CN111217686A - Preparation method of n-valeraldehyde and special Venturi ejector - Google Patents
Preparation method of n-valeraldehyde and special Venturi ejector Download PDFInfo
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- CN111217686A CN111217686A CN202010047598.5A CN202010047598A CN111217686A CN 111217686 A CN111217686 A CN 111217686A CN 202010047598 A CN202010047598 A CN 202010047598A CN 111217686 A CN111217686 A CN 111217686A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/30—Injector mixers
- B01F25/31—Injector mixers in conduits or tubes through which the main component flows
- B01F25/312—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/30—Injector mixers
- B01F25/31—Injector mixers in conduits or tubes through which the main component flows
- B01F25/312—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof
- B01F25/3125—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof characteristics of the Venturi parts
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
- B01F25/30—Injector mixers
- B01F25/31—Injector mixers in conduits or tubes through which the main component flows
- B01F25/312—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof
- B01F25/3125—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof characteristics of the Venturi parts
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Abstract
The invention discloses a preparation method of n-valeraldehyde and a special Venturi ejector, wherein the preparation method adopts a loop reactor to prepare the n-valeraldehyde through butene hydroformylation; wherein, the inner diameter of the opening of the venturi ejector inlet section in the loop reactor 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: (1.5-5): (2-8): (10-50): (600-1700), wherein the opening angle of the diffuser section is 12-38 degrees; the preparation method of n-valeraldehyde takes butylene, hydrogen and carbon monoxide as raw materials, toluene as a solvent, Triphenylphosphine (TPP) and rhodium dicarbonyl acetylacetonate as catalysts, and the linear velocity of liquid at a nozzle of a Venturi ejector is controlled to be 50-110 m/s in the reaction process. The invention can effectively improve the normal-to-iso ratio of the product valeraldehyde by designing the loop reactor.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a method for preparing valeraldehyde by performing hydroformylation reaction by adopting novel reactor equipment, namely a loop reactor.
Background
Valeraldehyde is an important organic synthesis intermediate and can be used for preparing products such as n-valeraldehyde, n-pentanol, n-pentanoic acid, n-pentylamine and the like, wherein the n-valeraldehyde is a raw material for synthesizing 2-propyl-1-heptanol (2-PH) in strong demand at home and abroad, and the 2-PH can be used for further synthesizing a novel environment-friendly plasticizer, namely di (2-propylheptyl) phthalate (DPHP).
The main production methods of valeraldehyde include dichromate oxidation, bio-enzyme catalysis and hydroformylation. Among them, the dichromate oxidation method has the disadvantages that raw material amyl alcohol is expensive, and dichromate is toxic and harmful. Bio-enzyme catalysis is currently under the exploration phase. Neither of these processes achieves scale-up production. The hydroformylation reaction of butene and synthetic gas as material is the main method for synthesizing valeraldehyde and is also the common method for producing valeraldehyde in China.
In the technical report of preparing valeraldehyde by a hydroformylation method, the problems of low normal-to-iso ratio in the product (namely the molar ratio of the main product n-valeraldehyde to the byproduct isovaleraldehyde is about (9-15): 1), high catalyst dosage (namely the concentration of rhodium element in a reaction system is generally 150-250 mug/g) and the like still exist (Beijing university of chemical industry: 2014, 41 (6): 35-41; chemical engineering 2014, 42 (3): 49-53).
