A method and apparatus for the continuous production of trisubstituted phosphine derivatives in a tower

Abstract

This invention relates to the field of continuous synthesis of organophosphine compounds, and discloses a method and apparatus for the preparation of trisubstituted phosphine derivatives by continuous tower addition, comprising the following steps: S1. Phosphine and a liquid-phase feedstock containing carbon-carbon unsaturated bonds are continuously introduced into a first reaction tower serving as the absorption and preliminary addition zone for phosphine absorption and preliminary addition reaction; S2. The qualified reaction liquid collected from the first reaction tower is sent to a second reaction tower, and a liquid-phase feedstock containing carbon-carbon unsaturated bonds is added to continue the addition reaction; S3. The qualified reaction liquid collected from the second reaction tower is sent to a third reaction tower, and a liquid-phase feedstock containing carbon-carbon unsaturated bonds is added to promote the conversion of the low-substituted phosphorus intermediate into the trisubstituted phosphine derivative; This application obtains the low-substituted phosphorus intermediate by first performing phosphine absorption and preliminary addition reaction, and then continues the conversion of the low-substituted phosphorus intermediate in the main reaction and post-maturation stages, reducing the residues of monosubstituted and disubstituted products and significantly improving the selectivity of the trisubstituted phosphine derivative.

Description

Technical Field

[0001] This invention relates to the field of continuous synthesis of organophosphorus compounds, and specifically to a method and apparatus for preparing trisubstituted phosphine derivatives by tower-type continuous addition. Background Technology

[0002] Trisubstituted phosphine derivatives are an important class of organophosphine compounds, used as intermediates in pharmaceuticals, pesticides, catalyst ligands, functional materials, metal extractants, and specialty chemicals. Typical products include tris(3-hydroxypropyl)phosphine, obtained by the addition of phosphine to allyl alcohol, and trioctylphosphine, obtained by the addition of phosphine to olefins such as octene. These reactions typically involve gas-liquid contact, absorption, mass transfer, and stepwise addition between phosphine gas and liquid feedstock containing carbon-carbon unsaturated bonds.

[0003] Phosphines possess hazardous properties such as high toxicity and flammability. Traditional batch-gas reactors suffer from problems including large gas phase space, high instantaneous phosphine holding capacity, large fluctuations in tail gas composition, phosphine loss due to nitrogen replacement, and difficulty in accurately measuring the effective absorption of phosphine. Furthermore, for the preparation of trisubstituted phosphine derivatives, a single phosphine molecule needs to undergo stepwise addition with multiple carbon-containing unsaturated bonds. If there is localized phosphine excess, insufficient liquid-phase feedstock, uneven gas-liquid mass transfer, or insufficient residence time, low-substituted phosphorus intermediates such as monosubstituted and disubstituted phosphines can easily remain, leading to a decrease in the selectivity and quality stability of the target product.

[0004] Continuous tower reactors can enhance gas-liquid mass transfer through packing, trays, spraying, liquid distribution, gas distribution, and online monitoring, and are conducive to achieving closed-loop, automated, and low-hold-load operation. However, when a single continuous tower reactor is divided into axial sections, it is difficult to optimize the pressure, residence time, replenishment liquid feed location, and detection circulation strategy for each functional zone separately, especially to simultaneously take into account pressurized phosphine absorption, atmospheric pressure main reaction, and atmospheric pressure post-reaction ripening. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide a method and apparatus for preparing trisubstituted phosphine derivatives by continuous addition in a tower manner. The method involves first performing phosphine absorption and preliminary addition reaction to obtain a low-substituted phosphorus-containing intermediate, and then further converting the low-substituted phosphorus-containing intermediate in the main reaction and post-maturation stages to reduce the residues of monosubstituted and disubstituted products and significantly improve the selectivity of trisubstituted phosphine derivatives.

[0006] The technical solution adopted in this invention is as follows: A method for preparing trisubstituted phosphine derivatives by continuous addition in a tower configuration includes at least the following steps: S1. Phosphine and carbon-containing unsaturated carbon-phase raw materials are continuously introduced into the first reaction tower, which serves as the absorption and preliminary addition zone. Phosphine absorption and preliminary addition reactions are carried out under pressure in the first reaction tower and in the atmosphere of catalyst and solvent. S2. The qualified reaction liquid collected from the first reaction tower is sent to the second reaction tower, which is the main reaction zone. Carbon-containing unsaturated carbon-carbon raw materials are added to the second reaction tower, and the addition reaction continues under atmospheric pressure in the second reaction tower. S3. The qualified reaction liquid collected from the second reaction tower is sent to the third reaction tower. Carbon-containing unsaturated carbon bond liquid phase raw material is added to the third reaction tower. The third reaction tower serves as the post-reaction maturation zone. Under normal pressure conditions, it promotes the conversion of low-substituted phosphorus intermediates into trisubstituted phosphine derivatives. S4. Qualified trisubstituted phosphine derivative product liquid is collected through the third reaction tower.

