of 110 ℃, immediately introducing the synthetic gas to the reaction pressure of 2.0MPa, adjusting the circulating pump 4 to control the linear velocity of the liquid at the nozzle of the Venturi ejector to be 85m/s, and recording the linear velocity as the reaction starting time. In the reaction process, the pressure of the synthetic gas connected with the reaction kettle is controlled to be constant at 2.0MPa, the temperature is 110 +/-1 ℃, and the linear velocity of the liquid at the nozzle of the Venturi ejector is 85m/s. And (3) reacting for 45min, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (about 15 min), emptying the gas in the kettle, discharging the liquid in the kettle, standing for 5h for layering, adding an upper organic phase into an internal standard isopropanol to analyze the composition of the organic phase, and calculating the conversion rate of the reactant and the selectivity of the product.
The detailed design size of the adopted Venturi ejector is specifically the inner diameter D1 of an inlet section opening: nozzle inner diameter D2: air chamber binding off internal diameter D3: length of mixed segment L1: the ratio of the diffusion section length L2 is 38:2.5:3.8:40:1000 with the diffuser section opening angle alpha at 21 deg., as shown in fig. 2. The lowest insertion position of the venturi ejector is located at 10% of the height of the whole reaction kettle.
Through analysis and calculation, the conversion rate of 1-octene in the reaction process is 90%, and the molar ratio of n-nonanal to isononanal (normal-iso ratio) in the reaction product is 12.3. The catalyst water phase is recycled after being layered and separated, the reaction process conditions are unchanged, after the reaction is circulated for 14 times, the conversion rate of 1-octene is 89%, and the normal-to-iso ratio is 12.4. The results show that the activity of the catalyst is basically maintained stable after multiple cycles of reaction, and the activity is not reduced. By ICP determination, no Rh loss in the catalyst water phase was detected.
Example 2
To a 5L loop reactor (reactor volume 5L), TPPTS and RhCl were charged 3 ·3H 2 Dissolving O in water to form a catalyst solution (water phase) and reacting raw material 1-octene (organic phase), wherein the volume ratio of the catalyst water phase to the reactant organic phase is 2.1:1, the molar ratio of TPPTS to Rh element is 70:1, molar ratio 1450 of reactant 1-octene to Rh element: 1. the total volume of the materials in the reaction kettle is 4025ml, and the liquid level in the reaction kettle of the loop reactor is 75 +/-2% of the height of the whole reaction kettle.
Introducing synthetic gas (the volume ratio of hydrogen to carbon monoxide is 1:1) into the reactor until the system pressure is 1MPa, starting a circulating pump 4 to enable liquid in the reactor to slowly flow, emptying, repeatedly replacing air in the loop reactor for 6 times, heating (the heating time is about 15 min) to a preset reaction temperature of 90 ℃, immediately introducing the synthetic gas until the reaction pressure is 2.3MPa, adjusting the circulating pump 4 to control the linear velocity of the liquid at the nozzle of a Venturi ejector to be 73m/s, and recording the linear velocity as the reaction starting time. In the reaction process, the pressure of the synthesis gas connected with the reaction kettle is controlled to be constant at 2.3MPa, the temperature is 90 +/-1 ℃, and the linear velocity of the liquid at the nozzle of the Venturi ejector is 73m/s. And (3) reacting for 45min, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (about 15 min), emptying the gas in the kettle, discharging the liquid in the kettle, standing for 5h for layering, adding an upper organic phase into an internal standard isopropanol to analyze the composition of the organic phase, and calculating the conversion rate of the reactant and the selectivity of the product.
The detailed design size of the adopted Venturi ejector is specifically the inner diameter D1 of an inlet section opening: nozzle inner diameter D2: air chamber binding off internal diameter D3: length of mixed segment L1: the ratio of the diffusion section length L2 is 38:2:3.5:62:700, the diffuser section opening angle alpha is 16 deg., as shown in fig. 2. The lowest insertion position of the venturi ejector is located at 10% of the height of the whole reaction kettle.
Through analysis and calculation, the conversion rate of 1-octene in the reaction process is 69%, and the molar ratio of n-nonanal to isononanal in the reaction product is 8.7. The catalyst water phase is recycled after being layered and separated, the reaction process conditions are unchanged, and after the reaction is cycled for 14 times, the conversion rate of 1-octene is 68%, the normal-to-iso ratio is 8.2, and basically no reduction is caused. By ICP determination, no Rh loss in the catalyst water phase was detected.