In the reaction for preparing valeraldehyde by the butene hydroformylation reaction, the reaction process is shown as above. The presence of a suitable amount of phosphine ligand promotes the production of the active species of the catalyst, i.e. promotes the conversion of butenes. At lower phosphine ligand contents, HRh (CO)3(PPh3) The relative content of the intermediate is high, and the generation of isovaleraldehyde in the product is promoted. As the phosphine to rhodium ratio increases, Triphenylphosphine (TPP) concentrations are relatively high, leading to HRh (CO)3(PPh3)2The content of the intermediate is increased, and the reaction is promoted to the n-valeraldehyde, namely the normal-to-iso ratio of the reaction product is increased. When the ratio of phosphine to rhodium exceeds a certain value, the coordination saturation of the coordination saturated complex HRh (CO) (PPh) without catalytic activity in the catalytic system3)3Plays a leading role in reducing the reaction conversion rate and the catalyst conversion frequency。
The amount of rhodium used as a catalyst in the reaction system is also critical. The normal-iso ratio of the valeraldehyde product shows a trend of increasing and then decreasing along with the increase of the catalyst dosage, and an optimal rhodium dosage interval exists. In the specific reaction process of butene hydroformylation, relevant process parameters such as reaction temperature, pressure, catalyst dosage, phosphine-rhodium ratio and the like jointly act on the final reaction conversion rate and the normal-iso ratio and influence and restrict each other.
Loop reactors are multiphase reactors which have been rapidly developed in recent years and are suitable for many types of reactions, consisting of a reaction vessel, a circulation pump, a heat exchanger and a venturi ejector (mixer). In the multiphase mixing and mass transfer process, compared with the traditional multiphase reactor, the loop reactor can provide better mixing effect and higher mass transfer coefficient, thereby having obvious advantages in the aspects of improving the utilization rate of raw materials, the yield of products and the like. And the amount of catalyst used can be significantly reduced. Among them, the venturi ejector is a key component of the loop reactor, and its working efficiency and working stability directly affect the working efficiency of the loop reactor. In the process of preparing valeraldehyde by a butene hydroformylation reaction method, gas-liquid two-phase mixing is involved, and a loop reactor is the best choice, so that the mass transfer speed can be accelerated, and the reaction time can be shortened.
In the loop reactor process, the venturi ejector is a key core component. Its design size can affect the mass transfer effect between specific chemical reaction substances, further affect the chemical reactor rate, reaction conversion rate and product selectivity. In patent 101679173A, although the rotation speed of the circulating pump is adjusted, the nozzle diameter of the venturi tube is optimized, and a certain range of improvement and optimization are simply carried out on the reaction equipment, the reaction rate is accelerated, and the energy consumption is reduced, but the control on the normal-to-abnormal ratio and the conversion rate of the final product valeraldehyde is not involved, and the venturi ejector serving as the core part of the loop reactor is not optimized, so the normal-to-abnormal ratio and the conversion rate of the previously mentioned product are not improved. Meanwhile, with the change of the size of the reactor, the amount of the catalyst and the related reaction process parameters also can finally influence the reaction conversion effect.
Disclosure of Invention
The invention provides a method for preparing valeraldehyde by butylene hydroformylation, which solves the problems of low normal-to-iso ratio, high catalyst consumption and the like in the prior art by optimizing design parameters and relevant process parameters of a venturi ejector which is a core component of a loop reactor.
In order to achieve the above object, the present invention provides a method for preparing n-valeraldehyde, which comprises preparing n-valeraldehyde by a butene hydroformylation reaction in a loop reactor; wherein, the inner diameter of the opening of the venturi ejector inlet section in the loop reactor 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: (1.5-5): (2-8): (10-50): (600-1700), wherein the opening angle of the diffuser section is 12-38 degrees; the preparation method of n-valeraldehyde takes butylene, hydrogen and carbon monoxide as raw materials, toluene as a solvent, Triphenylphosphine (TPP) and rhodium dicarbonyl acetylacetonate as catalysts, and the linear velocity of liquid at a nozzle of a Venturi ejector is controlled to be 50-110 m/s in the reaction process.
In the initial stage of the butene hydroformylation reaction, a catalyst is dissolved in a solvent to form a catalyst solution, and the catalyst solution is placed in a reaction kettle of a loop reactor; the content of rhodium element in the catalyst solution is 50-110 mu g/g, and the molar ratio of triphenylphosphine to rhodium element is (140-270): 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: 3: 4: 34: 850, the opening angle of the diffusion section is 23 degrees; the linear velocity of the liquid at the nozzle of the venturi ejector during the reaction was controlled to 80 m/s.
