A phosphorus pentachloride synthesis reactor, continuous synthesis system and method

Abstract

The application discloses a phosphorus pentachloride synthesis reactor, a continuous synthesis system and a method, which comprise a reactor body, one nozzle arranged at the top of the reactor body and at least one nozzle group arranged at the side of the reactor body, each nozzle group comprising at least two nozzles; the distance between the top of the reactor body and the nozzle group adjacent to the top is 3-5 times the inner diameter of the reactor body; the application improves the uniformity of the distribution of the material in the space of the reactor body by arranging multiple nozzles on the reactor body in layers, thereby improving the heat exchange effect of the material and the heat exchange medium, reducing or eliminating the high-temperature area in the reactor body; in some embodiments of the application, the temperature in the reactor can be controlled within 50-70 DEG C.

Description

TECHNICAL FIELD

[0001] The present application relates to a phosphorus pentachloride synthesis reactor, a continuous synthesis system and method. BACKGROUND

[0002] Phosphorus pentachloride (PCl5) is an important non-polar compound, which is widely used as a chlorinating agent, a catalyst, a dehydrating agent, etc. in organic synthesis. It can be used as a raw material to prepare chemical products such as phosphazene chloride, phosphorus oxychloride, lithium hexafluorophosphate, etc., and to produce chemical fibers. It can also be used as a pharmaceutical intermediate and a dye intermediate. With the rise of the new energy battery industry, phosphorus pentachloride is widely used in the production of lithium battery electrolyte lithium hexafluorophosphate, etc.

[0003] The synthesis method of phosphorus pentachloride is to react phosphorus trichloride and chlorine gas as raw materials. Generally, a gas-liquid reaction method is adopted, in which chlorine gas reacts with liquid phosphorus trichloride. The traditional production process mainly adopts a batch kettle type reaction. As disclosed in patent document CN107117591A, chlorine gas is introduced into the reactor to react with the liquid phosphorus trichloride. The chlorine gas needs to be continuously introduced until the solution is converted into completely dry crystalline product through pasting, i.e. the phosphorus pentachloride product is obtained. However, the phosphorus pentachloride product is a solid. With the increase of the conversion rate of phosphorus trichloride, the stirring of the system becomes more and more difficult, and even it is difficult to stir. In order to make the phosphorus trichloride react as completely as possible, an excessive amount of chlorine gas is introduced for chlorination. After the reaction is completed, dry carbon dioxide gas is introduced to discharge the residual chlorine gas. However, even so, the content of residual phosphorus trichloride in the product is still high, generally more than 0.05% or even 0.1%. Moreover, the chlorine gas cannot be completely discharged, which leads to the problems of uneven product particles, strong hygroscopicity, poor flowability, etc. In addition, there are problems of large tail gas emission and poor operating environment, etc.

[0004] In recent years, some continuous method phosphorus pentachloride production processes have also been developed. For example, patent document CN116920764A has the feature that the phosphorus trichloride is atomized into droplets to react with gaseous chlorine to generate phosphorus pentachloride particles. In order to control the reaction temperature, a large amount of CO2 or N2 is needed as a diluent and circulating gas for cooling, which leads to a large reactor volume and difficulty in temperature control of the system. SUMMARY

[0005] The technical problem to be solved by the present application is to overcome the problems of difficulty in temperature control of the system and low product purity in the existing production of phosphorus pentachloride. The present application provides a phosphorus pentachloride synthesis reactor, a continuous synthesis system and method. The liquid phosphorus trichloride is atomized and controlled, and then added in stages, so that the temperature control in the reactor is uniform, and the temperature is within 50-70℃. The high temperature zone in the reactor is eliminated, and the obtained phosphorus pentachloride particles have large diameter and high purity.

[0006] The present application solves the above technical problems by the following technical solutions:

[0007] The application also provides a phosphorus pentachloride synthesis reactor, which comprises a reactor body, one nozzle arranged at the top of the reactor body, and at least one nozzle group arranged at the side of the reactor body, each of the nozzle groups comprising at least two nozzles; the distance between the top of the reactor body and the nozzle group adjacent thereto is 3-5 times the inner diameter of the reactor body.

[0008] When the number of nozzle groups is greater than or equal to 2, the nozzle groups are arranged in sequence from top to bottom along the reactor axis; the distance between adjacent nozzle groups along the axial direction of the reactor body is 2-5 times the inner diameter of the reactor body.

[0009] In the application, when the nozzle distance is too small, less than 2 times the inner diameter of the reactor body, the reaction zones corresponding to two nozzles overlap, the temperature increases greatly, which is not conducive to the generation of solid PCl5; when the nozzle distance is too large, greater than 5 times the inner diameter of the reactor body, the reaction zones corresponding to two nozzles are further separated, the cooling effect is not obvious, and the investment increases.

[0010] In the application, by arranging multiple nozzles in layers on the reactor, the uniformity of the distribution of the material in the space of the reactor body is improved, and then the heat exchange effect of the material and the heat exchange medium (such as the cooled circulating gas) is improved, and the high-temperature zone in the reactor body is reduced or eliminated.

[0011] In the application, the number of nozzles in each nozzle group is preferably an even number, and the nozzles in each nozzle group are arranged symmetrically about the axis of the reactor body. The nozzles in each nozzle group are arranged in pairs, which can further improve the uniformity of the distribution of the material in the space of the reactor body, so that the heat exchange effect in the reactor is better, and local high temperature is reduced; the number of nozzles is, for example, 3, 5 or 7.

[0012] In a preferred embodiment of the application, the total number of nozzles is 3, one of which is arranged at the top of the reactor body, and the other two are arranged symmetrically about the axis of the reactor body around the side of the reactor body.

[0013] In a preferred embodiment of the application, the number of nozzles is 7, one of which is arranged at the top of the reactor body, and the other six are arranged in three groups, each group comprising two nozzles, the three groups being arranged in sequence from top to bottom along the axial direction of the reactor body, the two nozzles in each group being arranged symmetrically about the axis of the reactor body around the side of the reactor body, and the projections of the nozzles in the three groups on the cross section of the reactor body being distributed equidistantly along the circumferential direction of the reactor body.

[0014] In the present application, the projections of the nozzles in two adjacent nozzle groups on the cross section of the reactor body are equidistantly distributed along the circumference of the reactor body, the cross section of the reactor body refers to the plane perpendicular to the axis of the reactor body. The uniformity of the distribution of the material in the space of the reactor body is further improved.