[0007] Preferably, the carbon-carbon unsaturated bond liquid phase raw material includes at least one of olefins, unsaturated alcohols, alkenyl ethers, alkenyl esters, unsaturated carboxylic acid esters, heteroatom-substituted olefins, or functionalized organic raw materials containing carbon-carbon double bonds; the trisubstituted phosphine derivative is tris(3-hydroxypropyl)phosphine, trioctylphosphine, or other trisubstituted phosphine derivatives formed by the addition of phosphine with the carbon-carbon unsaturated bond liquid phase raw material.

[0008] Preferably, when the reaction liquid collected from each reaction tower fails to meet the preset qualified conditions, the unqualified reaction liquid is returned to the corresponding reaction tower from which it was collected; catalyst and / or solvent are added to the second reaction tower; and catalyst and / or solvent are added to the third reaction tower.

[0009] Preferably, in the first reaction tower in step S1, the feed volume ratio of the carbon-carbon unsaturated bond liquid phase feedstock to the solvent ranges from 1:0.7 to 1.5, and its molar ratio to phosphine feed is 0.35 to 1.2:1, while the catalyst accounts for 2-8% of the phosphine feed mass; in the second reaction tower in step S2, the volume ratio of the added carbon-carbon unsaturated bond liquid phase feedstock to the added solvent ranges from 1:0.7 to 1.5, and its molar ratio to that in step S1 is 0.35 to 1.2:1. The molar ratio of the feed phosphine is 0.35-1.2:1, and the mass ratio of the added catalyst to the feed phosphine in step S1 is 2-8%. In step S3, the volume ratio of the carbon-containing unsaturated carbon bond liquid phase feedstock to the added solvent in the third reaction tower is 1:0.7-1.5, and the molar ratio of the added catalyst to the feed phosphine in step S1 is 0.35-1.2:1. The mass ratio of the added catalyst to the feed phosphine in step S1 is 2-8%.

[0010] Preferably, the preset qualification conditions for the qualified reaction liquid collected from the first reaction tower are: the content of unreacted liquid phase material containing carbon-carbon unsaturated bonds is not higher than a first preset threshold, the first preset threshold being in the range of 5-15 wt%, and / or, the content of dissolved phosphine is not higher than 1.0 wt%, more preferably not higher than 0.5 wt%; The preset qualification conditions for the qualified reaction liquid collected from the second reaction tower are as follows: the content of unreacted liquid phase material containing carbon-carbon unsaturated bonds is not higher than the second preset threshold, which is in the range of 2-5 wt%; and / or, the mass fraction of low-substituted phosphorus intermediates in the total organophosphorus compounds is not higher than the third preset threshold, which is in the range of 10-15%. The preset qualification conditions for the qualified trisubstituted phosphine derivative product liquid collected from the third reaction tower are: the content of unreacted carbon-carbon unsaturated bond liquid phase material is not higher than 1.0 wt%, more preferably not higher than 0.5 wt%, and / or the target trisubstituted phosphine derivative accounts for ≥95% of the total organophosphorus compounds by mass fraction.

[0011] Preferably, the catalyst is a free radical initiating catalyst, a transition metal catalytic catalyst, or a photo / thermal initiating catalyst; the solvent is an organic solvent, an aqueous solvent, or a mixed solvent.

[0012] Preferably, the operating pressure range of the first reaction tower is set at 0.6-2.0 MPa (A) to form pressurized conditions; the operating pressure range of the second and third reaction towers is set at 0.1-0.12 MPa (A) to form atmospheric pressure conditions; and the operating temperature of the first, second, and third reaction towers is set at 70-90℃.

[0013] Preferably, an apparatus for the continuous addition reaction of a tower to prepare trisubstituted phosphine derivatives includes: First reaction tower; Second reaction tower; Third reaction tower; The first reaction tower is equipped with a phosphine inlet pipeline, a liquid raw material inlet pipeline containing carbon-carbon unsaturated bonds, and a reaction liquid outlet pipeline located in the bottom of the tower. It is also equipped with a gas outlet at the top. The gas phase is condensed by the condenser and the liquid phase flows back into the tower. The gas phase tail gas is discharged through the tail gas outlet pipeline. The second reaction tower is respectively equipped with a second reaction tower feed pipeline connected to the reaction liquid outflow pipeline of the first reaction tower, a second reaction tower replenishment liquid feed pipeline located at the top of the tower, and a second reaction tower reaction liquid outflow pipeline located at the bottom of the tower; The third reaction tower is respectively equipped with a third reaction tower feed pipeline connected to the reaction liquid outflow pipeline of the second reaction tower, a third reaction tower replenishment liquid feed pipeline located at the top of the tower, and a third reaction tower reaction liquid outflow pipeline at the bottom of the tower. A first detection unit is provided between the reaction liquid outlet pipeline of the first reaction tower and the feed pipeline of the second reaction tower. A first circulation pipeline is provided between the unqualified outlet of the first detection unit and the first reaction tower, and its qualified outlet is connected to the feed pipeline of the second reaction tower. A second detection unit is provided between the reaction liquid outlet pipeline of the second reaction tower and the feed pipeline of the third reaction tower. A second circulation pipeline is provided between the unqualified outlet of the second detection unit and the second reaction tower, and its qualified outlet is connected to the feed pipeline of the third reaction tower. The reaction liquid collection pipeline of the third reaction tower and the product tank are equipped with a third detection unit. The unqualified outlet of the third detection unit is connected to the third reaction tower with a third circulation pipeline, and its qualified outlet is connected to the product tank. Trisubstituted phosphine derivatives were prepared using the method described above for preparing trisubstituted phosphine derivatives by continuous tower addition.