Further, the content of rhodium element in the catalyst solution is 70 μ g/g, the molar ratio of triphenylphosphine to rhodium element is 190: 1.
and further controlling reaction parameters: in the butene hydroformylation reaction process, the pressure of a reaction system is controlled to be 1.8MPa to 2.6MPa, and the reaction temperature is controlled to be 80 ℃ to 115 ℃.
Preferably, in the butene hydroformylation reaction process, the pressure of the reaction system is controlled to be 2.2MPa, and the reaction temperature is controlled to be 100 +/-1 ℃.
Further, the liquid level in the reaction kettle of the loop reactor is controlled to be 70% of the height of the whole reaction kettle in the initial state of the butene hydroformylation reaction.
Furthermore, 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 located at 10% of the height of the whole reaction kettle.
The invention also provides a special Venturi ejector for preparing the n-valeraldehyde by adopting the method, wherein 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: (1.5-5): (2-8): (10-50): (600-1700), and the opening angle of the diffuser section is 12-38 degrees.
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: 3: 4: 34: 850, the opening angle of the diffuser section is 23 °.
The invention can reach the best positive-to-differential ratio of the reaction product, reduce the dosage of rhodium catalyst, control the circulation loop, effectively save the cost and realize the green and energy saving by the design of the venturi ejector which is the key device of the loop reactor and the exploration of the process parameters under the novel reactor.
Compared with the existing loop reactor for preparing valeraldehyde by butene hydroformylation, the method has the following advantages:
1. a loop reactor is adopted as key process equipment to carry out the continuous production of valeraldehyde by the butene hydroformylation reaction. Through optimizing the structural design of the Venturi ejector, the gas-liquid mass transfer process is promoted, and the optimal positive-to-differential ratio and the optimal conversion rate are achieved.
2. Compared with the prior art, the method greatly reduces the consumption of noble metals, thereby reducing the production cost.
3. The n-valeraldehyde concentration in the reaction product is high, the subsequent separation link can be saved, and the reaction product can be directly used for synthesizing 2-propyl-1-heptanol (2-PH).
Drawings
FIG. 1 is a schematic view of the structure of a loop reactor for the production of n-valeraldehyde according to the 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 valeraldehyde production of the invention adopts a loop reactor to carry out butene hydroformylation reaction. 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 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 in the reaction process, and controls the fluctuation of the reaction temperature to +/-1 ℃. 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 between 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 a loop reactor at room temperature, a quantity of rhodium dicarbonyl acetylacetonate Rh (acac) (CO)2(Zhejiang metallurgy research institute Co., Ltd.) and triphenylphosphine (TPP, Shanghai reagent Co., Ltd.) were dissolved in toluene, and the solution was introduced into the reaction vessel 1 through the inlet. Synthetic gas (distributed in Nanjing special gas plant, volume ratio of hydrogen to carbon monoxide is 1.1: 1) is introduced into the reactor through the gas inlet until the system pressure is 1MPa, the circulating pump 4 is started to make the liquid in the reactor slowly flow, the air is discharged, and the air in the loop reactor is replaced for six times. A certain amount of butylene (purity is more than 99.9 percent in Nanjing special gas plant) is introduced under the pressure operation (the pressure of the synthesis gas is 0.6MPa), the temperature is increased to the preset reaction temperature (the temperature rise time is about 0.5h), then the mixed synthesis gas is immediately introduced to the reaction pressure, and the circulating pump 4 is adjusted until the flow rate reaches a certain value and is recorded as the reaction start time.