[0015] In the present application, the distance between the nozzle arranged at the top of the reactor body and the adjacent nozzle group can be 2-5 times the inner diameter of the reactor body.

[0016] In the present application, the distance between the adjacent nozzle groups along the axis direction of the reactor body can be 2-5 times the inner diameter of the reactor body.

[0017] In the present application, the end of the outlet of the nozzle is flush with the inner wall surface of the reactor body, which can make the radial reaction zone in the reactor body as large as possible, and make the high temperature zone close to the wall surface, which is beneficial to the wall heat exchange.

[0018] In the present application, the nozzle is a conventional gas-liquid two-channel nozzle in the art, which can be a pressure type atomizing nozzle or an airflow type atomizing nozzle.

[0019] In the present application, the outlet axis of the nozzle is perpendicular to the axis of the reactor body or inclined downward.

[0020] In the present application, the reactor body is a conventional tank body capable of bearing a certain pressure and temperature in the art. The pressure is generally not greater than 2 MPaG, and the temperature is generally not greater than 300 DEG C.

[0021] In the present application, the reactor body can also be provided with a chlorine source inlet, a discharge outlet and a circulating gas outlet, the chlorine source inlet is located at the upper part of the reactor body, and the discharge outlet and the circulating gas outlet are both located at the lower part of the reactor body.

[0022] Preferably, the number of chlorine source inlets corresponds to the number of nozzle groups, and one chlorine source inlet is arranged above each nozzle group.

[0023] In the present application, the material reaction process in the reactor is that the phosphorus trichloride liquid is divided into multiple streams, which are respectively added into the reactor body through the nozzles and chemically react with Cl2 in the circulating gas to generate phosphorus pentachloride particles.

[0024] The present application also provides a continuous phosphorus pentachloride synthesis system, which comprises the foregoing reactor and a first fan.

[0025] The reactor body is provided with a chlorine source inlet, a discharge outlet, a circulating gas outlet and a circulating gas inlet.

[0026] The first fan is connected between the circulating gas outlet and the circulating gas inlet.

[0027] In the present application, the nozzle can be a pressure atomizing nozzle or an airflow atomizing nozzle, preferably an airflow atomizing nozzle.

[0028] When the nozzle is an airflow atomizing nozzle, the gas channel of the nozzle is preferably connected with the circulating gas outlet, and the circulating gas is used as atomizing gas.

[0029] A second fan and a second cooling device are preferably connected between the gas channel of the nozzle and the circulating gas outlet, and the second fan and the second cooling device are sequentially arranged along the flow direction of the circulating gas, the second fan is used to compress the circulating gas into high-pressure gas, and the second cooling device is used to cool the circulating gas.

[0030] The second cooling device can be a heat exchanger commonly used in the art.

[0031] The heat exchange medium temperature of the second cooling device can be room temperature, which is used to cool the circulating gas to room temperature.

[0032] When the nozzle is a pressure atomizing nozzle, a first feed pump is connected to the liquid inlet of the nozzle, and the first feed pump is used to pressurize the phosphorus trichloride liquid to realize the pressurized atomization of the phosphorus trichloride in the nozzle.

[0033] In the present application, the chlorine source inlet is preferably located in the area where the nozzle is arranged, more preferably, the number of chlorine source inlets corresponds to the number of nozzle groups, and the chlorine source inlets are arranged above each nozzle group.

[0034] In the present application, the chlorine source inlet is preferably connected with a chlorine source pipeline, and the end of the chlorine source pipeline extends to the inner center position of the reactor body. The end of the chlorine source pipeline is preferably connected with a chlorine source nozzle. By arranging the chlorine source pipeline and the chlorine source nozzle, the chlorine source can be more uniformly sprayed in the interior of the reactor body.

[0035] In the present application, the chlorine source is preferably liquid chlorine. Compared with traditional chlorine gas, liquid chlorine absorbs heat and evaporates to generate chlorine gas after entering the reactor, which not only provides chlorine gas but also plays a role in cooling the reactor.

[0036] In the present application, the circulating gas inlet is preferably close to the nozzle, and more preferably, one circulating gas inlet is arranged on the reactor body near each nozzle group, so that the cooled circulating gas can more effectively cool the reaction zone near the nozzle.

[0037] In the application, the circulating gas outlet is preferably arranged at the lower side of the reactor body.

[0038] In the application, the discharge outlet is preferably arranged at the bottom of the reactor body.

[0039] In the application, the wall surface of the reactor body is preferably arranged as a water-cooled wall for heat removal.

[0040] In the application, the phosphorus pentachloride continuous synthesis system can further comprise a first cooling device connected between the first fan and the circulating gas inlet, and the first cooling device is used for cooling the circulating gas.

[0041] Preferably, the first cooling device comprises a primary cooling device and a secondary cooling device connected in sequence along the circulating gas flow direction, the heat exchange medium temperature of the primary cooling device is normal temperature, and the heat exchange medium temperature of the secondary cooling device is 10-30℃. By arranging two-stage cooling, the circulating gas at a lower temperature enters the reactor to cool the inside of the reactor.

[0042] The primary cooling device and the secondary cooling device can be conventional heat exchangers in the art.

[0043] In the application, the phosphorus pentachloride continuous synthesis system can further comprise a gas separation and purification device arranged between the circulating gas outlet and the first fan, and the gas separation and purification device is used for purifying the circulating gas.

[0044] Preferably, the gas separation and purification device comprises a cyclone dust collector and a bag dust collector connected in sequence along the circulating gas flow direction, the cyclone dust collector is connected with the circulating gas outlet, and the bag dust collector is connected with the first fan.

[0045] When the second fan and the second cooling device are arranged, the second fan and the second cooling device are arranged in sequence along the circulating gas flow direction, the bag dust collector is further connected with the second fan, the second fan is used for compressing the circulating gas into high-pressure gas, and the second cooling device is used for cooling the circulating gas.

[0046] In the application, the phosphorus pentachloride continuous synthesis system can further comprise a material discharge flow aid device arranged at the discharge outlet, the material discharge flow aid device is provided with a fluidization gas inlet, the fluidization gas inlet is connected with the circulating gas outlet, and the circulating gas is used for fluidization treatment of phosphorus pentachloride particles to improve intermittent or continuous stable discharge of the particles.