[0014] Preferably, the first reaction tower, the second reaction tower, and the third reaction tower are all equipped with catalyst feeding channels and solvent feeding channels; wherein, the catalyst feeding channel or solvent feeding channel is an independent feeding channel directly connected to its corresponding reaction tower, or is merged into the feed pipeline or circulation pipeline corresponding to each reaction tower.

[0015] Preferably, at least one of the first, second, and third reaction towers is provided with an enhanced mass transfer or enhanced mixing element, wherein the enhanced mass transfer or enhanced mixing element includes at least one of structured packing, random packing, trays, sprayers, liquid distributors, gas distributors, static mixing elements, liquid film forming structures, and bubble distributors.

[0016] Compared with existing technologies, the present invention has the following main advantages: 1. This invention creatively sets up a three-stage tower reaction process route, with a first reaction tower, a second reaction tower, and a third reaction tower respectively. By setting independent and flexible process conditions for the staged continuous reaction towers, each reaction tower undertakes the functions of absorption and preliminary addition, main reaction, and post-reaction maturation, resulting in greater process controllability. In particular, the first reaction tower operates under pressurized conditions, which helps to increase the partial pressure of phosphine, extend the gas-liquid contact path of phosphine, and improve the absorption effect of phosphine, thereby reducing the phosphine content in the tail gas at the top of the tower. At the same time, the second and third reaction towers operate under atmospheric pressure conditions. By adding carbon-containing unsaturated carbon-phase raw materials, the low-substituted phosphorus-containing intermediates continue to be transformed in the main reaction and post-maturation stages, reducing the residue of mono- and di-substituted products and significantly improving the selectivity of tri-substituted phosphine derivatives.

[0017] 2. In this invention, the reaction liquids collected from each stage of the reaction tower are all tested according to preset qualification conditions, and a circulation return mechanism is established between the unqualified reaction liquids and their corresponding reaction towers. The reaction liquids that do not meet the preset qualification indicators are returned to the corresponding reaction towers to continue the reaction, and only the reaction liquids that meet the preset indicators enter the next stage of the reaction tower or the product tank, which is beneficial to stabilizing product composition and batch-to-batch quality. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of the connection structure of the apparatus for the three-stage tower-type continuous addition preparation of trisubstituted phosphine derivatives according to an embodiment of the present invention.

[0019] Figure 2 This is a schematic diagram of the operation flow of the three-stage tower-type continuous addition method for preparing trisubstituted phosphine derivatives according to an embodiment of the present invention.

[0020] Figure 3 The image shows the phosphorus nuclear magnetic resonance spectrum of the tri(3-hydroxypropyl)phosphine product after the product liquid obtained in Example 1 of this invention has been purified by a subsequent vacuum distillation column.

[0021] Figure 4 The image shows the phosphorus nuclear magnetic resonance spectrum of the trioctylphosphine product obtained after the product liquid obtained in Example 2 of this invention has been purified by a vacuum distillation column.

[0022] Figure 5 The image shows a gas chromatogram of the trioctylphosphine product obtained after the product liquid obtained in Example 2 of this invention has been purified by a vacuum distillation column. Detailed Implementation

[0023] Please see Figure 1 As shown, this embodiment discloses a tower-type continuous addition apparatus for preparing trisubstituted phosphine derivatives, comprising: First reaction tower 1; Second reaction tower 11; Third reaction tower 17; The first reaction tower 1 is equipped with a phosphine inlet pipeline 2 (its inlet is located below the side of the first reaction tower 1), a liquid raw material inlet pipeline 4 containing carbon-carbon unsaturated bonds (its inlet is located above the side of the first reaction tower 1), and a first reaction tower reaction liquid outlet pipeline 7 located in the bottom of the tower. It is also equipped with a gas phase outlet at the top. The gas phase is condensed by the condenser 6 and the liquid phase flows back into the first reaction tower 1. The gas phase tail gas is discharged through the tail gas outlet pipeline 5, which facilitates the subsequent recovery, absorption or safe treatment of the tail gas. The second reaction tower 11 is respectively provided with a second reaction tower feed pipeline 12 connected to the first reaction tower reaction liquid outflow pipeline 7, a second reaction tower replenishment liquid raw material feed pipeline 13 located at the top of the tower, and a second reaction tower reaction liquid outflow pipeline 14 located at the bottom of the tower. The third reaction tower 17 is respectively equipped with a third reaction tower feed pipeline 16 connected to the reaction liquid collection pipeline 14 of the second reaction tower, a third reaction tower replenishment liquid feed pipeline 19 located at the top of the tower, and a third reaction tower reaction liquid collection pipeline 20 at the bottom of the tower. A first detection unit 8a is provided between the reaction liquid outlet pipeline 7 of the first reaction tower and the feed pipeline 12 of the second reaction tower. A first circulation pipeline 9 is provided between the unqualified outlet of the first detection unit 8a and the first reaction tower 1 (specifically, it can be connected to the feed pipeline 4 of the carbon-containing unsaturated bond liquid phase raw material via the circulation pump 3), and its qualified outlet is connected to the feed pipeline 12 of the second reaction tower. A second detection unit 8b is provided between the reaction liquid outlet pipeline 14 of the second reaction tower and the feed pipeline 16 of the third reaction tower. A second circulation pipeline 15 is provided between the unqualified outlet of the second detection unit 8b and the second reaction tower 11, and its qualified outlet is connected to the feed pipeline 16 of the third reaction tower. The reaction liquid collection pipeline 20 of the third reaction tower and the product tank are equipped with a third detection unit 8c. The unqualified outlet of the third detection unit 8c and the third reaction tower 17 are connected to a third circulation pipeline 22, and its qualified outlet is connected to the product tank.