Example 3
To a 5L loop reactor (reactor volume 5L), TPPTS and RhCl were charged 3 ·3H 2 Dissolving O in water to form a catalyst solution (aqueous phase) and reacting raw material 1-octene (organic phase), wherein the volume ratio of the catalyst aqueous phase to the reactant organic phase is 0.7:1, the molar ratio of TPPTS to Rh element is 28:1, molar ratio 2230 of reactant 1-octene to Rh element: 1. the total volume of the materials in the reaction kettle is 4025ml, and the liquid level in the reaction kettle of the loop reactor is 75 +/-2% of the height of the whole reaction kettle.
Introducing synthetic gas (the volume ratio of hydrogen to carbon monoxide is 1:1) into the reactor to the system pressure of 1MPa, starting the circulating pump 4 to enable liquid in the reactor to slowly flow, emptying, repeatedly replacing air in the loop reactor for 6 times, raising the temperature (the temperature rise time is about 15 min) to the preset reaction temperature of 90 ℃, immediately introducing the synthetic gas to the reaction pressure of 1.6MPa, adjusting the circulating pump 4 to control the linear velocity of the liquid at the nozzle of the Venturi ejector to be 98m/s, and recording the linear velocity as the reaction starting time. In the reaction process, the pressure of the synthesis gas connected with the reaction kettle is controlled to be constant at 1.6MPa, the temperature is controlled to be 90 +/-1 ℃, and the linear velocity of the liquid at the nozzle of the Venturi ejector is controlled to be 98m/s. And (3) reacting for 45min, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (about 15 min), emptying the gas in the kettle, discharging the liquid in the kettle, standing for 5h for layering, adding an upper organic phase into an internal standard isopropanol to analyze the composition of the organic phase, and calculating the conversion rate of the reactant and the selectivity of the product.
The detailed design size of the adopted Venturi ejector is specifically the inner diameter D1 of an inlet section opening: nozzle inner diameter D2: air chamber binding off internal diameter D3: length of mixed segment L1: the ratio of the diffusion section length L2 is 38:3:5:29:1350 and the diffuser section opening angle alpha is 27 deg., as shown in fig. 2. The inserted position of the lowest end of the Venturi ejector is positioned at 10 percent of the height of the whole reaction kettle.
Through analysis and calculation, the conversion rate of 1-octene in the reaction process is 65%, and the molar ratio of n-nonanal to isononanal in the reaction product is 6.4. The catalyst water phase is recycled after being layered and separated, the reaction process conditions are unchanged, and after the reaction is cycled for 14 times, the 1-octene conversion rate is 62 percent, and the normal-to-iso ratio is 6.4, and basically does not decrease. By ICP determination, no Rh loss in the catalyst water phase was detected.
Example 4
To a 5L loop reactor (5L reactor volume), addTPPTS and RhCl 3 ·3H 2 Dissolving O in water to form a catalyst solution (water phase) and reacting raw material 1-octene (organic phase), wherein the volume ratio of the catalyst water phase to the reactant organic phase is 2.6:1, the molar ratio of TPPTS to Rh element was 67:1, molar ratio of 1-octene reactant to Rh element 2670:1. the total volume of the materials in the reaction kettle is 4025ml, and the liquid level in the reaction kettle of the loop reactor is 75 +/-2% of the height of the whole reaction kettle.
Introducing synthetic gas (the volume ratio of hydrogen to carbon monoxide is 1:1) into the reactor to the system pressure of 1MPa, starting the circulating pump 4 to enable liquid in the reactor to slowly flow, emptying, repeatedly replacing air in the loop reactor for 6 times, raising the temperature (the temperature rise time is about 15 min) to the preset reaction temperature of 120 ℃, immediately introducing the synthetic gas to the reaction pressure of 2.2MPa, adjusting the circulating pump 4 to control the linear velocity of the liquid at the nozzle of the Venturi ejector to be 107m/s, and recording the linear velocity as the reaction starting time. In the reaction process, the pressure of the synthesis gas connected with the reaction kettle is controlled to be constant at 2.2MPa, the temperature is 120 +/-1 ℃, and the linear velocity of the liquid at the nozzle of the Venturi ejector is 107m/s. And (3) reacting for 45min, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (about 15 min), emptying the gas in the kettle, discharging the liquid in the kettle, standing for 5h for layering, adding an upper organic phase into an internal standard isopropanol to analyze the composition of the organic phase, and calculating the conversion rate of the reactant and the selectivity of the product.
The detailed design size of the adopted Venturi ejector is specifically the inner diameter D1 of an inlet section opening: nozzle inner diameter D2: air chamber binding off internal diameter D3: length of mixing segment L1: the ratio of the diffusion section length L2 is 38:3.5:6.5:50:1100, the diffuser section opening angle alpha is 35 deg., as shown in fig. 2. The lowest insertion position of the venturi ejector is located at 10% of the height of the whole reaction kettle.