At the end of the reaction, the circulation pump 4 was immediately lowered in flow rate and rapidly cooled to room temperature (about 0.5 h). After emptying, the liquid product was taken and analyzed by WLFX 9790 gas chromatography (column PEG20M, 30 m.times.0.25 mm.times.0.33 μm, FID detector). Besides the main product of n-valeraldehyde, the liquid phase product also contains byproducts of isovaleraldehyde and trace n-amyl alcohol (less than 0.03 percent, neglecting and not calculating), a correction factor is introduced, and the total amount of valeraldehyde in the liquid composition is calculated by adopting the peak area ratio of the n-valeraldehyde, the isovaleraldehyde and the toluene and the initial addition amount of the toluene. During the reaction, the conversion of butene was calculated as the ratio of butene consumed to produce valeraldehyde to the initial charge of butene feed. The positive-to-differential ratio of the reaction products is calculated by using the chromatographic peak area ratio of n-valeraldehyde to isovaleraldehyde (the correction factors are the same). The noble metal dosage in the reaction system, namely the rhodium content in the toluene solution which is added into the reaction kettle in advance, is determined by JY38S-ICP emission spectrum. Under the reaction pressure, the reaction raw material butylene exists in a liquid form, and the liquid level in the reaction kettle is measured by the sum of the volumes of the toluene solution and the liquid butylene.
The research on the dosage of the catalyst rhodium in the reaction process finds that: the normal-iso ratio of the valeraldehyde product shows a trend of increasing and then decreasing along with the increase of the catalyst dosage, and an optimal rhodium dosage interval exists.
Best mode 1
2650ml of toluene solvent of dicarbonylacetylacetonate rhodium and triphenylphosphine was added into a 5L loop reactor (volume of the reaction kettle is 5L), the content of rhodium element in the catalyst solution was 70. mu.g/g, and the molar ratio of TPP to Rh was 190. Introducing synthetic gas (the volume ratio of hydrogen to carbon monoxide is 1.1: 1) into the reactor through the air inlet until the system pressure is 1MPa, starting a circulating pump to enable liquid in the reactor to slowly flow, emptying, and repeatedly replacing air in the loop reactor for six times. Under-pressure operation (synthesis gas pressure 0.6MPa), introducing 700g of butene, heating to a preset reaction temperature of 100 ℃, immediately introducing mixed gas to a reaction pressure of 2.2MPa, and adjusting a circulating pump 4 until the flow rate reaches a certain value, and recording 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, and the temperature is controlled to be 100 +/-1 ℃. Reacting for 45min, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (about 0.5h), and taking a liquid product after emptying to analyze and calculate the conversion rate and the selectivity.
In the reaction process, the linear velocity of liquid at the nozzle of the Venturi ejector is controlled to be 80m/s, the detailed design dimensions are that the ratio of the inlet section opening inner diameter D1, the nozzle inner diameter D2, the air chamber closing-in inner diameter D3, the mixing section length L1 and the diffusion section length L2 is 38: 3: 4: 34: 850, the diffusion section opening angle α is 23 degrees, as shown in FIG. 2, the insertion position of the bottommost end of the Venturi ejector is located at 10% of the height of the whole reaction kettle, and after the butylene is fed, the liquid level of materials in the reaction kettle is 70% of the height of the whole reaction kettle in the initial reaction state.
The product is analyzed, the conversion rate of the butene in the reaction process is 98 percent, and the n-iso ratio of the valeraldehyde in the reaction product is 53, so that the product can be directly used as a raw material for the subsequent synthesis of 2-propyl-1-heptanol (2-PH).
Example 2
A5L loop reactor (reactor volume 5L) was charged with 2650ml of toluene solvent of rhodium dicarbonylacetylacetonate and triphenylphosphine, catalyst rhodium content 60. mu.g/g, and molar ratio of TPP to Rh 210. Introducing synthetic gas (the volume ratio of hydrogen to carbon monoxide is 1.1: 1) into the reactor through the air inlet until the system pressure is 1MPa, starting a circulating pump to enable liquid in the reactor to slowly flow, emptying, and repeatedly replacing air in the loop reactor for six times. Under-pressure operation (synthesis gas pressure 0.6MPa), introducing 700g of butene, heating to a preset reaction temperature of 105 ℃, immediately introducing mixed gas to a reaction pressure of 1.9MPa, and adjusting a circulating pump 4 until the flow rate reaches a certain value, and recording 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 1.9MPa, and the temperature is controlled to be 105 +/-1 ℃. Reacting for 45min, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (about 0.5h), and taking a liquid product after emptying to analyze and calculate the conversion rate and the selectivity.
