CN113321585A - Triphosgene preparation method based on crystallization drying - Google Patents
Triphosgene preparation method based on crystallization drying Download PDFInfo
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- CN113321585A CN113321585A CN202110631854.XA CN202110631854A CN113321585A CN 113321585 A CN113321585 A CN 113321585A CN 202110631854 A CN202110631854 A CN 202110631854A CN 113321585 A CN113321585 A CN 113321585A
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
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Abstract
The application discloses triphosgene preparation reaction unit and triphosgene preparation method based on crystallization drying, triphosgene preparation reaction unit include the retort, set up ultraviolet emitter in the retort, still include fan, water suction tank and booster pump, the air inlet of fan communicates with each other with the retort, be provided with gaseous check valve between fan and the retort, gaseous check valve is used for preventing gas to be flowed against in to the retort by the fan, and the gas outlet of fan meets with the air inlet of water suction tank, and the gas outlet of water suction tank meets with the booster pump, the booster pump is used for with gas pressurization back pump income retort in with the reaction liquid further reaction, and is provided with the heat exchanger between booster pump and the retort, the heat exchanger is used for the gas heating of pump income retort.
Description
The application is a divisional application with the application date of 2019, 2, 28 and the application number of 201910148986X and the patent name of triphosgene preparation reaction device and preparation process.
Technical Field
The invention relates to the field of chemical equipment, in particular to a triphosgene preparation method based on crystallization drying.
Background
The method for preparing the triphosgene comprises the steps of firstly putting dimethyl carbonate into a reaction kettle after metering, then introducing chlorine, and realizing the reaction of the chlorine and the dimethyl carbonate under the condition of ultraviolet illumination to obtain the bis (trichloromethyl) carbonate, wherein the reaction temperature is 60-80 ℃, the reaction time is about 7 hours, and a large amount of reaction waste gas (the components of the waste gas are hydrogen chloride and chlorine) is generated in the reaction process. The existing industrial production method for treating the waste gas comprises the steps of introducing the waste gas into clean water (hydrogen chloride in the tail gas is basically and completely absorbed by water, and only a small amount of chlorine is absorbed by water), and introducing the residual chlorine in the tail gas into alkali liquor for absorption after the chlorine in the tail gas is absorbed by the clean water.
Although zero emission of waste gas is realized in the production process, chlorine in the waste gas is a reaction raw material, and the chlorine is directly absorbed by alkali liquor to waste the raw material.
Disclosure of Invention
The invention provides a triphosgene preparation reaction device and a preparation process aiming at the problems.
The technical scheme adopted by the invention is as follows:
the utility model provides a triphosgene preparation reaction unit, includes the retort, set up ultraviolet emitter in the retort, still include fan, water suction tank and booster pump, the air inlet and the retort of fan communicate with each other, be provided with gaseous check valve between fan and the retort, gaseous check valve is used for preventing gaseous in to the retort adverse current by the fan, and the gas outlet of fan meets with the air inlet of water suction tank, and the gas outlet and the booster pump of water suction tank meet, the booster pump is used for pumping into the retort with the reaction liquid further reaction after the gas pressure boost in, and is provided with the heat exchanger between booster pump and the retort, the heat exchanger is used for pumping into the gas heating in the retort into for the pump.
The saturated sodium chloride solution is arranged in the water absorption tank, the reaction tank continuously generates chlorine and hydrogen chloride gas, the mixed gas is pumped out of the reaction tank by a fan, the mixed gas firstly absorbs the hydrogen chloride gas through the water absorption tank, then the residual chlorine is pressurized by a booster pump and enters a heat exchanger, and the heat exchanger raises the temperature of the chlorine and then enters the reaction tank to further react with the liquid.
The device can recycle the hydrogen chloride and the chlorine generated in the reaction process respectively, and the recycled chlorine is used as a reaction raw material for further reaction, so that the raw material is saved.
Optionally, the reactor further comprises an air outlet pipe, wherein a gas-liquid two-phase check valve is arranged on the air outlet pipe and used for preventing liquid from flowing back to the air inlet pipe and the air outlet pipe from the reaction kettle.
The gas-liquid two-phase check valve belongs to the existing mature technology, and has the following functions that when the air pressure in the air outlet pipe is lower than a rated value, the gas-liquid two-phase check valve is in a closed state, the gas in the air outlet pipe cannot enter the reaction tank, when the air pressure in the air outlet pipe reaches or is higher than the rated value, the gas-liquid two-phase check valve is opened instantly, the gas in the air outlet pipe is sprayed into the reaction tank to be in violent contact with the reaction liquid, and the reaction speed of the chlorine and the reaction liquid can be accelerated because the reaction liquid is in violent contact with the chlorine. The purpose of arranging the booster pump here is to gradually increase the gas pressure in the reaction tank, and meanwhile, the pressure resistance of the heat exchanger used as a matched heat exchanger needs to be superior to that of a conventional heat exchanger, and because a heat exchanger manufacturer can specifically customize the heat exchanger according to the pressure resistance using requirements of users, the heat exchanger is not specifically further stated.