[0047] Preferably, when the second fan and the second cooling device are provided, the second fan and the second cooling device are sequentially arranged along the flow direction of the circulating gas, the second fan is connected to the circulating gas outlet, the second fan is used for compressing the circulating gas into high-pressure gas, the second cooling device is used for cooling the circulating gas, and the fluidization gas inlet is connected to the outlet of the second cooling device, and the cooled circulating gas can also enter the fluidization gas inlet as fluidization gas.

[0048] Preferably, the fluidization gas inlets are even in number, and the plurality of fluidization gas inlets are symmetrically arranged.

[0049] Preferably, the material discharge flow aid device is a fluidizer.

[0050] Preferably, the circulating gas outlet is located on the side of the reactor body above the material discharge flow aid device.

[0051] In the present application, the phosphorus pentachloride continuous synthesis system can further comprise product tanks, preferably comprising a first product tank and a second product tank, the first product tank being connected to the discharge outlet, and the second product tank being connected to the outlet of the first product tank. By arranging the first product tank, the pressure of the gas flow from the reactor body is adjusted, thereby reducing the influence of the circulating gas on product collection.

[0052] Preferably, when the discharge outlet is further provided with the aforementioned material discharge flow aid device, the first product tank is connected to the outlet of the material discharge flow aid device.

[0053] Preferably, the first product tank is further provided with a filter, the discharge outlet of the filter is connected to the first product tank, the gas outlet of the filter is connected between the circulating gas outlet and the circulating gas inlet, and the filter is used for dust removal of the material in the first product tank.

[0054] Preferably, when the gas separation and purification device is further provided, the gas outlet of the filter is connected to the inlet of the gas separation and purification device.

[0055] Preferably, the bottom of the first product tank is further provided with the aforementioned material discharge flow aid device, the fluidization gas inlet of the material discharge flow aid device is connected to the circulating gas outlet, and the material in the first product tank is subjected to fluidization treatment.

[0056] Preferably, a second fan and a second cooling device are connected between the fluidizing gas inlet and the circulating gas outlet, and are arranged in sequence along the flow direction of the circulating gas, the second fan is connected to the circulating gas outlet, and is used to compress the circulating gas into high-pressure gas, and the fluidizing gas inlet is connected to the outlet of the second cooling device, and is used to cool the circulating gas.

[0057] In the present application, the phosphorus pentachloride continuous synthesis system can further comprise a phosphorus trichloride storage tank and a chlorine source storage tank, the phosphorus trichloride storage tank is connected to the liquid channel of the nozzle, and the chlorine source storage tank is connected to the chlorine source inlet.

[0058] In the present application, the circulating gas is formed in a conventional manner in the art, generally, chlorine gas and carbon dioxide are introduced into the reactor body to form a mixed gas, and a closed circulation loop is formed under the first fan, and liquid chlorine is introduced into the chlorine gas generated after vaporization to supplement the circulating gas.

[0059] The present application also provides a phosphorus pentachloride continuous synthesis method, which uses the aforementioned phosphorus pentachloride continuous synthesis system for synthesis, and comprises the following steps: introducing the phosphorus trichloride liquid into the reactor body through the nozzle, the circulating gas is a mixed gas of chlorine gas and carbon dioxide, introducing the chlorine source into the reactor body through the chlorine source inlet, and performing a reaction.

[0060] In the present application, the volume concentration of the chlorine gas in the circulating gas is preferably 10-30%, for example, 20%.

[0061] In the present application, when the nozzle is an air flow type atomizing nozzle, the speed of the circulating gas at the outlet of the nozzle is preferably 20-100 m / s, for example, 60 m / s. The speed of the phosphorus trichloride liquid at the outlet of the nozzle is preferably 0.2-2 m / s, for example, 1 m / s. More preferably, the speed of the circulating gas at the outlet of the nozzle gradually increases from top to bottom along the axis direction of the reactor body, for example, when one nozzle group is provided, the speed of the circulating gas at the outlet of the nozzle at the top of the reactor body is 60 m / s, and the speed of the circulating gas at the outlet of each nozzle in the nozzle group is 70 m / s.

[0062] When the nozzle is a pressure type atomizing nozzle, the pressure drop of the nozzle is preferably 0.1-0.5 MPaG. The speed of the phosphorus trichloride liquid at the outlet of the nozzle is preferably 2-10 m / s, for example, 4 m / s.

[0063] More preferably, the pressure drop of the nozzles gradually increases from top to bottom along the axis of the reactor body, for example, when three nozzle groups are provided, the pressure drop of the nozzles at the top of the reactor body is 0.1 MPaG, the pressure drop of each nozzle in the first nozzle group is 0.3 MPaG, the pressure drop of each nozzle in the second nozzle group is 0.4 MPaG, and the pressure drop of each nozzle in the third nozzle group is 0.5 MPaG.

[0064] In the present application, the flow rate of the circulating gas is determined according to the actual reaction scale, the larger the load, the larger the circulating gas amount; under the condition of a certain load, the larger the flow rate of the circulating gas, the better the cooling effect; but when the circulating gas amount is too large, the residence time is short and the reaction conversion rate is low. The flow rate of the circulating gas is preferably 9000-18000 Nm 3 / h.

[0065] In the present application, the mass flow rate of the phosphorus trichloride is preferably 1.37-54.8 tons / h.

[0066] In the present application, the flow rate of the chlorine source is determined according to the flow rate of the phosphorus trichloride, wherein the molar ratio K of chlorine to phosphorus trichloride is preferably 1.0-1.05.

[0067] In the present application, the temperature of the reaction is preferably 20-60℃, more preferably 30-40℃.

[0068] In the present application, preferably, the atomized particle size of the phosphorus trichloride decreases from top to bottom along the reactor body.

[0069] The atomized particle size distribution of the phosphorus trichloride can be two-stage distribution, three-stage distribution or four-stage distribution;

[0070] In the two-stage distribution, the first-stage atomized particle size is preferably 0.1-0.5 mm, the second-stage atomized particle size is preferably 0.1-0.15 mm, and the first-stage atomized particle size is more preferably 0.1-0.2 mm;

[0071] In the three-stage distribution, the first-stage atomized particle size is preferably 0.2-1 mm, more preferably 0.2-0.4 mm, the second-stage atomized particle size is preferably 0.1-0.5 mm, more preferably 0.1-0.2 mm, and the third-stage atomized particle size is preferably 0.1-0.15 mm.