During the reaction, the linear velocity of the liquid at the nozzle of the Venturi ejector is controlled to be 80m/s, the detailed design dimensions are that the ratio of the inlet section opening inner diameter D1, the nozzle inner diameter D2, the air chamber closing-in inner diameter D3, the mixing section length L1 and the diffusion section length L2 is 38: 2.5: 5: 40: 850, the diffusion section opening angle α is 20 degrees, as shown in FIG. 2, the insertion position of the bottom end of the Venturi ejector is located at 10% of the height of the whole reaction kettle, and the liquid level of the material in the reaction kettle is 70% of the height of the whole reaction kettle.
The product is analyzed, the conversion rate of the butene in the reaction process is 92 percent, and the n-iso ratio of the valeraldehyde in the reaction product is 32, so that the product can be directly used as a raw material for the subsequent synthesis of 2-propyl-1-heptanol (2-PH).
Example 3
A5L loop reactor (reactor volume 5L) was charged with 2650ml of toluene solvent of rhodium dicarbonylacetylacetonate and triphenylphosphine, catalyst rhodium content 80. mu.g/g, and molar ratio of TPP to Rh 250. Introducing synthetic gas (the volume ratio of hydrogen to carbon monoxide is 1.1: 1) into the reactor through the air inlet until the system pressure is 1MPa, starting a circulating pump to enable liquid in the reactor to slowly flow, emptying, and repeatedly replacing air in the loop reactor for six times. Under-pressure operation (synthesis gas pressure 0.6MPa), introducing 700g of butene, heating to a preset reaction temperature of 95 ℃, immediately introducing mixed gas to a reaction pressure of 2.0MPa, and adjusting a circulating pump 4 until the flow rate reaches a certain value, and recording 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 2.0MPa, and the temperature is controlled to be 95 +/-1 ℃. Reacting for 45min, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (about 0.5h), and taking a liquid product after emptying to analyze and calculate the conversion rate and the selectivity.
During the reaction, the linear velocity of the liquid at the nozzle of the Venturi ejector is controlled to be 60m/s, the detailed design dimensions are that the ratio of the inlet section opening inner diameter D1, the nozzle inner diameter D2, the air chamber closing-in inner diameter D3, the mixing section length L1 and the diffusion section length L2 is 38: 2: 3: 15: 750, the diffusion section opening angle α is 17 degrees, as shown in FIG. 2, the insertion position of the bottommost end of the Venturi ejector is located at 10% of the height of the whole reaction kettle, and the liquid level of the material in the reaction kettle is 70% of the height of the whole reaction kettle.
The product is analyzed, the conversion rate of butylene in the reaction process is 89%, and the n-iso ratio of valeraldehyde in the reaction product is 44, so that the product can be directly used as a raw material for the subsequent synthesis of 2-propyl-1-heptanol (2-PH).
Example 4
A5L loop reactor (reactor volume 5L) was charged with 2650ml of toluene solvent of rhodium dicarbonylacetylacetonate and triphenylphosphine, catalyst rhodium content 90. mu.g/g, and molar ratio of TPP to Rh 150. Introducing synthetic gas (the volume ratio of hydrogen to carbon monoxide is 1.1: 1) into the reactor through the air inlet until the system pressure is 1MPa, starting a circulating pump to enable liquid in the reactor to slowly flow, emptying, and repeatedly replacing air in the loop reactor for six times. Under-pressure operation (synthesis gas pressure 0.6MPa), introducing 700g of butene, heating to a preset reaction temperature of 90 ℃, immediately introducing mixed gas to a reaction pressure of 2.5MPa, and adjusting a circulating pump 4 until the flow rate reaches a certain value, and recording 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 2.5MPa, and the temperature is controlled to be 90 +/-1 ℃. Reacting for 45min, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (about 0.5h), and taking a liquid product after emptying to analyze and calculate the conversion rate and the selectivity.