It should be noted that the gas-liquid two-phase check valve can be used for one-way communication between gas-liquid two phases, and can also be used for one-way communication between gas-gas two phases and between liquid-liquid two phases.
Optionally, the reaction tank is a non-ferrous reaction tank, the air outlet pipe is a non-ferrous air outlet pipe, a magnet piston is arranged in the air outlet pipe, a non-ferrous support rod is arranged in the reaction tank, a rotating plate made of a non-ferrous material is rotatably mounted on the support rod, and an iron bead is arranged in the rotating plate; when the magnet piston moves in the air outlet pipe, the rotating plate rotates around the supporting rod.
In order to ensure that the magnet piston is not corroded by chlorine gas, the outer surface of the magnet piston is coated with corrosion-resistant paint. The setting mode of the concrete magnet piston in the reaction tank is as follows, because the reaction tank is vertically arranged, the air outlet pipe is arranged at the tank bottom of the reaction tank, the air outlet pipe is vertical to the tank bottom of the reaction tank, the gas-liquid two-phase check valve is arranged on the side wall of the air outlet pipe, the magnet piston is movably sealed in the air outlet pipe, when the booster pump does not start to inflate into the air outlet pipe, the magnet piston is positioned at the bottom of the air outlet pipe, when the booster pump starts to work, the magnet piston slowly moves from the bottom to the top of the air outlet pipe, the space in the air outlet pipe is divided into two spaces of an upper air cavity and a lower air cavity by the magnet piston (the volumes of the upper air cavity and the lower air cavity are variable), the volume of the upper air cavity is gradually reduced, the volume of the lower air cavity is gradually increased, the position of the gas-liquid two-phase check valve is changed from the upper air cavity into the lower air cavity, when the pressure in the lower air cavity reaches the rated value of the gas-liquid two-liquid one-phase check valve, most of the gas in the lower gas cavity instantly gushes into the reaction liquid (simultaneously, the gas-liquid two-phase one-way valve) and is also instantly closed, and the magnet piston moves from the upper end of the gas outlet pipe to the bottom under the action of the pressure of the upper gas cavity and the self-generated gravity.
The installation position relationship between the rotating plate and the supporting rod is somewhat similar to a seesaw, the rotating plate rotates around the supporting rod and is somewhat similar to a seesaw rotating around the supporting point, because the iron ball is arranged at one end of the rotating plate and the magnet piston always has attraction effect on the iron ball, so that the magnet piston can drive the rotating plate to move continuously like a seesaw in the process of moving in the air outlet pipe, the rotating plate can continuously stir the liquid in the reaction tank in the moving process, the liquid can accelerate the reaction speed in the moving process, the reaction efficiency is higher, meanwhile, the rotation of the rotating plate can promote the gas (the mixture of chlorine and hydrogen chloride) in the liquid to escape quickly, but the hydrogen chloride gas can be recovered and then sent back to the reaction liquid again, because hydrogen chloride is actually a product after reaction, the reaction speed and the conversion rate of raw materials can be increased after the hydrogen chloride is removed according to the Lexhlet's series equilibrium shift principle.
Therefore, the reaction speed can be greatly improved and the conversion rate of raw materials can be improved by arranging the magnet piston and the rotating plate.
Optionally, the support rod is a T-shaped support rod, the rotating plate is rotatably sleeved on the support rod through a rotating ring of the rotating plate, and the support rod is a hollow support rod.
Because need cool off the crystallization after the reaction, so choose inside hollow bracing piece for use, can fill low-temperature water to the bracing piece after the reaction finishes and cool down like this, so specifically can set up some pipes and be linked together with the inside space of bracing piece on the retort, fill low-temperature water through the pipe in to the bracing piece and cool down. Of course, in order to ensure the cooling crystallization effect and speed, a plurality of condensing pipes can be separately arranged in the reaction tank.
Optionally, the system further comprises a recovery tank, wherein the recovery tank is arranged between the fan and the water absorption tank, a plurality of adsorption fillers are arranged in the recovery tank, and the temperature of the adsorption fillers is 4-10 ℃.
Because the whole reaction is carried out at the temperature of 60-80 ℃, the boiling point of the dimethyl carbonate is 90.1 ℃, the two temperature points are very close, part of dimethyl carbonate can escape as steam in the reaction process, a recovery tank is arranged to recover the part of dimethyl carbonate gas, the adsorption filler is actually a block, and the dimethyl carbonate can be adsorbed on the block in a liquid form after meeting the low-temperature block due to the low temperature (4-10 ℃) of the block. Because it is prior art to set up the absorption filler in the recovery jar, this scheme does not make concrete detailed statement, and this scheme provides a recovery jar and the realization mode of absorption filler according to the actual conditions of this device simultaneously, and the recovery jar is the corrosion-resistant jar that has air inlet and gas outlet, and the absorption filler is ordinary glass bottle, and glass bottle internal seal has been filled with water (and the temperature is 4 ℃ -10 ℃), and glass bottle stopper has been filled with corrosion-resistant jar. The liquid dimethyl carbonate accumulated on the outer wall of the glass bottle can be further recovered, so that the recovery of the dimethyl carbonate raw material is realized.