[0072] In the four-stage distribution, the first-stage atomized particle size is preferably 0.3-2 mm, more preferably 0.4-0.6 mm, the second-stage atomized particle size is preferably 0.2-1 mm, more preferably 0.2-0.4 mm, the third-stage atomized particle size is preferably 0.1-0.5 mm, more preferably 0.1-0.2 mm, and the fourth-stage atomized particle size is preferably 0.1-0.15 mm.

[0073] The atomized particle size distribution of the phosphorus trichloride is preferably the four-stage distribution, so that the large particle size phosphorus trichloride particles are located at the top and gradually react during the falling process, and the small particle size phosphorus trichloride particles are located at the bottom, which can prolong the entire reaction process and improve the reaction load.

[0074] The atomized particle size distribution of the phosphorus trichloride can also be more than four-stage distribution. When it is more than four-stage distribution, the atomized particle size of the phosphorus trichloride after four stages is generally 0.1-0.15 mm, but the four-stage distribution is preferred from the perspective of atomization cost.

[0075] The positive progress effect of the present application is that:

[0076] (1) The present application improves the uniformity of the distribution of the material in the space of the reactor body by layering multiple nozzles on the reactor body, thereby improving the heat exchange effect of the material and the heat exchange medium (such as the cooled circulating gas), reducing or eliminating the high temperature zone in the reactor body. In some embodiments of the present application, the temperature in the reactor can be controlled within 50-70°C.

[0077] (2) The continuous synthesis system of the present application further cools the material in the reactor using cooled circulating gas to reduce local high temperature in the reactor; further using liquid chlorine as a chlorine source, compared with traditional chlorine gas, liquid chlorine evaporates to produce chlorine gas after entering the reactor, which provides chlorine gas and at the same time can play a role in cooling the reactor.

[0078] (3) The continuous synthesis system of the present application synthesizes phosphorus pentachloride particles with large particle diameter and high purity. BRIEF DESCRIPTION OF DRAWINGS

[0079] Figure 1 It is a structure schematic diagram of the continuous synthesis system of phosphorus pentachloride of Example 1.

[0080] Figure 2 It is a structure schematic diagram of the continuous synthesis system of phosphorus pentachloride of Example 2.

[0081] Figure 3 It is a structure schematic diagram of the continuous synthesis system of phosphorus pentachloride of Example 2.

[0082] BRIEF DESCRIPTION OF DRAWINGS

[0083] Reactor 1

[0084] Reactor body 101

[0085] Nozzle 102

[0086] Chlorine source inlet 103

[0087] Discharge port 104

[0088] Circulating gas outlet 105

[0089] Circulating gas inlet 106

[0090] Gas separation and purification device 2

[0091] Cyclone dust collector 201

[0092] Baghouse dust collector 202

[0093] First Wind Turbine 3

[0094] First cooling device 4

[0095] Primary cooling unit 401

[0096] Secondary cooling unit 402

[0097] Second fan 5

[0098] Second cooling device 6

[0099] Material discharge flow aid device 7

[0100] Fluidizing gas inlet 701

[0101] Phosphorus trichloride storage tank 8

[0102] Chlorine source storage tank 9

[0103] First product tank 10

[0104] Second product tank 11

[0105] Filter 12

[0106] First feed pump 13

[0107] Second feed pump 14 Detailed Implementation

[0108] The present invention will be further illustrated by way of embodiments below, but the present invention is not limited to the scope of the embodiments described herein.

[0109] Example 1

[0110] This embodiment discloses a continuous synthesis system for phosphorus pentachloride, such as Figure 1 As shown, it includes a reactor 1, a gas separation and purification device 2, a first blower 3, a first cooling device 4, a second blower 5, a second cooling device 6, a material discharge flow aid device 7, a phosphorus trichloride storage tank 8, a chlorine source storage tank 9, a first product tank 10, a second product tank 11, a filter 12, a first feed pump 13, and a second feed pump 14.

[0111] The reactor 1 comprises a reactor body 101, one nozzle 102 arranged at the top of the reactor body 101, and one nozzle group arranged at the side of the reactor body 101, wherein the nozzle group is composed of two nozzles 102 arranged symmetrically with the axis of the reactor body 101 as the center, the spacing between the top nozzle 102 and the nozzle group in the axial direction of the reactor body 101 is 3 times the inner diameter of the reactor body 101, and the nozzle is a gas flow type atomizing nozzle.

[0112] The reactor body 101 is provided with a chlorine source inlet 103, a discharge outlet 104, a circulating gas outlet 105, and a circulating gas inlet 106, wherein the chlorine source inlet 103 is arranged above the nozzle group, the chlorine source inlet 103 is connected with a chlorine source pipeline, the end of the chlorine source pipeline is deep into the inner center position of the reactor body 101, and the end of the chlorine source pipeline is connected with a chlorine source nozzle. The discharge outlet 104 is located at the bottom of the reactor body 101, the circulating gas outlet 105 is located at the lower side of the reactor body 101, and the circulating gas inlet 106 is arranged on the reactor body 101 close to the nozzle group. The wall surface of the reactor body 101 adopts water-cooled wall for heat exchange.

[0113] The gas separation and purification device 2 comprises a cyclone dust collector 201 and a bag dust collector 202 connected in sequence along the circulating gas flow direction, the circulating gas outlet 105 is connected with the cyclone dust collector 201, and the first fan 3 and the second fan 5 are connected in parallel on the bag dust collector 202.

[0114] The first cooling device 4 comprises a primary cooling device 401 and a secondary cooling device 402 connected in sequence along the circulating gas flow direction, the heat exchange medium of the primary cooling device 401 is normal temperature water, and the heat exchange medium of the secondary cooling device 402 is an ice water mixture with a temperature of about 10℃, which is used to cool the circulating gas to normal temperature. The primary cooling device 401 is connected at the outlet of the first fan 3, the first fan 3 is a circulating fan, and the outlet of the secondary cooling device 402 is connected with the inlet of the circulating gas.

[0115] The outlet of the second cooling device 6 is connected with the gas passages of all nozzles 102, and the second fan 5 is a high-pressure fan used for compressing the circulating gas into atomizing gas.