During the reaction, the linear velocity of the liquid at the nozzle of the Venturi ejector is controlled to be 90m/s, the detailed design dimensions are that the ratio of the inlet section opening inner diameter D1, the nozzle inner diameter D2, the air chamber closing-in inner diameter D3, the mixing section length L1 and the diffusion section length L2 is 38: 4: 5: 45: 1500, the diffusion section opening angle α is 30 degrees, as shown in FIG. 2, the insertion position of the bottommost end of the Venturi ejector is located at 10% of the height of the whole reaction kettle, and the liquid level of the material in the reaction kettle is 70% of the height of the whole reaction kettle.
The product is analyzed, the conversion rate of the butene in the reaction process is 81 percent, and the n-iso ratio of the valeraldehyde in the reaction product is 31, so that the product can be directly used as a raw material for the subsequent synthesis of the 2-propyl-1-heptanol (2-PH).
Example 5
A5L loop reactor (reactor volume 5L) was charged with 2650ml of toluene solvent of rhodium dicarbonylacetylacetonate and triphenylphosphine, catalyst rhodium content 100. mu.g/g, and molar ratio of TPP to Rh 180. Introducing synthetic gas (the volume ratio of hydrogen to carbon monoxide is 1.1: 1) into the reactor through the air inlet until the system pressure is 1MPa, starting a circulating pump to enable liquid in the reactor to slowly flow, emptying, and repeatedly replacing air in the loop reactor for six times. Under-pressure operation (synthesis gas pressure 0.6MPa), introducing 700g of butene, heating to a preset reaction temperature of 90 ℃, immediately introducing mixed gas to a reaction pressure of 2.0MPa, and adjusting a circulating pump 4 until the flow rate reaches a certain value, and recording 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 2.0MPa, and the temperature is controlled to be 90 +/-1 ℃. Reacting for 45min, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (about 0.5h), and taking a liquid product after emptying to analyze and calculate the conversion rate and the selectivity.
During the reaction, the linear velocity of the liquid at the nozzle of the Venturi ejector is controlled to be 100m/s, the detailed design dimensions are that the ratio of the inlet section opening inner diameter D1, the nozzle inner diameter D2, the air chamber closing-in inner diameter D3, the mixing section length L1 and the diffusion section length L2 is 38: 3.5: 4.5: 20: 1000, the opening angle α of the diffusion section is 33 degrees, as shown in FIG. 2, the insertion position of the bottom end of the Venturi ejector is located at 10% of the height of the whole reaction kettle, and the liquid level of the material in the reaction kettle is 70% of the height of the whole reaction kettle.
The product is analyzed, the conversion rate of the butene in the reaction process is 96 percent, and the n-iso ratio of the valeraldehyde in the reaction product is 32, so that the product can be directly used as a raw material for the subsequent synthesis of the 2-propyl-1-heptanol (2-PH).
Comparative example 1
A5L loop reactor (reactor volume 5L) was charged with 2650ml of toluene solvent of rhodium dicarbonylacetylacetonate and triphenylphosphine, catalyst rhodium content 135. mu.g/g, and molar ratio of TPP to Rh 203. Introducing synthetic gas (the volume ratio of hydrogen to carbon monoxide is 1.1: 1) into the reactor through the air inlet until the system pressure is 1MPa, starting a circulating pump to enable liquid in the reactor to slowly flow, emptying, and repeatedly replacing air in the loop reactor for six times. Under-pressure operation (synthesis gas pressure 0.6MPa), introducing 700g of butene, heating to a preset reaction temperature of 100 ℃, immediately introducing mixed gas to a reaction pressure of 2.0MPa, and adjusting a circulating pump 4 until the flow rate reaches a certain value, and recording 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 2.0MPa, and the temperature is controlled to be 90 +/-1 ℃. Reacting for 45min, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (about 0.5h), and taking a liquid product after emptying to analyze and calculate the conversion rate and the selectivity.
During the reaction, the linear velocity of the liquid at the nozzle of the Venturi ejector is controlled to be 45m/s, the detailed design dimensions are that the ratio of the inlet section opening inner diameter D1, the nozzle inner diameter D2, the air chamber closing-in inner diameter D3, the mixing section length L1 and the diffusion section length L2 is 38: 2: 3.5: 40: 1000, the diffusion section opening angle α is 24 degrees, as shown in FIG. 2, the insertion position of the bottom end of the Venturi ejector is located at 10% of the height of the whole reaction kettle, and the liquid level of the material in the reaction kettle is 70% of the height of the whole reaction kettle.