The reason why the temperature of the adsorption filler is controlled to be not lower than 4 ℃ in the device is that the dimethyl carbonate can be separated out in the form of solid particles at the temperature of lower than 4 ℃, and the solid particles can block a recovery tank.
Optionally, still include the three-way valve, the three-way valve sets up between jar and the booster pump are inhaled to water, and two interfaces of three-way valve meet with jar and booster pump are inhaled to water respectively, have connect the regeneration tank on another interface of three-way valve, be provided with the carbon tetrachloride liquid in the regeneration tank.
Because the whole process of preparing the triphosgene can be divided into four parts of reaction, cooling crystallization, vacuumizing and deacidification and vacuum drying, after the two parts of reaction and cooling crystallization are finished, vacuumizing and deacidification are needed to be carried out in the reaction tank, the extracted gas is actually three parts (hydrogen chloride, chlorine and dimethyl carbonate), the dimethyl carbonate can be adsorbed by the recovery tank, the hydrogen chloride is adsorbed by the water absorption tank, and the chlorine can be adsorbed by carbon tetrachloride in the regeneration tank. Particularly, the three-way valve and the booster pump are closed and are not communicated in the process of vacuumizing and deacidifying gas, and the heat exchanger and the booster pump are both idle.
Optionally, the system further comprises a mixing ejector and a gas storage tank, wherein a gas inlet of the booster pump is respectively connected with the three-way valve and the mixing ejector, the remaining two interfaces of the mixing ejector are respectively connected with the gas storage tank and the regeneration tank, and the mixing ejector is used for mixing gas in the gas storage tank and gas exhausted from the regeneration tank and then conveying the mixture to the booster pump; and control valves are arranged between the mixing ejector and the gas storage tank and between the mixing ejector and the regeneration tank.
After cooling crystallization is completed, the inside of the reaction tank is basically full of solid particles (a small amount of liquid drops can be remained on the surface), nitrogen (or other similar inert gases) is filled in a gas storage tank in the device, the nitrogen in the gas storage tank enters a heat exchanger through a booster pump to be heated (the temperature of the heated nitrogen is between 30 ℃ and 35 ℃) and then enters a gas outlet pipe, then a magnet piston is pushed to move in the gas outlet pipe, the magnet piston still drives a rotating plate to move, the rotating plate can disturb the solid particles in the reaction tank in the moving process, and the instantly sprayed high-temperature nitrogen (30 ℃ to 35 ℃) can blow liquid on the surfaces of the solid particles, so that the solid particles are stirred and are instantly blown by high-temperature nitrogen, and the liquid on the surfaces of the solid particles can be quickly blown and dried. Meanwhile, the fan still extracts the gas in the reaction tank in the process, the gas extracted by the fan comprises nitrogen, chlorine and a very small amount of dimethyl carbonate, the chlorine and the dimethyl carbonate are absorbed, and the nitrogen from the regeneration tank is mixed with fresh nitrogen under the action of the mixing ejector and then enters the next circulation for continuous operation. The above process is also vacuum drying of solid particles (i.e. product), but this vacuum drying process is different from conventional "vacuum drying".
Particularly, the three-way valve and the booster pump are closed and are not communicated in the nitrogen blowing process.
Optionally, the system further comprises a cold blowing pipe, wherein an air outlet of the booster pump is respectively connected with the cold blowing pipe and the heat exchanger, two ends of the cold blowing pipe are respectively connected with the booster pump and the reaction tank, a control valve is arranged on the cold blowing pipe, and a control valve is arranged between the booster pump and the heat exchanger.
The hot nitrogen can blow dry most of liquid on the surface of solid particles (namely products), and simultaneously can keep the solid particles at a higher temperature which is not beneficial to carrying and packaging of the products, so the products must be cooled, control valves between a mixing injector and a gas storage tank and between the mixing injector and a regeneration tank are closed, a control valve on a cold blow pipe is opened, the three-way valve and a booster pump are kept closed and are not communicated, then cold nitrogen (the temperature is 10-15 ℃) is blown against the solid particles, the temperature on the surface of the solid particles is reduced on one hand, and the liquid on the surface of the solid particles is blown dry completely on the other hand. Meanwhile, it should be noted that the fan still needs to be started in the process, the gas extracted from the reaction tank needs to be sequentially adsorbed by the recovery tank, the water absorption tank and the regeneration tank, and the gas discharged from the regeneration tank can be directly discharged, because the discharged gas is basically nitrogen, the gas is harmless to the environment, but in consideration of resource conservation, a nitrogen receiving pipe (provided with a control valve) can be connected to the regeneration tank, and the nitrogen is conveyed to other recycling equipment by the nitrogen receiving pipe.
Specifically, the fan in the device is connected with the top of the reaction tank through a pipeline, and the cold blowing pipe is connected with the bottom of the reaction tank.