[0024] Preferably, in this embodiment, the first reaction tower 1, the second reaction tower 11, and the third reaction tower 17 are all provided with a catalyst feeding channel 23 and a solvent feeding channel 24; wherein, the catalyst feeding channel or the solvent feeding channel is an independent feeding channel directly connected to its corresponding reaction tower, or is merged into the feed pipeline or circulation pipeline corresponding to each reaction tower; specifically preferably, in this embodiment, the catalyst feeding channel 23 and the solvent feeding channel 24 of the first reaction tower 1 are merged into the feed pipeline 4 of the carbon-containing unsaturated bond liquid phase raw material; the catalyst feeding channel 23 and the solvent feeding channel 24 of the second reaction tower 11 are merged into the second circulation pipeline 15; the catalyst feeding channel 23 and the solvent feeding channel 24 of the third reaction tower 17 are merged into the third circulation pipeline 22; preferably, in this embodiment, in order to facilitate uniform mixing of materials, a static mixer 26 is respectively provided on the feed pipeline 4 of the carbon-containing unsaturated bond liquid phase raw material, the second circulation pipeline 15, and the third circulation pipeline 22.

[0025] Preferably, in this embodiment, at least one of the first reaction tower 1, the second reaction tower 11, and the third reaction tower 17 is provided with an enhanced mass transfer or enhanced mixing element. This enhanced mass transfer or enhanced mixing element includes at least one of structured packing, random packing, trays, sprayers, liquid distributors, gas distributors, static mixing elements, liquid film forming structures, and bubble distributors. Through these structures, the reaction liquid forms a liquid film, droplets, or dispersed flow state within its corresponding reaction tower, increasing the gas-liquid or liquid-liquid contact area and improving mass transfer and reaction uniformity. More preferably, the first reaction tower 1, the second reaction tower 11, and the third reaction tower 17 are all provided with enhanced mass transfer or enhanced mixing elements, forming a packed tower, a tray tower, a bubble tower, a spray tower, a tower reactor with a static mixing structure, or a tower reactor formed by a combination of the above structures. Specifically, preferably, in this embodiment, the first reaction tower 1, the second reaction tower 11, and the third reaction tower 17 are each provided with one enhanced mass transfer or enhanced mixing element 25 (specifically using corrugated structured packing) at the top and bottom.

[0026] More preferably, in this embodiment, in order to further facilitate the control of the operating conditions of each reaction tower, the first reaction tower 1, the second reaction tower 11 and the third reaction tower 17 can be further equipped with temperature detection points, pressure detection points, liquid level detection points, pressure drop detection points, sampling ports and circulation ports. In order to achieve the preset operating temperature, temperature control units such as cooling jackets, heating jackets or internal coils can be further provided respectively.

[0027] More preferably, in this embodiment, the online monitoring unit (including each detection point or each detection unit) and interlock control unit involved in this application can be connected to the phosphine gas feed valve, the liquid phase feed pump, the circulation pump, the inert gas replacement valve, the pressure control valve, and the emergency shut-off valve; wherein, when the phosphine concentration of the tail gas, the pressure, temperature, or liquid level of the reaction tower are found to exceed the preset range, the system can automatically alarm, shut off the phosphine gas, adjust the liquid phase feed, or start the inert gas replacement.

[0028] Please refer to the above for further details. Figure 2 As shown, this embodiment utilizes the tower-type continuous addition apparatus for preparing trisubstituted phosphine derivatives, and provides a method for preparing trisubstituted phosphine derivatives using the tower-type continuous addition apparatus, comprising the following steps: S1. Phosphine and carbon-containing unsaturated liquid-phase feedstock are continuously introduced into the first reaction tower 1 (i.e., the absorption and preliminary addition zone). Figure 2 The marked "Reaction Tower 1" is used for the phosphine absorption and preliminary addition reaction under pressurized conditions and in the atmosphere of catalyst and solvent. S2. The qualified reaction liquid collected from the first reaction tower 1 is sent to the second reaction tower 11, which serves as the main reaction zone (i.e., the... Figure 2 The marked "Reaction Tower 2" adds a liquid raw material containing carbon-carbon unsaturated bonds to the second reaction tower 11, and the addition reaction continues under atmospheric pressure conditions in the second reaction tower 11; S3. The qualified reaction solution collected from the second reaction tower 11 is sent to the third reaction tower 17 (i.e., the... Figure 2 The marked "Reaction Tower 3" adds carbon-containing unsaturated carbon-carbon liquid raw material to the third reaction tower 17. The third reaction tower 17 serves as a post-reaction maturation zone, promoting the conversion of low-substituted phosphorus intermediates into trisubstituted phosphine derivatives under normal pressure conditions. S4. Qualified trisubstituted phosphine derivative product liquid is collected through the third reaction tower 17 and sent to the product tank; the product liquid in the product tank is further purified by distillation to obtain a high-purity product.