[0116] The primary cooling device 401, the secondary cooling device 402, and the second cooling device 6 are all heat exchangers.

[0117] The material discharge flow aid 7 is arranged at the discharge port 104 to fluidize the phosphorus pentachloride particles, and the material discharge flow aid 7 is a fluidizer, and two fluidizing gas inlets 701 are symmetrically arranged at the bottom of the material discharge flow aid 7 and are connected in parallel to the outlet of the second cooling device 6. The circulating gas outlet 105 is arranged at the side of the reactor body 101 above the material discharge flow aid 7.

[0118] The phosphorus trichloride storage tank 8 is connected to the liquid channel of all the nozzles 102, the first feed pump 13 is arranged between the phosphorus trichloride storage tank 8 and the nozzles 102, the chlorine source storage tank 9 is connected to the chlorine source inlet 103, the chlorine source is liquid chlorine, and the second feed pump 14 is arranged between the chlorine source storage tank 9 and the chlorine source inlet 103.

[0119] The first product tank 10 is connected to the outlet of the material discharge flow aid 7, and the second product tank 11 is connected to the outlet of the first product tank 10, so that the high-pressure gas stream from the reactor body 101 is pressure-adjusted through the first product tank 10.

[0120] The bottom of the first product tank 10 is also provided with a material discharge flow aid 7, and the second product tank 11 is connected to the bottom of the material discharge flow aid 7, and the two fluidizing gas inlets at the bottom of the material discharge flow aid 7 are also connected in parallel to the outlet of the second cooling device 6.

[0121] The filter 12 is arranged on the first product tank 10, the discharge outlet of the filter 12 is connected to the first product tank 10, and the gas outlet of the filter 12 is connected to the outlet of the bag-type dust collector 202 for dust removal of the material in the first product tank 10.

[0122] In this embodiment, the mixed gas of carbon dioxide and chlorine is first introduced into the reactor body 101 to form circulating gas under the action of the first fan 3, the chlorine source and the phosphorus trichloride liquid are introduced into the reactor body 101, the phosphorus trichloride liquid particles react with chlorine to generate phosphorus pentachloride, the circulating gas flows out from the circulating gas outlet 105, is separated and purified by the gas separation and purification device 2, is cooled and cooled by the first fan 3 and the first cooling device 4, and then enters the reactor body 101 through the circulating gas inlet 106 to cool the inside of the reactor body 101, and the other part is compressed into high-pressure gas by the second fan 5, is cooled and cooled by the second cooling device 6, and then enters the nozzles 102 and the material discharge flow aid 7, and circulates according to the above process.

[0123] The continuous synthesis system of this embodiment has a phosphorus pentachloride production scale of 500 tons per day.

[0124] The phosphorus pentachloride is synthesized by using the above continuous synthesis system, and the synthesis method comprises the following steps:

[0125] The circulating gas is used as the atomizing gas of the nozzle, and the phosphorus trichloride liquid is introduced into the reactor body 101 through the nozzle 102, and the liquid chlorine is introduced into the reactor body 101 through the chlorine source inlet 103, and the reaction is carried out;

[0126] The nozzle is an air flow type atomizing nozzle, as shown in the figure, the contraction angle a of the nozzle channel is 60°, and the air flow type nozzle structure is the structure described in the document “Cao Xiankui, Xu Jianliang. Coaxial double-channel air flow type atomizing nozzle primary atomization process [J]. Chemical Industry, 2006, 57(11): 2592”. Figure 3 Figure 1 The nozzle is an air flow type atomizing nozzle, as shown in the figure, the contraction angle a of the nozzle channel is 60°, and the air flow type nozzle structure is the structure described in the document “Cao Xiankui, Xu Jianliang. Coaxial double-channel air flow type atomizing nozzle primary atomization process [J]. Chemical Industry, 2006, 57(11): 2592”.

[0127] The speed of the circulating gas at the nozzle outlet is 60 m / s, and the speed of the phosphorus trichloride liquid at the nozzle outlet is 1 m / s in the nozzle at the top, and the speed of the circulating gas at the nozzle outlet is 70 m / s in the two nozzles at the side, and the speed of the phosphorus trichloride liquid at the nozzle outlet is 1 m / s.

[0128] The mass flow rate of the phosphorus trichloride is 13.7 tons / h, the mass flow rate of the liquid chlorine is 7.21 tons / h, the molar ratio K of Cl2 and PCl3 is 1.02, the circulating gas is a mixture of chlorine and carbon dioxide, the volume concentration of chlorine in the circulating gas is 20%, the flow rate of the circulating gas is 9000 Nm 3 / h, the internal pressure of the reactor body is 20 kPa G, and the reaction temperature is set to 40°C.

[0129] The particle size of the phosphorus trichloride is measured by a laser particle size analyzer, and the particle size of the phosphorus trichloride in this embodiment is two-stage distribution: the primary atomization particle size is 0.1-0.2 mm, and the secondary atomization particle size is 0.1-0.15 mm.

[0130] The maximum temperature in the furnace in this embodiment is 50°C, the average particle size SMD of the phosphorus pentachloride is 50 um, and the purity of the phosphorus pentachloride is 99.99%.

[0131] Comparative Example 1

[0132] This comparative example uses the synthesis system described in Example 1 of patent CN116920764A to synthesize, the number of nozzles is 1, the circulating gas is the same as Example 1, the flow rate of the circulating gas is 18000 Nm 3 / h, the reactor pressure is 0.1 MPa, the flow rate of the phosphorus trichloride is 13.7 tons / h, and the reactor pressure is 0.1 MPa G.

[0133] The nozzle of this comparative example is the same as Example 1, the speed of the circulating gas at the nozzle outlet is 70 m / s, and the speed of the phosphorus trichloride liquid at the nozzle outlet is 1 m / s.

[0134] The production scale, the reactor inner diameter and the synthesis setting temperature are the same as Example 1.​

[0135] The particle size of phosphorus trichloride in this comparative example was 0.1-0.15 mm.

[0136] The maximum temperature in the furnace of this comparative example was 90°C, the average particle size SMD of phosphorus pentachloride was 15 um, and the purity of phosphorus pentachloride was 99.80%.