Based on the device, the scheme further provides a triphosgene preparation method based on the equipment and based on crystallization drying, which comprises the following steps:
s1: introducing chlorine into dimethyl carbonate, maintaining the temperature of the whole reaction system at 60-80 ℃, then continuously stirring the reaction liquid, continuously pumping air into the reaction tank and replenishing the chlorine into the reaction liquid, maintaining the state for 7 hours, and continuously irradiating by using ultraviolet rays in the whole process;
s2, cooling and crystallizing, and vacuumizing the reaction tank after crystallization is finished;
s3: after the vacuum pumping is finished, blowing nitrogen at 30-35 ℃ against the crystallized solid, and then blowing nitrogen at 10-15 ℃ against the crystallized solid.
The triphosgene prepared by the process has the following beneficial effects: one reactant in the reaction product can be transferred away in time, so that the reaction rate is improved, the conversion rate of the raw material is greatly improved, and the purity of the prepared product is higher.
The invention has the beneficial effects that: the hydrogen chloride and the chlorine generated in the reaction process can be respectively recycled, and the recycled chlorine is used as a reaction raw material for further reaction, so that the raw material is saved; and the product preparation speed is higher, and the raw material conversion rate is high.
Description of the drawings:
FIG. 1 is a schematic diagram of the internal structure of a reaction tank;
FIG. 2 is a schematic view of the fitting relationship between the rotating plate and the supporting rod;
FIG. 3 is a schematic diagram showing the structure of each part of a triphosgene preparation reaction apparatus;
FIG. 4 is a schematic view of a simple reaction vessel.
The figures are numbered:
1. the device comprises a reaction tank, 101, a support rod, 102, a rotating plate, 103, an iron ball, 104, a magnet piston, 105, a lower gas cavity, 106, a gas-liquid two-phase one-way valve, 107, an upper gas cavity, 108, a rotating ring, 109, a condensing pipe, 1010, an ultraviolet emission device, 1011, a tail gas outlet, 1012, a chlorine gas inlet, 1013, a discharge port, 2, a fan, 3, a recovery tank, 4, a water suction tank, 5, a regeneration tank, 6, a gas storage tank, 7, a control valve, 8, a mixing ejector, 9, a three-way valve, 10, a booster pump, 11, a preheater, 12, a cold blowing pipe, 13, a nitrogen receiving pipe, 14 and a gas one-way valve.
The specific implementation mode is as follows:
the present invention will be described in detail below with reference to the accompanying drawings.
As shown in attached drawings 1, 2 and 3, the triphosgene preparation reaction device comprises a reaction tank 1, wherein an ultraviolet emission device is arranged in the reaction tank 1, the triphosgene preparation reaction device further comprises a fan 2, a water suction tank 4 and a booster pump 10, an air inlet of the fan 2 is communicated with the reaction tank 1, an air one-way valve 14 is arranged between the fan 2 and the reaction tank 1 and used for preventing gas from flowing back into the reaction tank 1 from the fan 2, an air outlet of the fan 2 is connected with an air inlet of the water suction tank 4, an air outlet of the water suction tank 4 is connected with the booster pump 10, the booster pump 10 is used for boosting the gas and then pumping the gas into the reaction tank 1 to further react with reaction liquid, a heat exchanger 11 is arranged between the booster pump 10 and the reaction tank 1, and the heat exchanger 11 is used for heating the gas pumped into the reaction tank 1.
It should be noted that the water absorption tank 4 is filled with a saturated sodium chloride solution, the saturated sodium chloride solution has a good absorption effect on hydrogen chloride gas, but has almost no absorption effect on chlorine gas, so the saturated sodium chloride solution is arranged here, in the device, the reaction tank 1 continuously generates chlorine gas and hydrogen chloride gas through reaction, the mixed gas is pumped out of the reaction tank 1 by the fan 2, the mixed gas firstly absorbs the hydrogen chloride gas through the water absorption tank 4, then the rest chlorine gas is pressurized by the booster pump 10 and enters the heat exchanger 11, and the heat exchanger 11 raises the temperature of the chlorine gas and then enters the reaction tank 1 to further react with the liquid.
The device can recycle the hydrogen chloride and the chlorine generated in the reaction process respectively, and the recycled chlorine is used as a reaction raw material for further reaction, so that the raw material is saved.
As shown in fig. 1, fig. 2 and fig. 3, the reactor further comprises a gas outlet pipe, a gas-liquid two-phase check valve 106 is arranged on the gas outlet pipe, and the gas-liquid two-phase check valve 106 is used for preventing liquid from flowing back to the gas inlet pipe from the reaction kettle.