[0029] Preferably, in this embodiment, the liquid phase raw material containing carbon-carbon unsaturated bonds includes at least one of olefins, unsaturated alcohols, alkenyl ethers, alkenyl esters, unsaturated carboxylic acid esters, heteroatom-substituted olefins, or functionalized organic raw materials containing carbon-carbon double bonds; the trisubstituted phosphine derivative is tris-3-hydroxypropylphosphine, trioctylphosphine, or other trisubstituted phosphine derivatives formed by the addition of phosphine to the liquid phase raw material containing carbon-carbon unsaturated bonds.

[0030] Preferably, in this embodiment, when the reaction liquid collected from each reaction tower fails to meet the preset qualified conditions, the unqualified reaction liquid is returned to the corresponding reaction tower from which it was collected; catalyst and / or solvent are added to the second reaction tower 11; and catalyst and / or solvent are added to the third reaction tower 17.

[0031] Preferably, in this embodiment, in the first reaction tower 1 of step S1, the feed volume ratio of the carbon-carbon unsaturated bond liquid phase raw material to the solvent ranges from 1:0.7 to 1.5, and its feed molar ratio to phosphine is 0.35 to 1.2:1, while the catalyst accounts for 2-8% of the phosphine feed mass; in the second reaction tower 11 of step S2, the volume ratio of the added carbon-carbon unsaturated bond liquid phase raw material to the added solvent ranges from 1:0.7 to 1.5, and its feed molar ratio to phosphine is 0.35 to 1.2:1, while the catalyst accounts for 2-8% of the phosphine feed mass. In step S1, the molar ratio of the feed phosphine is 0.35-1.2:1, and the added catalyst accounts for 2-8% of the mass of the feed phosphine in step S1. In step S3, the volume ratio of the carbon-containing unsaturated carbon bond liquid phase feedstock to the added solvent in the third reaction tower 17 is 1:0.7-1.5, and the molar ratio of the added catalyst to the feed phosphine in step S1 is 0.35-1.2:1, while the added catalyst accounts for 2-8% of the mass of the feed phosphine in step S1.

[0032] Preferably, in this embodiment, the preset qualified conditions for the qualified reaction liquid collected from the first reaction tower 1 are: the content of unreacted liquid phase material containing carbon-carbon unsaturated bonds is not higher than a first preset threshold, the range of the first preset threshold is set to 5-15 wt%, and / or, the content of dissolved phosphine is not higher than 1.0 wt%, more preferably not higher than 0.5 wt%; The preset qualified conditions for the qualified reaction liquid collected from the second reaction tower 11 are as follows: the content of unreacted liquid phase material containing carbon-carbon unsaturated bonds is not higher than the second preset threshold, the range of the second preset threshold is set to 2-5 wt%, and / or, the mass fraction of low-substituted phosphorus intermediates in the total organophosphorus compounds is not higher than the third preset threshold, the range of the third preset threshold is set to 10-15%; The preset qualification conditions for the qualified trisubstituted phosphine derivative product liquid collected from the third reaction tower 17 are: the content of unreacted carbon-carbon unsaturated bond liquid phase material is not higher than 1.0 wt%, more preferably not higher than 0.5 wt%, and / or the target trisubstituted phosphine derivative accounts for ≥95% of the total organophosphorus compounds by mass fraction.

[0033] It should be noted that the first detection unit 8a, the second detection unit 8b and the third detection unit 8c involved in this application are configured according to the preset qualified conditions set by their corresponding reaction towers, so as to realize the monitoring of their preset qualified conditions. These are all conventional technical choices that can be made by those skilled in the art based on the implementation content of this application. Therefore, the specific detection results adopted will not be described in detail, and the detection units themselves are not considered as innovative content of this application.

[0034] Preferably, in this embodiment, the catalyst is a free radical initiating catalyst, a transition metal catalytic catalyst, or a photo / thermal initiating catalyst, which can be specifically selected according to actual needs; the solvent is an organic solvent, an aqueous solvent, or a mixed solvent, which is used to dissolve or disperse reactants, adjust viscosity, and improve mass transfer, and can be specifically selected according to actual needs.

[0035] Preferably, in this embodiment, the operating pressure range of the first reaction tower 1 is set at 0.6-1.2 MPa (A) to form pressurized conditions; the operating pressure range of the second reaction tower 11 and the third reaction tower 17 is set at 0.1-0.12 MPa (A); it should be noted that "(A)" specifically marked in this application represents absolute pressure, forming atmospheric pressure conditions; the operating temperature of the first reaction tower 1, the second reaction tower 11 and the third reaction tower 17 is set at 70-90℃.

[0036] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of the embodiments of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.