[0137] Example 2

[0138] The structure of the phosphorus pentachloride continuous synthesis system of this example is shown in Figure 2 , which is basically the same as that of Example 1, with the difference being that:

[0139] The number of nozzles 102 in this example was 7, as shown in Figure 1 , one of which was arranged at the top of the reactor body 101, and the remaining six were arranged in three nozzle groups, two nozzles per group, symmetrically arranged around the axis of the reactor body 101, and all the nozzles 102 in the three nozzle groups were distributed equidistantly along the circumference of the reactor body 101 in the cross-sectional projection of the reactor body 101; each nozzle group was provided with a liquid chlorine inlet 103 above it.

[0140] The outlet of the second cooling device 6 was not connected to the nozzles 102, and the pressure atomization of the nozzles 102 was formed by controlling the pressure and flow rate of the first feed pump 13.

[0141] The diameter of the reactor body was 1.2 times that of Example 1, and the height-to-diameter ratio of the reactor body was the same as that of Example 1.

[0142] The nozzles 102 were pressure atomizing nozzles, and the structure of the pressure nozzles was the nozzle structure described in Example 1 of CN1164442A.

[0143] From the top of the reactor body downward, the pressure drop of the nozzle at the top was 0.1 MPaG, the pressure drop of each nozzle in the first nozzle group was 0.3 MPaG, the pressure drop of each nozzle in the second nozzle group was 0.4 MPaG, and the pressure drop of each nozzle in the third nozzle group was 0.5 MPaG. The flow rate of phosphorus trichloride at the outlet of each nozzle was equal, all being 4 m / s.

[0144] The production scale was 1000 tons per day, the internal pressure of the reactor body 101 was 20 kPa, the circulating gas volume was 18000 Nm 3 / h, and the flow rate of phosphorus trichloride was 27.4 tons / h.

[0145] The remaining structure, steps and parameters were the same as those of Example 1.

[0146] The particle size of phosphorus trichloride was measured by a laser particle size analyzer. The physicochemical particle size of phosphorus trichloride in the reactor was a four-stage distribution: the primary atomized particle size was 0.4-0.6 mm, the secondary atomized particle size was 0.2-0.4 mm, the tertiary atomized particle size was 0.1-0.2 mm, and the quaternary atomized particle size was 0.1-0.15 mm.

[0147] The maximum temperature in the furnace of this example was 60°C, the average particle size SMD of phosphorus pentachloride was 40 um, and the purity of phosphorus pentachloride was 99.99%.

[0148] Comparative Example 2

[0149] This comparative example used the synthesis system described in Example 1 of patent CN116920764A for synthesis, the number of nozzles was 1, the circulating gas was the same as in Example 1, the flow rate of the circulating gas was 36000 Nm 3 / h, the inner diameter of the reactor was twice that of Example 2, the reactor pressure was 0.1 MPaG, and the flow rate of phosphorus trichloride was 27.4 tons / h.

[0150] The nozzles of this comparative example were the same as in Example 2, the pressure drop of the nozzles was 0.5 MPaG, and the liquid velocity of phosphorus trichloride at the nozzle outlet was 4 m / s.

[0151] The production scale, the inner diameter of the reactor, and the synthesis set temperature were all the same as in Example 2.

[0152] The particle size of phosphorus trichloride was measured by a laser particle size analyzer. The atomized particle size was 0.1-0.15 mm.

[0153] The maximum temperature in the furnace of this comparative example was 120°C, the average particle size SMD of phosphorus pentachloride was 10 um, and the purity of phosphorus pentachloride was 99.80%.

[0154] Example 3

[0155] The difference between this example and Example 1 was only that the nozzles 102 of this example were pressure-type atomizing nozzles, and the structure of the pressure-type nozzles was the same as in Example 2.

[0156] The outlet of the second cooling device 6 was not connected to the nozzles 102, and the pressure-type atomization of the nozzles 102 was formed by controlling the pressure and flow rate of the first feed pump 13.

[0157] From the top of the reactor body downward, the pressure drop of the nozzle at the top was 0.4 MPaG, the pressure drop of the two nozzles in the nozzle group was 0.5 MPaG, and the flow rate of phosphorus trichloride at the outlet of each nozzle was equal, both being 4 m / s.

[0158] The remaining structure, steps, and parameters were all the same as in Example 1.

[0159] The phosphorus trichloride atomized particle size of this embodiment is the same as that of Example 1.

[0160] The highest temperature in the furnace of this embodiment is 50℃, the average particle size SMD of phosphorus pentachloride is 50um, and the purity of phosphorus pentachloride is 99.99%.

[0161] Example 4

[0162] The difference between this embodiment and Example 2 is that the nozzle 102 of this embodiment is a gas flow type atomizing nozzle, and the structure of the gas flow type atomizing nozzle is the same as that of Example 1. The outlet of the second cooling device 6 is connected with the gas passage of all nozzles 102.

[0163] From the top of the reactor body to the bottom, the speed of the circulating gas at the outlet of the top nozzle is 40m / s; in the first nozzle group, the speed of the circulating gas at the outlet of each nozzle is 50m / s; in the second nozzle group, the speed of the circulating gas at the outlet of each nozzle is 60m / s; in the third nozzle group, the speed of the circulating gas at the outlet of each nozzle is 70m / s; and the speed of the phosphorus trichloride liquid at the outlet of each nozzle is 1m / s.

[0164] The remaining structure, steps and parameters are the same as those of Example 2.

[0165] The particle size of the phosphorus trichloride is measured by a laser particle size analyzer, and the physicochemical particle size of the phosphorus trichloride in the reactor is a four-level distribution: the first-level atomized particle size is 0.4-0.6mm, the second-level atomized particle size is 0.2-0.4mm, the third-level atomized particle size is 0.1-0.2mm, and the fourth-level atomized particle size is 0.1-0.15mm.

[0166] The highest temperature in the furnace of this embodiment is 60℃, the average particle size SMD of phosphorus pentachloride is 40um, and the purity of phosphorus pentachloride is 99.99%.

[0167] Comparative Example 3

[0168] The difference between this comparative example and Example 1 is that the nozzle spacing of this comparative example is 1.5 times the inner diameter of the reactor body, and the remaining structure, steps and parameters are the same as those of Example 1.

[0169] The particle size of the phosphorus trichloride is measured by a laser particle size analyzer, and the particle size of the phosphorus trichloride is a two-level distribution: the first-level atomized particle size is 0.1-0.2mm, and the second-level atomized particle size is 0.1-0.15mm.