The gas-liquid two-phase check valve 106 belongs to the existing mature technology, and the gas-liquid two-phase check valve 106 has the following specific effects that when the air pressure in the air outlet pipe is lower than a rated value, the gas-liquid two-phase check valve 106 is in a closed state, the gas in the air outlet pipe cannot enter the reaction tank 1, when the air pressure in the air outlet pipe reaches or is higher than the rated value, the gas-liquid two-phase check valve 106 is opened instantly, the gas in the air outlet pipe flows into the reaction tank 1 and is in violent contact with the reaction liquid, and the reaction speed of the chlorine and the reaction liquid can be accelerated because the reaction liquid is in violent contact with the chlorine. The purpose of the booster pump 10 is to gradually increase the gas pressure in the reaction tank 1, and the pressure resistance of the heat exchanger 11 used as a complete set is better than that of the conventional heat exchanger 11, because the manufacturer of the heat exchanger 11 can specifically customize the heat exchanger 11 according to the pressure resistance requirement of the user, so that no further description is made on the heat exchanger 11.
It should be noted that the gas-liquid two-phase check valve 106 may be used for one-way communication between gas and liquid phases, and may also be used for one-way communication between gas and liquid phases and between liquid and liquid phases.
As shown in fig. 1, fig. 2 and fig. 3, the reaction tank 1 is a non-ferrous reaction tank 1, the air outlet pipe is a non-ferrous air outlet pipe, a magnet piston 104 is arranged in the air outlet pipe, a non-ferrous support rod 101 is arranged in the reaction tank 1, a non-ferrous rotating plate 102 is rotatably arranged on the support rod 101, and an iron bead is arranged in the rotating plate 102; when the magnet piston 104 moves in the outlet pipe, the rotating plate 102 rotates around the support rod 101.
To ensure that the magnet piston 104 is not corroded by chlorine gas, the outer surface of the magnet piston 104 is coated with some corrosion-resistant paint. The specific arrangement mode of the magnet piston 104 in the reaction tank 1 is as follows, because the reaction tank 1 is vertically arranged, the air outlet pipe is arranged at the bottom of the reaction tank 1, the air outlet pipe is vertical to the bottom of the reaction tank 1, the gas-liquid two-phase check valve 106 is arranged on the side wall of the air outlet pipe, the magnet piston 104 is movably and hermetically arranged in the air outlet pipe, when the booster pump 10 does not start to charge air into the air outlet pipe, the magnet piston 104 is positioned at the bottom of the air outlet pipe, when the booster pump 10 starts to work, the magnet piston 104 slowly moves from the bottom of the air outlet pipe to the top, the magnet piston 104 divides the space in the air outlet pipe into an upper air cavity 107 and a lower air cavity 105 (the specific volumes of the upper air cavity 107 and the lower air cavity 105 are variable), the volume of the upper air cavity 107 gradually decreases, the volume of the lower air cavity 105 gradually increases, the position of the gas-liquid two-phase check valve 106 changes from the upper air cavity 107 to the lower air cavity 105, when the air pressure in the lower air cavity 105 reaches the rated value of the gas-liquid two-phase check valve 106, most of the air in the lower air cavity 105 instantly gushes into the reaction liquid (meanwhile, the gas-liquid two-phase check valve 106) and is also instantly closed, and the magnet piston 104 moves from the upper end of the air outlet pipe to the bottom under the action of the pressure of the upper air cavity 107 and the self-generated gravity.
The installation position relation of the rotating plate 102 and the supporting rod 101 is somewhat similar to that of a seesaw, the rotating plate 102 rotates around the supporting rod 101 and somewhat similar to that of a seesaw and rotates around a supporting point, because an iron ball 103 is arranged at one end of the rotating plate 102, and the magnet piston 104 has an attraction effect on the iron ball 103 all the time, the magnet piston 104 can drive the rotating plate 102 to move continuously like a seesaw in the process of moving in the air outlet pipe, the rotating plate 102 can stir the liquid in the reaction tank 1 continuously in the moving process, the liquid can accelerate the reaction speed in the moving process, the reaction efficiency is higher, meanwhile, the rotating plate 102 rotates to accelerate the escape of gas (the mixture of chlorine and hydrogen chloride) in the liquid, but the hydrogen chloride gas can be recovered and then sent back to the reaction liquid again, because a product obtained after the hydrogen chloride actually reacts is based on the principle of Lexhlet's column balance movement, after the hydrogen chloride is removed, the reaction speed and the conversion rate of the raw materials can be increased.
Therefore, by providing the magnet piston 104 and the rotating plate 102, the reaction rate can be greatly increased, and the conversion rate of the raw material can be increased.
As shown in fig. 1, fig. 2 and fig. 3, the supporting rod 101 is a T-shaped supporting rod 101, the rotating plate 102 is rotatably sleeved on the supporting rod 101 through a rotating ring 108 thereof, and the supporting rod 101 is a supporting rod 101 with a hollow interior.
Because need cool off the crystallization after the reaction, so choose inside hollow bracing piece 101 for use, can fill low-temperature water to the bracing piece 101 after the reaction finishes and cool down like this, so specifically can set up some pipes and be linked together with the inside space of bracing piece 101 on retort 1, fill low-temperature water through the pipe in to bracing piece 101 and cool down. Of course, in order to ensure the cooling crystallization effect and the cooling crystallization speed, a plurality of condensation pipes can be separately arranged in the reaction tank 1.