[0037] It should be noted that, based on the above-described implementation scheme of this application, this application also specifically proposes the following Specific Embodiment 1 and Embodiment 2:

[0038] Example 1: Continuous three-stage tower preparation of tris(3-hydroxypropyl)phosphine

[0039] In this embodiment 1, the diameter of the first reaction tower 1, the second reaction tower 11, and the third reaction tower 17 are all 500 mm, and the height of each tower is 10,000 mm. Each tower is equipped with corrugated structured packing as a mass transfer enhancement or mixing enhancement element 25 to improve phosphine absorption efficiency, liquid phase mixing uniformity, and addition reaction conversion efficiency. The first reaction tower 1 is a pressurized reaction tower, while the second reaction tower 11 and the third reaction tower 17 are atmospheric pressure reaction towers.

[0040] Pressurized phosphine gas is continuously fed into the first reaction tower 1 via phosphine inlet line 2 at a mass feed rate of 10 kg / h. Allyl alcohol and anhydrous ethanol are mixed at a volume ratio of 1:1 to prepare a liquid feedstock, which is then continuously fed into the first reaction tower 1 via carbon-carbon unsaturated bond liquid feedstock line 4 at a volume feed rate of 40 L / h. Azobisisobutyronitrile (AIBN) is used as the catalyst and is added to the first reaction tower 1 via catalyst feed channel 23 at a feed rate of 450 g / h. The operating pressure of the first reaction tower 1 is 1.0 MPa (A), and the operating temperature is 80℃. Phosphine absorption and preliminary addition reactions are completed within this tower.

[0041] After the effluent from the first reaction tower 1 is detected by the first detection unit 8a and meets the preset control index, it enters the second reaction tower 11 through the second reaction tower feed pipeline 12. If the preset control index is not met, it returns to the first reaction tower 1 through the first circulation pipeline 9 to continue the reaction. The addition reaction continues in the second reaction tower 11, and the above-mentioned allyl alcohol / anhydrous ethanol liquid phase feedstock is added through the second reaction tower replenishment liquid phase feedstock feed pipeline 13 at a replenishment rate of 40 L / h; at the same time, azobisisobutyronitrile is added through the catalyst feed channel 23 at a replenishment rate of 450 g / h. The operating pressure of the second reaction tower 11 is 0.105 MPa (A), and the operating temperature is 80℃.

[0042] After the effluent from the second reaction tower 11 reaches the preset control index as detected by the second detection unit 8b, it enters the third reaction tower 17 via the third reaction tower feed line 16. If the preset control index is not reached, it returns to the second reaction tower 11 via the second circulation line 15 to continue the reaction. The third reaction tower 17 serves as a post-reaction maturation zone, used to promote the further conversion of low-substituted phosphorus intermediates into trisubstituted phosphine products. The above-mentioned allyl alcohol / anhydrous ethanol liquid phase feedstock is added to the third reaction tower 17 via the third reaction tower replenishment feed line 19 at a rate of 40 L / h; simultaneously, azobisisobutyronitrile is added via the catalyst feed channel 23 at a rate of 450 g / h. The operating pressure of the third reaction tower 17 is 0.105 MPa (A), and the operating temperature is 80℃.

[0043] The effluent from the third reaction tower 17, after being tested by the third detection unit 8c and meeting the preset product indicators, is discharged as the product liquid. If it does not meet the preset product indicators, it is returned to the third reaction tower 17 via the third circulation pipeline 22 for further maturation reaction. The resulting product liquid, after purification by a subsequent vacuum distillation tower, yields 62–63 kg / h of tris(3-hydroxypropyl)phosphine with a purity of 80%. Characterization information can be found in [link to relevant documentation]. Figure 3 As shown.

[0044] Example 2: Continuous preparation of trioctylphosphine using a three-stage tower

[0045] In this embodiment 2, the diameter of the first reaction tower 1, the second reaction tower 11, and the third reaction tower 17 are all 500 mm, and the height of the towers is all 10000 mm. Corrugated packing is installed inside each tower as a mass transfer enhancement or mixing enhancement element (25) to improve the contact efficiency and reaction uniformity between phosphine and liquid olefin materials. The first reaction tower 1 is a pressurized reaction tower, while the second reaction tower 11 and the third reaction tower 17 are atmospheric pressure reaction towers.

[0046] Pressurized phosphine gas is continuously fed into the first reaction tower 1 via phosphine inlet line 2 at a mass feed rate of 6 kg / h. Octene and toluene are mixed at a volume ratio of 1:1 to prepare a liquid feedstock, which is then continuously fed into the first reaction tower 1 via carbon-carbon unsaturated bond liquid feedstock line 4 at a volume feed rate of 60 L / h. Dimethyl azobisisobutyrate (DIBOB) is used as the catalyst and is added to the first reaction tower 1 via catalyst feed channel 23 at a feed rate of 950 g / h. The operating pressure of the first reaction tower 1 is 1.0 MPa (A), and the operating temperature is 85℃. Phosphine absorption and preliminary addition reactions are completed within this tower.

[0047] After the effluent from the first reaction tower 1 is detected by the first detection unit 8a and meets the preset control index, it enters the second reaction tower 11 through the second reaction tower feed line 12. If the preset control index is not met, it returns to the first reaction tower 1 through the first circulation line 9 to continue the reaction. The addition reaction continues in the second reaction tower 11, and the above-mentioned octene / toluene liquid phase feedstock is added through the second reaction tower replenishment liquid phase feedstock feed line 13 at a replenishment rate of 60 L / h; at the same time, dimethyl azobisisobutyrate is added through the catalyst feed channel 23 at a replenishment rate of 950 g / h. The operating pressure of the second reaction tower 11 is 0.105 MPa (A), and the operating temperature is 85℃.