[0170] The highest temperature in the furnace of this embodiment is 80℃, the diameter of phosphorus pentachloride is 20um, and the purity of phosphorus pentachloride is 99.99%.

[0171] Comparative Example 4

[0172] The difference between the present comparative example and Example 1 is that the nozzle spacing of the present comparative example is 6 times the inner diameter of the reactor body, and the rest of the structure, steps and parameters are the same as those of Example 1.

[0173] The particle size of phosphorus trichloride is measured by a laser particle size analyzer, and the particle size of phosphorus trichloride is two-level distribution: the primary atomized particle size is 0.1-0.2 mm, and the secondary atomized particle size is 0.1-0.15 mm.

[0174] The maximum temperature in the furnace of the present example is 40℃, the diameter of phosphorus pentachloride is 50um, the purity of phosphorus pentachloride is 99.99%, but the investment is increased by 3 times.

Claims

1. A phosphorus pentachloride synthesis reactor, characterized in that, It includes a reactor body, a nozzle disposed on the top of the reactor body, and at least two nozzle groups arranged horizontally around the side of the reactor body, each nozzle group including at least two nozzles; the distance between the top of the reactor body and the adjacent nozzle group is 2 to 5 times the inner diameter of the reactor body; Multiple nozzle groups are arranged sequentially from top to bottom along the axis of the reactor; the spacing between adjacent nozzle groups along the axis of the reactor body is 2 to 5 times the inner diameter of the reactor body.

2. The phosphorus pentachloride synthesis reactor as described in claim 1, characterized in that, The number of nozzles in each nozzle group is even, and the nozzles in each nozzle group are symmetrically arranged about the axis of the reactor body. And / or, the projections of the nozzles in two adjacent nozzle groups onto the cross-section of the reactor body are distributed at equal intervals along the circumference of the reactor body, where the cross-section of the reactor body refers to the surface perpendicular to the axis of the reactor body; And / or, the end of the nozzle outlet is flush with the inner wall surface of the reactor body; And / or, the nozzle is a pressure atomizing nozzle or an airflow atomizing nozzle; And / or, the axis of the nozzle outlet is perpendicular to the axis of the reactor body or inclined downwards; And / or, the reactor body is further provided with a chlorine source inlet, a discharge outlet, a circulating gas outlet, and a circulating gas inlet, the chlorine source inlet being located at the upper part of the reactor body, and the discharge outlet and the circulating gas outlet being located at the lower part of the reactor body.

3. The phosphorus pentachloride synthesis reactor as described in claim 2, characterized in that, The total number of nozzles is 3, 5, or 7; And / or, the number of chlorine source inlets corresponds to the number of nozzle groups, and each nozzle group is provided with a corresponding chlorine source inlet above it.

4. The phosphorus pentachloride synthesis reactor as described in claim 2, characterized in that, There are a total of 3 nozzles, one of which is located on the top of the reactor body, and the other two nozzles are arranged horizontally around the side of the reactor body symmetrically with the axis of the reactor body as the center. Alternatively, there are 7 nozzles, one of which is located at the top of the reactor body, and the remaining six nozzles are arranged in pairs to form three nozzle groups. The three nozzle groups are arranged sequentially from top to bottom along the axial direction of the reactor body. The two nozzles of each nozzle group are arranged horizontally around the side of the reactor body and symmetrically with the axis of the reactor body as the center. The projections of the nozzles in the three nozzle groups on the cross-section of the reactor body are distributed at equal intervals along the circumference of the reactor body.

5. A continuous synthesis system for phosphorus pentachloride, characterized in that, It includes the phosphorus pentachloride synthesis reactor and the first blower as described in any one of claims 1 to 4; The reactor body is equipped with a chlorine source inlet, a discharge outlet, a circulating gas outlet, and a circulating gas inlet. The first fan is connected between the circulating air outlet and the circulating air inlet.

6. The continuous synthesis system for phosphorus pentachloride as described in claim 5, characterized in that, When the nozzle is an airflow atomizing nozzle, the gas passage of the nozzle is connected to the circulating gas outlet; When the nozzle is a pressure atomizing nozzle, a first feed pump is connected to the liquid inlet of the nozzle, and the phosphorus trichloride liquid is pressurized by the first feed pump.

7. The continuous synthesis system for phosphorus pentachloride as described in claim 6, characterized in that, A second fan and a second cooling device are connected between the gas passage of the nozzle and the circulating gas outlet. The second fan and the second cooling device are arranged sequentially along the flow direction of the circulating gas. The second fan is used to compress the circulating gas into high-pressure gas, and the second cooling device is used to cool the circulating gas. The second cooling device is a heat exchanger.

8. The continuous synthesis system for phosphorus pentachloride as described in claim 5, characterized in that, The chlorine source inlet is connected to a chlorine source pipe, and the end of the chlorine source pipe extends into the center of the reactor body. And / or, the chlorine source is liquid chlorine; And / or, a circulating gas inlet is provided on the reactor body near each of the nozzle groups; And / or, the circulating gas outlet is located on the lower side of the reactor body; And / or, the discharge port is located at the bottom of the reactor body; And / or, the walls of the reactor body are configured as water-cooled walls.

9. The continuous synthesis system for phosphorus pentachloride as described in claim 5, characterized in that, The end of the chlorine source pipeline is connected to a chlorine source nozzle.

10. The continuous synthesis system for phosphorus pentachloride as described in claim 5, characterized in that, The continuous phosphorus pentachloride synthesis system further includes a first cooling device, which is connected between the first fan and the circulating gas inlet, and is used to cool the circulating gas. And / or, the continuous synthesis system of phosphorus pentachloride further includes a gas separation and purification device, which is disposed between the circulating gas outlet and the first blower for purifying the circulating gas; And / or, the continuous phosphorus pentachloride synthesis system further includes a material discharge flow aid device, which is located at the discharge port and has a fluidizing gas inlet connected to the circulating gas outlet.