As shown in attached figures 1, 2 and 3, the device also comprises a recovery tank 3, wherein the recovery tank 3 is arranged between the fan 2 and the water suction tank 4, a plurality of adsorption fillers are arranged in the recovery tank 3, and the temperature of the adsorption fillers is 4-10 ℃.
Because the whole reaction is carried out at the temperature of 60-80 ℃, the boiling point of dimethyl carbonate is 90.1 ℃, the two temperature points are very close, part of dimethyl carbonate can escape as steam in the reaction process, a recovery tank 3 is arranged to recover the part of dimethyl carbonate gas, the adsorption filler is actually a block, and the dimethyl carbonate can be adsorbed on the block in a liquid form after meeting the low-temperature block due to the low temperature of the block (4-10 ℃). Because it is prior art to set up the absorption filler in recovery jar 3, this scheme does not make concrete detailed statement, and this scheme provides a recovery jar 3 and the realization mode of absorption filler according to the actual conditions of this device simultaneously, and recovery jar 3 is the corrosion-resistant jar that has air inlet and gas outlet, and the absorption filler is ordinary glass bottle, and glass bottle internal seal has been filled with water (and the temperature is 4 ℃ -10 ℃), and glass bottle has been filled with corrosion-resistant jar. The liquid dimethyl carbonate accumulated on the outer wall of the glass bottle can be further recovered, so that the recovery of the dimethyl carbonate raw material is realized.
The reason why the temperature of the adsorption packing is controlled not to be lower than 4 ℃ in the present apparatus is that dimethyl carbonate is precipitated as solid particles at a temperature lower than 4 ℃ and the solid particles may block the recovery tank 3.
As shown in attached figures 1, 2 and 3, the device further comprises a three-way valve 9, the three-way valve 9 is arranged between the water absorption tank 4 and the booster pump 10, two interfaces of the three-way valve 9 are respectively connected with the water absorption tank 4 and the booster pump 10, the other interface of the three-way valve 9 is connected with a regeneration tank 5, and carbon tetrachloride liquid is arranged in the regeneration tank 5.
Because the whole process of preparing the triphosgene can be divided into four parts of reaction, cooling crystallization, vacuumizing and deacidification and vacuum drying, after the two parts of reaction and cooling crystallization are finished, vacuumizing and deacidification are needed to be carried out in the reaction tank 1, the gas to be pumped is actually three parts (hydrogen chloride, chlorine and dimethyl carbonate), the dimethyl carbonate is adsorbed by the recovery tank 3, the hydrogen chloride is adsorbed by the water absorption tank 4, and the chlorine can be adsorbed by the carbon tetrachloride in the regeneration tank 5. Particularly, in the process of vacuumizing to deacidify the gas, the three-way valve 9 and the booster pump 10 are closed and are not communicated, and the heat exchanger 11 and the booster pump 10 are both idle.
As shown in fig. 1, fig. 2 and fig. 3, the system further includes a mixing ejector 8 and a gas tank 6, wherein a gas inlet of the booster pump 10 is respectively connected to the three-way valve 9 and the mixing ejector 8, the remaining two ports of the mixing ejector 8 are respectively connected to the gas tank 6 and the regeneration tank 5, and the mixing ejector 8 is used for mixing the gas in the gas tank 6 and the gas discharged from the regeneration tank 5 and then delivering the mixture to the booster pump 10; and control valves 7 are arranged between the mixing injector 8 and the gas storage tank 6 and between the mixing injector 8 and the regeneration tank 5.
After cooling crystallization is completed, the inside of the reaction tank 1 is basically all solid particles (a small amount of liquid drops are remained on the surface), and nitrogen (or other similar inert gases) is filled in the gas storage tank 6 of the device, the working process of the design is as follows, the nitrogen in the gas storage tank 6 enters the heat exchanger 11 through the booster pump 10 to be heated and then enters the gas outlet pipe, then the magnet piston 104 is pushed to move in the gas outlet pipe, the magnet piston 104 still drives the rotating plate 102 to move, the rotating plate 102 can disturb the solid particles in the reaction tank 1 in the moving process, and the instantly sprayed high-temperature nitrogen can blow liquid on the surfaces of the solid particles, so that the high-temperature nitrogen is used for blowing the liquid on the surfaces of the solid particles instantly while stirring the solid particles, and the liquid on the surfaces of the solid particles can be blown fast. Meanwhile, in the process, the fan 2 still extracts the gas in the reaction tank 1, the gas extracted by the fan 2 comprises nitrogen, hydrogen chloride, chlorine and a very small amount of dimethyl carbonate, the hydrogen chloride, the chlorine and the dimethyl carbonate are absorbed, and the nitrogen from the regeneration tank 5 is mixed with fresh nitrogen under the action of the mixing ejector 8 and then enters the next cycle for continuous operation. The above process is also vacuum drying of solid particles (i.e. product), but this vacuum drying process is different from conventional "vacuum drying".
Particularly, the three-way valve 9 and the booster pump 10 are closed and are not communicated in the nitrogen blowing process.