Through analysis and calculation, the conversion rate of 1-octene in the reaction process is 75%, and the molar ratio of n-nonanal to isononanal in the reaction product is 8.7. The catalyst water phase is recycled after layered separation, the reaction process conditions are unchanged, and after 14 times of circulation, the conversion rate of 1-octene is 74%, and the normal-to-iso ratio is 8.7, which basically does not decrease. By ICP determination, no Rh loss in the catalyst water phase was detected.
Comparative example 1
Into a 5L loop reactor (reaction kettle)Volume 5L), TPPTS and RhCl were added 3 ·3H 2 Dissolving O in water to form a catalyst solution (water phase) and reacting raw material 1-octene (organic phase), wherein the volume ratio of the catalyst water phase to the reactant organic phase is 2.6:1, the molar ratio of TPPTS to Rh element was 67:1, molar ratio 2670 of reactant 1-octene to Rh element: 1. the total volume of the materials in the reaction kettle is 4025ml, and the liquid level in the reaction kettle of the loop reactor is 75 +/-2% of the height of the whole reaction kettle.
Introducing synthetic gas (the volume ratio of hydrogen to carbon monoxide is 1:1) into the reactor to the system pressure of 1MPa, starting the circulating pump 4 to enable liquid in the reactor to slowly flow, emptying, repeatedly replacing air in the loop reactor for 6 times, raising the temperature (the temperature rise time is about 15 min) to the preset reaction temperature of 120 ℃, immediately introducing the synthetic gas to the reaction pressure of 2.2MPa, adjusting the circulating pump 4 to control the linear velocity of the liquid at the nozzle of the Venturi ejector to be 107m/s, and recording the linear velocity as the reaction starting time. In the reaction process, the pressure of the synthetic gas connected with the reaction kettle is controlled to be constant at 2.2MPa, the temperature is 120 +/-1 ℃, and the linear velocity of the liquid at the nozzle of the Venturi ejector is 101m/s. And (3) reacting for 45min, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (about 15 min), emptying the gas in the kettle, discharging the liquid in the kettle, standing for 5h for layering, adding an upper organic phase into an internal standard isopropanol to analyze the composition of the organic phase, and calculating the conversion rate of the reactant and the selectivity of the product.
The detailed design size of the adopted Venturi ejector is specifically the inner diameter D1 of an inlet section opening: nozzle inner diameter D2: air chamber binding off internal diameter D3: length of mixing segment L1: the ratio of the diffusion section length L2 is 38:1.2:2.6:15:1000 with a diffuser opening angle alpha of 25 deg., as shown in fig. 2. The lowest insertion position of the venturi ejector is located at 10% of the height of the whole reaction kettle.
Through analysis and calculation, the conversion rate of 1-octene in the reaction process is 42%, and the molar ratio of n-nonanal to isononanal in the reaction product is 6.7.
Comparative example 2
To a 5L loop reactor (reactor volume 5L), TPPTS and RhCl were charged 3 ·3H 2 O is dissolved in water to form a catalyst solution (aqueous phase) and a reaction raw material 1-octene (organic phase), and the volume ratio of the catalyst aqueous phase to the reactant organic phase is4:1, the molar ratio of TPPTS to Rh element was 28:1, molar ratio 2230 of reactant 1-octene to Rh element: 1. the total volume of the materials in the reaction kettle is 4025ml, and the liquid level in the reaction kettle of the loop reactor is 75 +/-2% of the height of the whole reaction kettle.
Introducing synthetic gas (the volume ratio of hydrogen to carbon monoxide is 1:1) into the reactor until the system pressure is 1MPa, starting a circulating pump 4 to enable liquid in the reactor to slowly flow, emptying, repeatedly replacing air in the loop reactor for 6 times, heating (the heating time is about 15 min) to a preset reaction temperature of 90 ℃, immediately introducing the synthetic gas until the reaction pressure is 3.5MPa, adjusting the circulating pump 4 to control the linear velocity of the liquid at the nozzle of a Venturi ejector to be 98m/s, and recording the linear velocity as the reaction starting time. In the reaction process, the pressure of the synthetic gas connected with the reaction kettle is controlled to be constant at 3.5MPa, the temperature is 90 +/-1 ℃, and the linear velocity of the liquid at the nozzle of the Venturi ejector is 98m/s. And (3) reacting for 45min, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (about 15 min), emptying the gas in the kettle, discharging the liquid in the kettle, standing for 5h for layering, adding an upper organic phase into an internal standard isopropanol to analyze the composition of the organic phase, and calculating the conversion rate of the reactant and the selectivity of the product.