The product is analyzed, the conversion rate of the butene in the reaction process is 86 percent, and the normal-iso ratio of the valeraldehyde in the reaction product is 19.
Comparative example 2
A5L loop reactor (reactor volume 5L) was charged with 2650ml of toluene solvent of rhodium dicarbonylacetylacetonate and triphenylphosphine, catalyst rhodium content 75. mu.g/g, and molar ratio of TPP to Rh of 200. Introducing synthetic gas (the volume ratio of hydrogen to carbon monoxide is 1.1: 1) into the reactor through the air inlet until the system pressure is 1MPa, starting a circulating pump to enable liquid in the reactor to slowly flow, emptying, and repeatedly replacing air in the loop reactor for six times. Under-pressure operation (synthesis gas pressure 0.6MPa), introducing 700g of butene, heating to a preset reaction temperature of 95 ℃, immediately introducing mixed gas to a reaction pressure of 2.4MPa, and adjusting a circulating pump 4 until the flow rate reaches a certain value, and recording 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 2.4MPa, and the temperature is controlled to be 95 +/-1 ℃. Reacting for 45min, immediately reducing the flow rate of the circulating pump 4, rapidly cooling to room temperature (about 0.5h), and taking a liquid product after emptying to analyze and calculate the conversion rate and the selectivity.
During the reaction, the linear velocity of the liquid at the nozzle of the Venturi ejector is controlled to be 65m/s, the detailed design dimensions are that the ratio of the inlet section opening inner diameter D1, the nozzle inner diameter D2, the air chamber closing-in inner diameter D3, the mixing section length L1 and the diffusion section length L2 is 38: 9: 10: 9: 500, the diffusion section opening angle α is 10 degrees, as shown in FIG. 2, the insertion position of the bottommost end of the Venturi ejector is located at 10% of the height of the whole reaction kettle, and the liquid level of the material in the reaction kettle is 70% of the height of the whole reaction kettle.
The product is analyzed, the conversion rate of the butene in the reaction process is 41 percent, and the normal-iso ratio of the valeraldehyde in the reaction product is 25.
Claims (10)
1. A preparation method of n-valeraldehyde adopts a loop reactor to prepare n-valeraldehyde through butene hydroformylation; the method is characterized in that: the inner diameter of the opening of the venturi ejector inlet section in the loop reactor 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: (1.5-5): (2-8): (10-50): (600-1700), wherein the opening angle of the diffuser section is 12-38 degrees; the preparation method of the n-valeraldehyde takes butylene, hydrogen and carbon monoxide as raw materials, toluene as a solvent, triphenylphosphine and rhodium dicarbonyl acetylacetonate as catalysts, and the linear velocity of liquid at a nozzle of a Venturi ejector is controlled to be 50 m/s-110 m/s in the reaction process.
2. The method for producing n-valeraldehyde according to claim 1, wherein: in the initial stage of the butene hydroformylation reaction, a catalyst is dissolved in a solvent to form a catalyst solution which is placed in a reaction kettle of a loop reactor; the content of rhodium element in the catalyst solution is 50-110 mu g/g, and the molar ratio of triphenylphosphine to rhodium element is (140-270): 1.
3. the method for producing n-valeraldehyde according to claim 1 or claim 2, 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: 3: 4: 34: 850, the opening angle of the diffusion section is 23 degrees; the linear velocity of the liquid at the nozzle of the venturi ejector during the reaction was controlled to 80 m/s.
4. The method for producing n-valeraldehyde according to claim 3, wherein: the content of rhodium element in the catalyst is 70 mu g/g, and the molar ratio of triphenylphosphine to rhodium element is 190: 1.
5. The method for producing n-valeraldehyde according to claim 4, wherein: in the butene hydroformylation reaction process, the pressure of a reaction system is controlled to be 1.8MPa to 2.6MPa, and the reaction temperature is controlled to be 80 ℃ to 115 ℃.