As shown in the attached drawings 1, 2 and 3, the reactor further comprises a cold blowing pipe 12, an air outlet of the booster pump 10 is respectively connected with the cold blowing pipe 12 and the heat exchanger 11, two ends of the cold blowing pipe 12 are respectively connected with the booster pump 10 and the reaction tank 1, the cold blowing pipe 12 is provided with a control valve 7, and the control valve 7 is arranged between the booster pump 10 and the heat exchanger 11.
The hot nitrogen can blow dry most of liquid on the surface of solid particles (namely products), and simultaneously can keep the solid particles at a higher temperature, which is not beneficial to the carrying and packaging of the products, so the products must be cooled, therefore, the control valves 7 between the mixing injector 8 and the gas storage tank 6 and between the mixing injector 8 and the regeneration tank 5 are closed, the control valve 7 on the cold blow pipe 12 is opened, the three-way valve 9 and the booster pump 10 are kept closed and are not communicated, and then the cold nitrogen (with the temperature of 10-15 ℃) is blown against the solid particles, so that the temperature on the surface of the solid particles is reduced on one hand, and the liquid on the surface of the solid particles is thoroughly blown dry on the other hand. Meanwhile, it should be noted that the fan 2 still needs to be turned on in the process, the gas extracted from the reaction tank 1 needs to be sequentially adsorbed by the recovery tank 3, the water absorption tank 4 and the regeneration tank 5, and the gas coming out from the regeneration tank 5 can be directly discharged, because the discharged gas is basically nitrogen, the environment is not harmful, but in consideration of resource saving, a nitrogen receiving pipe 13 (the nitrogen receiving pipe 13 is also provided with the control valve 7) can be connected to the regeneration tank 5, and the nitrogen is conveyed to other recycling equipment by the nitrogen receiving pipe 13.
Specifically, the fan 2 in the device is connected with the top of the reaction tank 1 through a pipeline, and the cold blow pipe 12 is connected with the bottom of the reaction tank 1.
Further, the invention also provides a triphosgene preparation method based on crystallization drying, which comprises the following steps:
s1: introducing chlorine into dimethyl carbonate, maintaining the temperature of the whole reaction system at 60-80 ℃, then continuously stirring the reaction liquid, continuously pumping air into the reaction tank and replenishing the chlorine into the reaction liquid, maintaining the state for 7 hours, and continuously irradiating by using ultraviolet rays in the whole process;
s2, cooling and crystallizing, and vacuumizing the reaction tank after crystallization is finished;
s3: after the vacuum pumping is finished, blowing nitrogen at 30-35 ℃ against the crystallized solid, and then blowing nitrogen at 10-15 ℃ against the crystallized solid.
It should be further noted that the present embodiment also provides a simplified embodiment, the simplified embodiment uses a simple reaction kettle as shown in fig. 4, the simple reaction kettle includes a reaction tank 1, a condensation pipe 109 and an ultraviolet emission device 1010 are installed in the reaction tank 1, a tail gas outlet 1011, a chlorine inlet 1012 and a discharge port 1013 are arranged on the reaction tank 1, when the simple reaction kettle is installed, the tail gas outlet 1011 is connected with the gas one-way valve 14 through a pipeline, the chlorine inlet 1012 is connected with the cold blowing pipe 12, and the discharge port 1013 is connected with the preheater 11 through a pipeline.
The above description is only for the preferred embodiment of the present invention and is not intended to limit the scope of the present invention, and all equivalent structural changes made by using the contents of the present specification and the drawings can be directly or indirectly applied to other related technical fields and are included in the scope of the present invention.
Claims (4)
1. A triphosgene preparation method based on crystallization drying is characterized by comprising the following steps:
s1: introducing chlorine into dimethyl carbonate, maintaining the temperature of the whole reaction system at 60-80 ℃, continuously pumping air into the reaction tank and replenishing the chlorine into the reaction liquid, maintaining the state for 7 hours, and continuously irradiating by using ultraviolet rays in the whole process;
s2, cooling and crystallizing, and vacuumizing the reaction tank after crystallization is finished;
s3: after the vacuum pumping is finished, blowing nitrogen at 30-35 ℃ against the crystallized solid, and then blowing nitrogen at 10-15 ℃ against the crystallized solid;
the steps are carried out in a reaction device;
the reaction device comprises a reaction tank, an ultraviolet emission device is arranged in the reaction tank, and the reaction device further comprises a fan, a water absorption tank and a booster pump, wherein an air inlet of the fan is communicated with the reaction tank, a gas one-way valve is arranged between the fan and the reaction tank and used for preventing gas from flowing back into the reaction tank from the fan, an air outlet of the fan is connected with an air inlet of the water absorption tank, an air outlet of the water absorption tank is connected with the booster pump, the booster pump is used for pumping the gas into the reaction tank after being boosted to further react with reaction liquid, a heat exchanger is arranged between the booster pump and the reaction tank, and the heat exchanger is used for heating the gas pumped into the reaction tank;
the gas outlet pipe is provided with a gas-liquid two-phase one-way valve which is used for preventing liquid from flowing back to the gas inlet pipe and the gas outlet pipe from the reaction kettle;
the reaction tank is made of nonferrous materials, the air outlet pipe is made of nonferrous materials, a magnet piston is arranged in the air outlet pipe, a nonferrous material supporting rod is arranged in the reaction tank, a rotating plate made of nonferrous materials is rotatably arranged on the supporting rod, and an iron bead is arranged in the rotating plate; when the magnet piston moves in the air outlet pipe, the rotating plate rotates around the supporting rod;
the recovery tank is arranged between the fan and the water suction tank, a plurality of adsorption fillers are arranged in the recovery tank, and the temperature of the adsorption fillers is 4-1 ℃;
the carbon tetrachloride regeneration device also comprises a three-way valve, wherein the three-way valve is arranged between the water suction tank and the booster pump, two interfaces of the three-way valve are respectively connected with the water suction tank and the booster pump, the other interface of the three-way valve is connected with a regeneration tank, and carbon tetrachloride liquid is arranged in the regeneration tank; the regeneration tank is connected with a nitrogen-collecting pipe, and the nitrogen-collecting pipe is provided with a control valve.