11. The continuous synthesis system for phosphorus pentachloride as described in claim 10, characterized in that, The first cooling device includes a primary cooling device and a secondary cooling device connected sequentially along the flow direction of the circulating gas. The heat exchange medium temperature of the primary cooling device is room temperature, and the heat exchange medium temperature of the secondary cooling device is 10~30℃. Both the primary cooling device and the secondary cooling device are heat exchangers. And / or, the gas separation and purification device includes a cyclone dust collector and a bag dust collector connected in sequence along the flow direction of the circulating gas, the cyclone dust collector being connected to the outlet of the circulating gas, and the bag dust collector being connected to the first fan. And / or, when a second fan and a second cooling device are provided, the second fan and the second cooling device are arranged sequentially along the flow direction of the circulating gas, the second fan is connected to the bag filter, the second fan is used to compress the circulating gas into high-pressure gas, and the second cooling device is used to cool the circulating gas; And / or, when the continuous phosphorus pentachloride synthesis system further includes a second fan and a second cooling device, the second fan and the second cooling device are arranged sequentially along the flow direction of the circulating gas, the second fan is connected to the circulating gas outlet, the second fan is used to compress the circulating gas into high-pressure gas, the second cooling device is used to cool the circulating gas, and the fluidizing gas inlet is connected to the outlet of the second cooling device, so that the cooled circulating gas enters the fluidizing gas inlet; And / or, the number of fluidizing gas inlets is even, and the multiple fluidizing gas inlets are symmetrically arranged; And / or, the material discharge assist device is a fluidizer; And / or, the circulating gas outlet is located on the side of the reactor body above the material discharge flow aid device.

12. The continuous synthesis system for phosphorus pentachloride as described in claim 5, characterized in that, The continuous phosphorus pentachloride synthesis system also includes product tanks, which include a first product tank and a second product tank. The first product tank is connected to the discharge port, and the second product tank is connected to the outlet of the first product tank. And / or, the continuous phosphorus pentachloride synthesis system further includes a phosphorus trichloride storage tank and a chlorine source storage tank, wherein the phosphorus trichloride storage tank is connected to the liquid channel of the nozzle, and the chlorine source storage tank is connected to the chlorine source inlet.

13. The continuous synthesis system for phosphorus pentachloride as described in claim 12, characterized in that, When the discharge port is also provided with a material discharge aid device, the first product tank is connected to the outlet of the material discharge aid device, and the material discharge aid device is also provided with a fluidizing gas inlet, which is connected to the circulating gas outlet. And / or, the first product tank is further provided with a filter, the outlet of the filter is connected to the first product tank, and the air outlet of the filter is connected between the circulating gas outlet and the circulating gas inlet; And / or, the bottom of the first product tank is also provided with a material discharge flow aid device, the material discharge flow aid device is provided with a fluidizing gas inlet, and the fluidizing gas inlet is connected to the circulating gas outlet.

14. A continuous synthesis method for phosphorus pentachloride, characterized in that, The synthesis is carried out using the continuous phosphorus pentachloride synthesis system according to any one of claims 5 to 13, which includes the following steps: phosphorus trichloride liquid is introduced into the reactor body through the nozzle, the circulating gas is a mixture of chlorine and carbon dioxide, and a chlorine source is introduced into the reactor body through the chlorine source inlet to carry out the reaction.

15. The continuous synthesis method of phosphorus pentachloride as described in claim 14, characterized in that, When the nozzle is an airflow atomizing nozzle, the velocity of the circulating gas at the nozzle outlet is 20~100m / s, and the velocity of the phosphorus trichloride liquid at the nozzle outlet is 0.2~2m / s. When the nozzle is a pressure atomizing nozzle, the pressure drop of the nozzle is 0.1~0.5 MPaG, and the velocity of phosphorus trichloride liquid at the outlet of the nozzle is 2~10 m / s; And / or, the flow rate of the circulating gas is 9000~18000 Nm³. 3 / h; And / or, the mass flow rate of the phosphorus trichloride is 1.37~54.8 tons / h; And / or, the molar ratio K of the chlorine gas to the phosphorus trichloride is 1.0~1.05; And / or, the temperature of the reaction is 20~60°C; And / or, the atomized particle size of the phosphorus trichloride decreases sequentially from top to bottom along the reactor body.

16. The continuous synthesis method of phosphorus pentachloride as described in claim 15, characterized in that, When the nozzle is an airflow atomizing nozzle, the velocity of the circulating gas at the nozzle outlet is 60 m / s, and the velocity of the phosphorus trichloride liquid at the nozzle outlet is 1 m / s. When the nozzle is a pressure atomizing nozzle, the velocity of phosphorus trichloride liquid at the nozzle outlet is 4 m / s; And / or, the temperature of the reaction is 30~40℃; And / or, the atomized particle size distribution of the phosphorus trichloride is a two-stage, three-stage, or four-stage distribution, wherein in the two-stage distribution, the first-stage atomized particle size is 0.1~0.5mm and the second-stage atomized particle size is 0.1~0.15mm; In the three-stage distribution, the first-stage atomized particle size is 0.2~1mm, the second-stage atomized particle size is 0.1~0.5mm, and the third-stage atomized particle size is 0.1~0.15mm; In the four-level distribution, the first-level atomized particle size is 0.3~2mm, the second-level atomized particle size is 0.2~1mm, the third-level atomized particle size is 0.1~0.5mm, and the fourth-level atomized particle size is 0.1~0.15mm.

17. The continuous synthesis method of phosphorus pentachloride as described in claim 16, characterized in that, When the nozzle is an airflow atomizing nozzle, the velocity of the circulating gas at the outlet of the nozzle gradually increases from top to bottom along the axial direction of the reactor body; And / or, when the nozzle is a pressure atomizing nozzle, the pressure drop of the nozzle gradually increases from top to bottom along the axial direction of the reactor body. When three nozzle groups are provided, the pressure drop of the nozzle at the top of the reactor body is 0.1 MPaG, the pressure drop of each nozzle in the first nozzle group is 0.3 MPaG, the pressure drop of each nozzle in the second nozzle group is 0.4 MPaG, and the pressure drop of each nozzle in the third nozzle group is 0.5 MPaG. And / or, in the two-stage distribution, the first-stage atomized particle size is 0.1~0.2mm; In the three-level distribution, the first-level atomized particle size is 0.2~0.4mm, and the second-level atomized particle size is 0.1~0.2mm; In the four-level distribution, the first-level atomized particle size is 0.4~0.6mm, the second-level atomized particle size is 0.2~0.4mm, and the third-level atomized particle size is 0.1~0.2mm.

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