6. The method for producing n-valeraldehyde according to claim 5, wherein: in the butene hydroformylation reaction process, the pressure of a reaction system is controlled to be 2.2MPa, and the reaction temperature is controlled to be 100 +/-1 ℃.
7. The method for producing n-valeraldehyde according to claim 6, wherein: and controlling the liquid level in the reaction kettle of the loop reactor to be 70% of the height of the whole reaction kettle in the initial state of the butene hydroformylation reaction.
8. The method for producing n-valeraldehyde according to claim 7, wherein: the bottom end of the Venturi ejector stretches into the lower end in the reaction kettle, and the bottommost stretching position of the Venturi ejector is located at 10% of the height of the whole reaction kettle.
9. The venturi ejector for preparing the n-valeraldehyde is characterized in that: 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: (1.5-5): (2-8): (10-50): (600-1700), and the opening angle of the diffuser section is 12-38 degrees.
10. The venturi ejector of claim 9, 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: 3: 4: 34: 850, the opening angle of the diffuser section is 23 °.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113233965A (en) * | 2021-05-06 | 2021-08-10 | 江苏清泉化学股份有限公司 | Synthesis method of acetyl n-propanol |
| CN115430392A (en) * | 2022-08-31 | 2022-12-06 | 江苏诺盟化工有限公司 | Preparation method of benzil and special Venturi ejector |
| CN115819185A (en) * | 2022-12-28 | 2023-03-21 | 南京大学扬州化学化工研究院 | Method for synthesizing neopentyl glycol |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054342A (en) * | 2006-04-11 | 2007-10-17 | 中国科学院兰州化学物理研究所 | Process of continuously preparing n-pentanal |
| CN102272079A (en) * | 2009-01-16 | 2011-12-07 | Lg化学株式会社 | Apparatus for producing alcohols from olefins |
| CN104030900A (en) * | 2013-04-11 | 2014-09-10 | 中石化上海工程有限公司 | Method for preparing aldehyde by hydroformylation of low light olefins |
| CN110128251A (en) * | 2019-06-24 | 2019-08-16 | 上海华谊（集团）公司 | Hydroformylation process and equipment |
| CN110156580A (en) * | 2019-06-24 | 2019-08-23 | 上海华谊（集团）公司 | The method and apparatus of alkene aldehyde |
-
2020
- 2020-01-16 CN CN202010047598.5A patent/CN111217686B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054342A (en) * | 2006-04-11 | 2007-10-17 | 中国科学院兰州化学物理研究所 | Process of continuously preparing n-pentanal |
| CN102272079A (en) * | 2009-01-16 | 2011-12-07 | Lg化学株式会社 | Apparatus for producing alcohols from olefins |
| CN104030900A (en) * | 2013-04-11 | 2014-09-10 | 中石化上海工程有限公司 | Method for preparing aldehyde by hydroformylation of low light olefins |
| CN110128251A (en) * | 2019-06-24 | 2019-08-16 | 上海华谊（集团）公司 | Hydroformylation process and equipment |
| CN110156580A (en) * | 2019-06-24 | 2019-08-23 | 上海华谊（集团）公司 | The method and apparatus of alkene aldehyde |
Non-Patent Citations (1)
| Title |
|---|
| 李韶璞: "喷射回路反应器中文丘里喷射器混合特性的研究", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113233965A (en) * | 2021-05-06 | 2021-08-10 | 江苏清泉化学股份有限公司 | Synthesis method of acetyl n-propanol |
| CN115430392A (en) * | 2022-08-31 | 2022-12-06 | 江苏诺盟化工有限公司 | Preparation method of benzil and special Venturi ejector |
| CN115430392B (en) * | 2022-08-31 | 2024-04-16 | 江苏诺盟化工有限公司 | Preparation method of benzil and special venturi ejector |
| CN115819185A (en) * | 2022-12-28 | 2023-03-21 | 南京大学扬州化学化工研究院 | Method for synthesizing neopentyl glycol |
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