2. The method for preparing triphosgene based on crystallization drying as claimed in claim 1, wherein the supporting rod is a T-shaped supporting rod, and the rotating plate is rotatably sleeved on the supporting rod through its own rotating ring, and the supporting rod is a hollow supporting rod.
3. The method for preparing triphosgene based on crystallization drying according to claim 1, further comprising a mixing injector and a gas tank, wherein the gas inlet of the booster pump is connected to the three-way valve and the mixing injector, respectively, and the remaining two ports of the mixing injector are connected to the gas tank and the regeneration tank, respectively, and the mixing injector is used for mixing the gas in the gas tank and the gas discharged from the regeneration tank and then delivering the mixture to the booster pump; and control valves are arranged between the mixing ejector and the gas storage tank and between the mixing ejector and the regeneration tank.
4. The method for preparing triphosgene based on crystallization drying as claimed in claim 3, further comprising a cold blow pipe, wherein the air outlet of the booster pump is connected to the cold blow pipe and the heat exchanger, respectively, both ends of the cold blow pipe are connected to the booster pump and the reaction tank, respectively, the cold blow pipe is provided with a control valve, and the control valve is arranged between the booster pump and the heat exchanger.
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|---|---|---|---|---|
| CN114100323A (en) * | 2021-11-15 | 2022-03-01 | 德沃德科技(重庆)有限责任公司 | Solid phosgene tail gas separation process and equipment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3440141A1 (en) * | 1984-11-02 | 1986-05-07 | Heiner Dipl.-Chem. Dr. 8000 München Eckert | Use of bistrichloromethyl carbonate as a proreagent for phosgene |
| RU2288217C1 (en) * | 2005-06-27 | 2006-11-27 | Открытое Акционерное Общество "Каустик" | Method for preparing perchlorinated carbonic and chlorocarbonic acid methyl esters |
| CN106748794A (en) * | 2017-01-12 | 2017-05-31 | 山东德普化工科技有限公司 | A kind of two（Trichloromethyl）The synthesizer and method of carbonic ester |
| CN109053493A (en) * | 2018-09-13 | 2018-12-21 | 浙江丽水有邦新材料有限公司 | methylcyclohexyl diisocyanate preparation method and reaction kettle |
-
2019
- 2019-02-28 CN CN201910148986.XA patent/CN109761812B/en active Active
- 2019-02-28 CN CN202110631854.XA patent/CN113321585B/en active Active
- 2019-02-28 CN CN202110633528.2A patent/CN113292428B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3440141A1 (en) * | 1984-11-02 | 1986-05-07 | Heiner Dipl.-Chem. Dr. 8000 München Eckert | Use of bistrichloromethyl carbonate as a proreagent for phosgene |
| RU2288217C1 (en) * | 2005-06-27 | 2006-11-27 | Открытое Акционерное Общество "Каустик" | Method for preparing perchlorinated carbonic and chlorocarbonic acid methyl esters |
| CN106748794A (en) * | 2017-01-12 | 2017-05-31 | 山东德普化工科技有限公司 | A kind of two（Trichloromethyl）The synthesizer and method of carbonic ester |
| CN109053493A (en) * | 2018-09-13 | 2018-12-21 | 浙江丽水有邦新材料有限公司 | methylcyclohexyl diisocyanate preparation method and reaction kettle |
Non-Patent Citations (1)
| Title |
|---|
| 李林: "常用气体脱水干燥工艺介绍及应用", 《化工技术与开发》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114100323A (en) * | 2021-11-15 | 2022-03-01 | 德沃德科技(重庆)有限责任公司 | Solid phosgene tail gas separation process and equipment |
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| CN109761812A (en) | 2019-05-17 |
| CN113321585B (en) | 2022-03-22 |
| CN113292428A (en) | 2021-08-24 |
| CN109761812B (en) | 2021-07-27 |
| CN113292428B (en) | 2022-03-22 |
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