[0048] After the effluent from the second reaction tower 11 reaches the preset control index as detected by the second detection unit 8b, it enters the third reaction tower 17 via the feed pipeline 16. If the preset control index is not reached, it returns to the second reaction tower 11 via the second circulation pipeline 15 to continue the reaction. The third reaction tower 17 serves as a post-reaction maturation zone, used to extend the liquid-phase reaction time and promote the further addition of mono- and di-substituted phosphorus-containing intermediates to generate trioctylphosphine. The aforementioned octene / toluene liquid-phase feedstock is added to the third reaction tower 17 via the feed pipeline 19, at a rate of 60 L / h; simultaneously, dimethyl azobisisobutyrate is added via the catalyst feed channel 23, at a rate of 950 g / h. The operating pressure of the third reaction tower 17 is 0.105 MPa (A), and the operating temperature is 85°C.

[0049] The effluent from the third reaction tower 17, after being tested by the third detection unit 8c and meeting the preset product indicators, is discharged as the product liquid. If it does not meet the preset product indicators, it is returned to the third reaction tower 17 via the third circulation pipeline 22 for further ripening reaction. After purification by a subsequent vacuum distillation tower, the resulting product liquid yields 62–63 kg / h of trioctylphosphine, with a product purity greater than 97% (meeting the requirements for high-purity electronic grade products). Its characterization information can be found in [reference needed]. Figure 4 and Figure 5 As shown.

[0050] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

[0051] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A method for preparing trisubstituted phosphine derivatives by continuous tower addition, characterized in that, It should include at least the following steps: S1. Phosphine and carbon-containing unsaturated carbon-phase raw materials are continuously introduced into the first reaction tower (1), which serves as the absorption and preliminary addition zone. Phosphine absorption and preliminary addition reactions are carried out under pressure in the first reaction tower (1) and in the atmosphere of catalyst and solvent. S2. The qualified reaction liquid collected from the first reaction tower (1) is sent to the second reaction tower (11) which is the main reaction zone. Carbon-containing unsaturated carbon bond liquid raw materials are added to the second reaction tower (11) and the addition reaction continues under normal pressure conditions in the second reaction tower (11). S3. The qualified reaction liquid collected from the second reaction tower (11) is sent to the third reaction tower (17). Carbon-containing unsaturated carbon bond liquid raw materials are added to the third reaction tower (17). The third reaction tower (17) serves as the post-reaction maturation zone. Under normal pressure conditions, it promotes the conversion of low-substituted phosphorus intermediates into trisubstituted phosphine derivatives. The operating pressure range of the first reaction tower (1) is set at 0.6-2.0 MPa (A) to form pressurized conditions; the operating pressure range of the second reaction tower (11) and the third reaction tower (17) is set at 0.1-0.12 MPa (A) to form atmospheric pressure conditions; S4. Qualified trisubstituted phosphine derivative product liquid is collected through the third reaction tower (17).

2. The method for preparing trisubstituted phosphine derivatives by continuous tower addition according to claim 1, characterized in that, The carbon-carbon unsaturated bond liquid phase raw material includes at least one of olefins, unsaturated alcohols, alkenyl ethers, alkenyl esters, unsaturated carboxylic acid esters, heteroatom-substituted olefins, or functionalized organic raw materials containing carbon-carbon double bonds; the trisubstituted phosphine derivative is tris(3-hydroxypropyl)phosphine, trioctylphosphine, or other trisubstituted phosphine derivatives formed by the addition of phosphine with the carbon-carbon unsaturated bond liquid phase raw material.

3. The method for preparing trisubstituted phosphine derivatives by continuous tower addition according to claim 1, characterized in that, When the reaction liquid collected from each reaction tower fails to meet the preset qualified conditions, the unqualified reaction liquid is returned to the corresponding reaction tower from which it was collected; catalyst and / or solvent are added to the second reaction tower (11); catalyst and solvent are added to the third reaction tower (17).

4. The method for preparing trisubstituted phosphine derivatives by continuous addition in a tower manner according to claim 3, characterized in that, In the first reaction tower (1) of step S1, the feed volume ratio of carbon-carbon unsaturated bond liquid phase raw material to solvent ranges from 1:0.7 to 1.5, and its feed molar ratio to phosphine is 0.35 to 1.2:1, while the catalyst accounts for 2-8% of the phosphine feed mass; in the second reaction tower (11) of step S2, the volume ratio of the added carbon-carbon unsaturated bond liquid phase raw material to the added solvent ranges from 1:0.7 to 1.5, and its feed molar ratio to the solvent in step S1 is 0.35 to 1.2:1, while the catalyst accounts for 2-8% of the phosphine feed mass. The molar ratio of the feed phosphine is 0.35-1.2:1, and the mass ratio of the added catalyst to the feed phosphine in step S1 is 2-8%. In step S3, the volume ratio of the carbon-containing unsaturated carbon bond liquid phase feedstock to the added solvent in the third reaction tower (17) is 1:0.7-1.5, and the molar ratio of the added catalyst to the feed phosphine in step S1 is 0.35-1.2:

1. The mass ratio of the added catalyst to the feed phosphine in step S1 is 2-8%.

5. The method for preparing trisubstituted phosphine derivatives by continuous addition in a tower manner according to claim 1, 3, or 4, characterized in that, The preset qualification conditions for the qualified reaction liquid collected from the first reaction tower (1) are as follows: the content of unreacted liquid phase material containing carbon-carbon unsaturated bonds is not higher than the first preset threshold, the range of the first preset threshold is 5-15 wt%, and / or, the content of dissolved phosphine is not higher than 1.0 wt%; The preset qualified conditions set for the qualified reaction liquid collected from the second reaction tower (11) are as follows: the content of unreacted carbon-containing unsaturated carbon-carbon liquid phase material is not higher than the second preset threshold, the range of the second preset threshold is 2-5 wt%, and / or, the mass fraction of low-substituted phosphorus-containing intermediates in the total organophosphorus compounds is not higher than the third preset threshold, the range of the third preset threshold is 10-15%; The preset qualification conditions for the qualified trisubstituted phosphine derivative product liquid collected from the third reaction tower (17) are: the content of unreacted carbon-containing unsaturated carbon-carbon liquid phase material is not higher than 1.0 wt%, and / or the target trisubstituted phosphine derivative accounts for ≥95% of the total organic phosphorus compounds.

6. The method for preparing trisubstituted phosphine derivatives by continuous tower addition according to claim 3, characterized in that, The catalyst is a free radical initiating catalyst, a transition metal catalytic catalyst, or a photo / thermal initiating catalyst; the solvent is an organic solvent, an aqueous solvent, or a mixed solvent.

7. The method for preparing trisubstituted phosphine derivatives by continuous tower addition according to claim 1, characterized in that, The operating temperatures of the first reaction tower (1), the second reaction tower (11), and the third reaction tower (17) are all set at 70-90℃.

8. A tower-type continuous addition apparatus for preparing trisubstituted phosphine derivatives, characterized in that, include: First reaction tower (1); Second reaction tower (11); Third reaction tower (17); The first reaction tower (1) is equipped with a phosphine inlet pipeline (2), a carbon-containing unsaturated bond liquid raw material inlet pipeline (4) and a first reaction tower reaction liquid outlet pipeline (7) located in the bottom of the tower. It is also equipped with a gas outlet at the top. The gas phase is condensed by the condenser (6) and the liquid phase flows back into the tower. The gas phase tail gas is discharged through the tail gas outlet pipeline (5). The second reaction tower (11) is respectively provided with a second reaction tower feed line (12) connected to the first reaction tower reaction liquid outlet line (7), a second reaction tower replenishment liquid raw material feed line (13) located at the top of the tower, and a second reaction tower reaction liquid outlet line (14) located at the bottom of the tower. The third reaction tower (17) is respectively provided with a third reaction tower feed line (16) connected to the second reaction tower reaction liquid outflow line (14), a third reaction tower replenishment liquid raw material feed line (19) located at the top of the tower, and a third reaction tower reaction liquid outflow line (20) at the bottom of the tower. A first detection unit (8a) is provided between the reaction liquid outlet pipeline (7) of the first reaction tower and the feed pipeline (12) of the second reaction tower. A first circulation pipeline (9) is provided between the unqualified outlet of the first detection unit (8a) and the first reaction tower (1), and its qualified outlet is connected to the feed pipeline (12) of the second reaction tower. A second detection unit (8b) is provided between the reaction liquid outlet pipeline (14) of the second reaction tower and the feed pipeline (16) of the third reaction tower. A second circulation pipeline (15) is provided between the unqualified outlet of the second detection unit (8b) and the second reaction tower (11), and its qualified outlet is connected to the feed pipeline (16) of the third reaction tower. The reaction liquid collection pipeline (20) of the third reaction tower and the product tank are provided with a third detection unit (8c). The unqualified outlet of the third detection unit (8c) and the third reaction tower (17) are provided with a third circulation pipeline (22), and its qualified outlet is connected to the product tank. Trisubstituted phosphine derivatives are prepared by the method for preparing trisubstituted phosphine derivatives by tower-type continuous addition according to any one of claims 1-7.

9. The apparatus for the continuous addition preparation of trisubstituted phosphine derivatives by a tower according to claim 8, characterized in that, The first reaction tower (1), the second reaction tower (11), and the third reaction tower (17) are all equipped with catalyst feeding channels and solvent feeding channels; wherein, the catalyst feeding channel or solvent feeding channel adopts an independent feeding channel directly connected to its corresponding reaction tower, or is merged into the feed pipeline or circulation pipeline corresponding to each reaction tower.

10. The apparatus for the continuous addition preparation of trisubstituted phosphine derivatives by a tower according to claim 8, characterized in that, At least one of the first reaction tower (1), the second reaction tower (11), and the third reaction tower (17) is provided with an enhanced mass transfer or enhanced mixing element, wherein the enhanced mass transfer or enhanced mixing element includes at least one of structured packing, random packing, tray, sprayer, liquid distributor, gas distributor, static mixing element, liquid film forming structure, and bubble distributor.

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