The detailed design size of the adopted Venturi ejector is specifically the inner diameter D1 of an inlet section opening: nozzle inner diameter D2: air chamber binding off internal diameter D3: length of mixed segment L1: the ratio of the length L2 of the diffusion zone is 38:3:5:29:1350 and the diffuser section opening angle alpha is 27 deg., as shown in fig. 2. The lowest insertion position of the venturi ejector is located at 10% of the height of the whole reaction kettle.
Through analysis and calculation, the conversion rate of 1-octene in the reaction process is 29%, and the molar ratio of n-nonanal to isononanal in the reaction product is 3.4.
Claims (8)
1. A method for preparing nonanal by using a loop reactor, wherein n-nonanal is prepared by hydroformylation of octenes; the method is characterized in that: the preparation method of the n-nonanal comprises the steps of carrying out octene hydroformylation reaction by using 1-octene, hydrogen and carbon monoxide as raw materials and using triphenylphosphine sodium tri-meta-sulfonate and rhodium chloride as catalysts; and controlling the linear velocity of liquid at the nozzle of the Venturi ejector to be 70-120 m/s in the reaction process; at the initial stage of hydroformylation reaction, adding a catalyst aqueous phase solution formed by dissolving triphenylphosphine sodium tri-meta-sulfonate and rhodium chloride in water and organic phase 1-octene into a reaction kettle of the loop reactor; the volume ratio of the catalyst aqueous phase solution to the 1-octene is (0.5-3): 1, the molar ratio of triphenylphosphine sodium tri-meta-sulfonate to rhodium chloride is (20-80): 5363 and the molar ratio of 1,1-octene to rhodium in the aqueous solution of the catalyst is (1000-3000): 1; the preparation method adopts the following steps that the inner diameter of an opening of an inlet section of a Venturi ejector in a loop reactor is as follows: nozzle bore diameter: the inner diameter of the closed air chamber: length of mixing section: the ratio of the length of the diffusion section is 38: (1.5-4.5): (2-7): (20 to 70): (500-1500), the opening angle of the diffusion section is 10-40 degrees.
2. The method for producing nonanal according to claim 1, wherein: the volume of the catalyst aqueous phase solution is more than that of the 1-octene and less than 3 times that of the 1-octene.
3. The method for producing nonanal according to claim 2, wherein: the volume ratio of the catalyst aqueous phase solution to the 1-octene is 1.3:1, the molar ratio of triphenylphosphine sodium tri-meta-sulfonate to rhodium chloride is 50: 5363 and the molar ratio of 1,1-octene to rhodium in the aqueous catalyst solution is 2000:1.
4. the method for producing nonanal according to claim 3, wherein: the inner diameter of the opening of the venturi ejector inlet section is as follows: nozzle bore diameter: the inner diameter of the closed air chamber: length of mixed section: the ratio of the length of the diffusion section is 38:2.5:3.8:40:1000, the opening angle of the diffusion section is 21 degrees; the linear velocity of the liquid at the nozzle of the venturi ejector during the reaction was controlled to 85m/s.
5. The method for producing nonanal according to claim 4, wherein: in the hydroformylation reaction process of the octenes, the pressure of a reaction system is controlled to be 1.5MPa to 2.5MPa, and the reaction temperature is controlled to be 80 ℃ to 130 ℃.
6. The method for producing nonanal according to claim 5, wherein: in the hydroformylation reaction process of the octene, the pressure of a reaction system is controlled to be 2.0MPa, and the reaction temperature is controlled to be 110 +/-1 ℃.
7. The method for producing nonanal according to claim 6, wherein: when the initial state of the hydroformylation of the octenes is controlled, the liquid level in the reaction kettle of the loop reactor is 75% +/-2% of the height of the whole reaction kettle.
8. The method for preparing nonanal according to claim 7, wherein: the bottom end of the Venturi ejector stretches into the lower end inside the reaction kettle, and the bottommost end of the Venturi ejector stretches into a position which is 10% +/-3% of the height of the whole reaction kettle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010056904.1A CN111170839B (en) | 2020-01-16 | 2020-01-16 | Method for preparing nonanal by adopting loop reactor and Venturi ejector for preparing nonanal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010056904.1A CN111170839B (en) | 2020-01-16 | 2020-01-16 | Method for preparing nonanal by adopting loop reactor and Venturi ejector for preparing nonanal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111170839A CN111170839A (en) | 2020-05-19 |
| CN111170839B true CN111170839B (en) | 2022-12-16 |
Family
ID=70651080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010056904.1A Active CN111170839B (en) | 2020-01-16 | 2020-01-16 | Method for preparing nonanal by adopting loop reactor and Venturi ejector for preparing nonanal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111170839B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112275295B (en) * | 2020-10-28 | 2022-10-28 | 杭州瑞思新材料有限公司 | Nano copper-manganese catalyst, preparation method thereof and method for preparing 4-dimethylaminopyridine |
| CN112390717B (en) * | 2020-11-19 | 2022-08-09 | 江苏苏御新材料科技有限公司 | Preparation method of dimethyl succinylsuccinate |
| CN112500418A (en) * | 2020-12-31 | 2021-03-16 | 山东中科新材料研究院有限公司 | Method for synthesizing 1, 8-diazabicycloundecen-7-ene by adopting loop reactor |
| CN113372206A (en) * | 2021-05-12 | 2021-09-10 | 上海簇睿低碳能源技术有限公司 | Method for synthesizing high-carbon aldehyde by using microchannel reaction device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102272079A (en) * | 2009-01-16 | 2011-12-07 | Lg化学株式会社 | Apparatus for producing alcohols from olefins |
| CN110128251A (en) * | 2019-06-24 | 2019-08-16 | 上海华谊（集团）公司 | Hydroformylation process and equipment |
-
2020
- 2020-01-16 CN CN202010056904.1A patent/CN111170839B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102272079A (en) * | 2009-01-16 | 2011-12-07 | Lg化学株式会社 | Apparatus for producing alcohols from olefins |
| CN110128251A (en) * | 2019-06-24 | 2019-08-16 | 上海华谊（集团）公司 | Hydroformylation process and equipment |
Non-Patent Citations (1)
| Title |
|---|
| 喷射回路反应器中文丘里喷射器混合特性的研究;李韶璞;《中国优秀博硕士学位论文全文数据库（硕士） 工程科技Ⅰ辑》;20181015;第3、5-6页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111170839A (en) | 2020-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111170839B (en) | Method for preparing nonanal by adopting loop reactor and Venturi ejector for preparing nonanal | |
| KR101206214B1 (en) | System For Producing Alcohol From Olefin | |
| CN111217686B (en) | Preparation method of n-valeraldehyde and special Venturi ejector | |
| Bhanage | Multiphase catalysis using water-soluble metal complexes in supercritical carbon dioxide | |
| US5961933A (en) | Process and apparatus for operation of a slurry bubble column with application to the fischer-tropsch synthesis | |
| CN103025695B (en) | An apparatus for coproduction of iso type aldehydes and alcohols from olefins, and a method for coproduction using the apparatus | |
| CN100595180C (en) | Improvements in or relating to hydroformylation | |
| CN102115433B (en) | Synthesis method of propionaldehyde by low-pressure carbonyl of ethylene | |
| CN113372206A (en) | Method for synthesizing high-carbon aldehyde by using microchannel reaction device | |
| CN113402551A (en) | Vinyl functionalized phosphine ligand, preparation and application thereof | |
| CN111151205A (en) | Propionaldehyde continuous production method and reaction system | |
| KR101448374B1 (en) | A method for the hydroformylation of olefin having excellent N／I ratio | |
| CN208275398U (en) | A kind of device preparing ketoisophorone | |
| CN108863738A (en) | A method of preparing cyclopentanone | |
| CN110526807B (en) | Continuous reaction device and method for preparing aldehyde through hydroformylation reaction | |
| US20240091737A1 (en) | Aldol condensation reaction apparatus | |
| KR101411133B1 (en) | A method for the hydroformylation of olefin having excellent N／I ratio | |
| CN108299177B (en) | Full continuous flow synthesis process of 2-methyl-1, 4-naphthoquinone | |
| Buchmüller et al. | Control of homogeneously catalyzed reactions by phase equilibria | |
| KR101298343B1 (en) | Reactor for the hydroformylation of olefin and method for the hydroformylation using the same | |
| CN111116346B (en) | Supercritical CO based on amorphous alloy2Hydrogenation process | |
| CN208554115U (en) | A kind of alpha-olefin hydroformylation reaction prepares the heterophase reactor of aldehyde | |
| CN115650833B (en) | Process method for strengthening olefin hydroformylation by microbubble flow | |
| CN112321411A (en) | Micro-interface preparation system and method for formic acid | |
| CN116143600A (en) | Method for preparing aldehyde compound by liquid-liquid continuous flow micro-channel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |