Device for producing benzophenone azine in same kettle

Abstract

The utility model provides a device for producing benzophenonetazine in the same kettle, which is characterized in that a reaction kettle adopts a self-suction stirrer, and ammonia gas in a gas phase at the top of the kettle is sucked back to a liquid phase for reuse; the method comprises the following steps: aminating a benzophenone raw material under the condition that water is used as a solvent to form benzophenone imine slurry; an ammonia water outlet is formed in the side surface of the reaction kettle and automatically discharges water after amination is finished; and after dewatering, oxidizing by using high-pressure air under a high-temperature condition to obtain a benzophenone azine solid. The method avoids the use of an organic solvent in a traditional method, the amination reaction and the oxidation reaction are carried out in the same reaction kettle, material transfer is not needed, and all production steps are completed by adopting an automatic means, so that the raw material utilization rate, the labor productivity and the high-quality rate of products are improved.

Description

Technical Field

[0001] This utility model relates to an apparatus for producing ketazine compounds, mainly an apparatus for producing benzophenone azide in the same reactor. Background Technology

[0002] Ketoazines are an important class of intermediates widely used in the synthesis of dyes, photosensitive materials, polymers, pharmaceuticals, and pesticides. Due to the presence of -C=NN=C- conjugated structures, they can undergo a variety of chemical reactions.

[0003] There are three common synthetic methods for ketadiazine compounds: the Bayer method, the hydrogen peroxide method, and the hydrazine hydrate method. The Bayer method involves oxidizing ammonia with chlorine or sodium hypochlorite in the presence of aliphatic ketones to obtain ketadiazine. This method uses inexpensive raw materials and has a yield close to the theoretical value; however, using chlorine as the oxidant causes significant environmental pollution. The hydrogen peroxide method first reacts a ketone with ammonia to form a ketimine, then oxidizes it with hydrogen peroxide to form an oxaisohydrazone, which is then aminated to generate ketadiazine. This method is slightly more complex and has higher investment costs. The hydrazine hydrate method uses hydrazine hydrate and a ketone as raw materials, preparing ketadiazine compounds through a ketone-hydrazine condensation reaction; this is currently the most common industrial method.

[0004] For example, Chinese Patent 202211505467.2 discloses a homogeneous and efficient process and reaction apparatus for synthesizing ketazine series compounds. Ketones, entrainers, and hydrazine hydrate are added to the reaction apparatus to produce ketazine series compounds. While this invention, based on the hydrazine hydrate method, improves the technology and reaction apparatus to ensure a homogeneous reaction process and increases the yield of ketazine to approximately 98%, the introduction of entrainers increases the difficulty of product separation and purification, resulting in higher energy consumption for separation.

[0005] Chinese patent 20111092115.1 discloses a process for preparing hydrazine hydrate using air oxidation. This process utilizes air oxidation of imine to dehydrate and condense benzophenone and ammonia to produce diphenylmethyleneamine. Then, under the action of cuprous chloride catalyst, the imine undergoes oxidative coupling to produce benzophenone azide. Finally, the ketone azide is hydrolyzed to obtain hydrazine hydrate. Although air oxidation is used to prepare ketone azide, the overall conversion rate is low. Furthermore, the process involves significant heat loss and material consumption, and the strong acid catalyst used can corrode equipment, making it unsuitable for industrial production. Utility Model Content

[0006] The purpose of this invention is to overcome the shortcomings of the existing technology and provide an apparatus for producing benzophenone azo in the same reactor.

[0007] The objective of this invention is achieved through the following technical solution: An apparatus for producing benzophenone azide in the same reactor, comprising:

[0008] A reaction vessel, used to carry out amination and oxidation reactions within the same reaction vessel;

[0009] The feeding port is located at the top of the reactor and is used to add benzophenone raw material in the amination reaction and cuprous chloride in the oxidation reaction.

[0010] The self-priming stirrer is installed inside the reactor and is used for self-priming stirring to draw ammonia gas from the gas phase at the top of the reactor back into the liquid phase for reuse.

[0011] The ammonia inlet valve is located on the side of the reactor and is used to introduce ammonia into the reactor.

[0012] The ammonia discharge valve is located on the side of the reactor and is used to automatically drain water after the amination reaction is completed.

[0013] The ammonia cylinder is connected to the reaction vessel via pipelines, a gas flow control valve, and a gas inlet valve, and is used to introduce ammonia gas during the amination reaction.

[0014] The nitrogen cylinder is connected to the reaction vessel via pipelines, a gas flow control valve, and a gas inlet valve. It is used to introduce nitrogen gas after the amination reaction to convert the gas inside the reaction vessel.

[0015] An oxygen cylinder is connected to the reaction vessel via pipelines, a gas flow control valve, and a gas inlet valve, and is used to introduce oxygen into the oxidation reaction.

[0016] The discharge port is located at the bottom of the reactor and is used to discharge the benzophenone azo solid obtained after the oxidation reaction.

[0017] The control console is used to acquire data and generate control signals.

[0018] The reactor is connected to a high-low temperature circulation tank via a pipeline on the left side, and to an absorption tank via a pipeline on the right side. A gas outlet valve is provided at the top of the reactor and is connected to the absorption tank via a pipeline.

[0019] Furthermore, the bottom of the reactor is equipped with a weighing module, which is used to weigh the metered benzophenone raw material and ammonia water after they are added during the amination reaction, and to compare the dosage.

[0020] Furthermore, the reactor is equipped with a temperature detector, a pressure detector, and a liquid level detector.

[0021] Furthermore, the ammonia water inlet and outlet are equipped with filter screens, which are used to filter benzophenone azo.

[0022] Furthermore, the ammonia inlet valve, ammonia outlet valve, oil pump, level detector, and weighing module for materials inside the reactor are coordinated and controlled by a control console. The weighing module and level detector detect changes in materials inside the reactor, generate adjustment signals, and transmit them to the control console. The control console generates control signals based on the adjustment signals and transmits them to the ammonia inlet valve, ammonia outlet valve, and oil pump, thereby enabling automatic feeding and discharging of ammonia into the reactor to coordinate with different stages of the reaction.

[0023] Furthermore, the gas inlet valve, gas outlet valve, pressure detector, self-priming stirrer, and gas flow regulating valve are coordinated and controlled by a control console. The pressure detector detects pressure changes inside the reactor, generates a pressure signal, and transmits it to the control console. The control console generates a control signal based on the pressure signal and transmits it to the gas inlet valve, gas flow regulating valve, self-priming stirrer, and gas outlet valve.

[0024] Compared with the prior art, the advantages of this utility model are as follows:

[0025] 1. Low raw material cost, no organic solvents involved in the reaction, avoidance of separation and purification, allowing each component in each reaction step to be easily separated and reused, and can be completed in the same reaction vessel, further reducing production costs.

[0026] 2. By utilizing the special properties of benzophenone, the pressure and temperature distribution within the reaction apparatus can be controlled, making component separation more convenient. At the same time, compared with other air oxidation methods, since two reactions need to be completed in the same reactor, this invention does not require additional water removal, and the water content of the components has little impact on the overall reaction conversion rate.

[0027] 3. The device of this utility model adopts automated control as a whole and is equipped with an emergency safety alarm system to realize automated and safe production and improve production efficiency.

[0028] 4. It avoids the use of organic solvents in traditional methods. At the same time, the amination and oxidation reactions are carried out in the same reactor, eliminating the need for material transfer. All production steps are completed by automation, thereby improving raw material utilization, labor productivity and product quality. Attached Figure Description

[0029] To more clearly illustrate the technical solutions in the embodiments of this utility model, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this utility model. For those skilled in the art or ordinary skills, other drawings can be obtained based on these drawings without creative effort.

[0030] Figure 1 This is a schematic diagram of the equipment process of this utility model.

[0031] Figure labeling: Reactor 1, Feed port 1-1, Discharge port 1-2, Self-priming agitator 2, Absorption tank 3, Control console 4, Ammonia inlet valve 5, Ammonia outlet valve 6, Temperature detector 7, Pressure detector 8, Liquid level detector 9, High and low temperature circulation tank 10, Weighing module 11, Oxygen cylinder 12, Ammonia cylinder 13, Nitrogen cylinder 14. A1 and A2 are gas inlet valves, A3 is a gas outlet valve, B1, B2, B3, and B4 are gas flow control valves, Drive device 2-1, Transmission device 2-2, Oil seal 2-3, Blade 2-4, Flow regulator 2-5, Gas transmission chamber 2-6, Pneumatic pump 2-7. Detailed Implementation

[0032] The technical solutions of the present utility model will be clearly and completely described below with reference to the accompanying drawings of the embodiments. Obviously, the described embodiments are only some embodiments of the present utility model, and not all embodiments. Based on the embodiments of the present utility model, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the protection scope of the present utility model.

[0033] like Figure 1 As shown, an apparatus for producing benzophenone azide in the same reactor includes:

[0034] Reactor 1 is used to carry out amination and oxidation reactions in the same reactor.

[0035] Feed port 1-1 is located at the top of the reactor and is used to feed benzophenone raw material in the amination reaction and cuprous chloride in the oxidation reaction; the benzophenone raw material is amination to form benzophenone imine slurry under water as solvent conditions.

[0036] The self-priming stirrer 2 is installed inside the reactor and is used for self-priming stirring to draw ammonia gas from the gas phase at the top of the reactor back into the liquid phase for reuse.

[0037] Ammonia water inlet valve 5 is located on the side of the reactor and is used to introduce ammonia water into the reactor.

[0038] Ammonia water discharge valve 6 is located on the side of the reactor and is used to automatically drain water after the amination reaction is completed. A filter screen is provided at the ammonia water inlet and outlet. The filter screen is used to filter benzophenone azo, and after water removal, it is oxidized by high pressure air under high temperature conditions to obtain benzophenone azo solid.

[0039] Ammonia cylinder 13 is connected to the reaction vessel via pipelines, gas flow control valves B2 and B4, and gas inlet valve A1, and is used to introduce ammonia gas during the amination reaction.

[0040] Nitrogen cylinder 14 is connected to the reaction vessel via pipeline, gas flow control valve B1, and gas inlet valve A2. It is used to introduce nitrogen after the amination reaction to convert the gas in the reaction vessel.

[0041] Oxygen cylinder 12 is connected to the reaction vessel via pipelines, gas flow control valves B3 and B4, and gas inlet valve A1, and is used to introduce oxygen in the oxidation reaction. It should be noted that nitrogen and oxygen are introduced sequentially in the two reactions, therefore, gas flow control valve B4 and gas inlet valve A1 can be shared.

[0042] The discharge ports 1-2 are located at the bottom of the reactor and are used to discharge the benzophenone azo solid obtained after the oxidation reaction.

[0043] Console 4 is used to collect data and generate control signals. The console is electrically connected to the gas inlet and outlet valves, ammonia inlet and outlet valves, material weighing module inside the vessel, high and low temperature circulation tank, temperature detector, self-priming stirrer, and liquid level controller.

[0044] The reactor 1 is connected to a high-low temperature circulation tank 10 via a pipeline on its left side and is equipped with a temperature controller featuring a temperature transmitter. The reactor 1 has a pipeline on its right side connecting an oil pump, ammonia inlet valve 5, ammonia outlet valve 6, and absorption tank 3 in series. A gas outlet valve is located at the top of the reactor 1 and is connected to the absorption tank 3 via a pipeline. A weighing module 11 is installed at the bottom of the reactor 1 for weighing and comparing the added amount of benzophenone raw material and ammonia during the amination reaction. The reactor 1 is equipped with a temperature detector 7, a pressure detector 8, and a liquid level detector 9.

[0045] The ammonia water inlet valve 5, ammonia water outlet valve 6, oil pump, liquid level detector 9, and weighing module 11 of the material in the reactor are coordinated and controlled by the control console 4. The weighing module 11 and liquid level detector 9 detect changes in the material in the reactor, generate adjustment signals, and transmit them to the control console. The control console 4 generates control signals based on the adjustment signal information and transmits them to the ammonia water inlet valve 5, ammonia water outlet valve 6, and oil pump, thereby realizing the automatic feeding and discharging of ammonia water into the reactor to coordinate with different stages of the reaction.

[0046] The gas inlet valve, gas outlet valve, pressure detector 8, self-priming stirrer 2, and gas flow regulating valve are coordinated and controlled by the control console 4. The pressure detector 8 detects the pressure change in the reactor 1, generates a pressure signal, and transmits it to the control console 4. The control console 4 generates a control signal based on the pressure signal and transmits it to the gas inlet valve, gas flow regulating valve, self-priming stirrer, and gas outlet valve.

[0047] Work process:

[0048] The reaction begins with benzophenone as a raw material. Due to its stable properties, immiscibility with water, and melting point of 60℃, it is a low-viscosity liquid under high-temperature conditions. This allows it to participate in the reaction both as a reactant and as a solvent to mix the various substances involved. A self-priming stirrer is used in the reaction. This further increases the contact area between the gas and liquid slurry, improving reaction efficiency. Furthermore, the water generated at high temperatures rapidly vaporizes and is separated and removed with the gas flow, suppressing the potential hydrolysis of the intermediate product, benzophenone imine.

[0049] Based on repeated experiments exploring the reaction conditions at each step, the reaction pressure decreased from high to low and the reaction temperature decreased from high to low between groups from start to finish. This facilitates phase separation of components between steps and minimizes heat loss. Simultaneously, various recovered liquids and gases involved in the reaction can be reused in the reactor after simple treatment. The materials can be repeatedly circulated within the device, avoiding the drawback of low conversion rates in single-step reactions and effectively improving the conversion rate of benzophenone diazonium.

[0050] Amination reaction

[0051] 1. In the settings interface of Reactor #1, set the amount of raw materials to be added. Set the operating temperature and operating pressure. Set the amount of ammonia water to be discharged.

[0052] 2. Add the measured amounts of benzophenone and ammonia to the quick-opening feed port of reactor #1. The weighing module compares the dosage; if the comparison is successful, proceed to the next step.

[0053] 3. Close the quick-opening feeding port.

[0054] 4. Start the high and low temperature integrated unit heating mode to raise the reactor temperature to the operating temperature (125℃).

[0055] 5. Purge with ammonia gas to maintain the reactor pressure at the operating pressure (0.8 MPa).

[0056] 6. The operating pressure of the reactor is controlled by PV-101, and some gas is discharged when it exceeds the set value.

[0057] 7. Adjust the high and low temperature integrated unit via TICA-101

[0058] 8. Observe the bubbling of gas in the container, adjust the opening of the ammonia valve, and record the ammonia flow rate.

[0059] 9. Take samples periodically during the experiment to analyze relevant data.

[0060] 10. When the set time is reached, close the ammonia inlet valve.

[0061] 11. Discharge ammonia water into the ton container according to the set amount of ammonia water to be discharged (close WV-101 according to the weight value to be discharged).

[0062] 12. Open the gas phase bypass valve, appropriately reduce the operating pressure, and release some ammonia gas. Close the bypass valve when the set value is reached.

[0063] 13. Use nitrogen gas for conversion.

[0064] Oxidation reaction

[0065] 1. In the settings interface of reactor #1, reset the operating temperature and operating pressure. Set the reactor temperature alarm temperature.

[0066] 2. Open the quick-opening feed port, add cuprous chloride, and then close the quick-opening feed port.

[0067] 3. Start the high and low temperature integrated machine in heating mode, switch the integrated machine to heat transfer mode, and control the pot temperature (125℃).

[0068] 4. Introduce oxygen to maintain the reactor pressure at the operating pressure (0.8 MPa).

[0069] 5. The operating pressure of the reactor is controlled by PV-101, and some gas is discharged when it exceeds the set value.

[0070] 6. Adjust the high and low temperature integrated machine through TICA-101. When the reactor temperature reaches the set reactor temperature alarm temperature, an alarm will be triggered and the oxygen feed valve PV-102 will be shut off.

[0071] 7. Observe the bubbling of gas in the container, adjust the opening of the oxygen valve, and record the oxygen flow rate.

[0072] 8. Take samples periodically during the experiment to analyze relevant data.

[0073] 9. When the set time is reached, close the oxygen supply valve.

[0074] Example 1:

[0075] 5 kg of benzophenone and glacial acetic acid were added to the reactor through the solid feed port at a mass ratio of 200:1. An equal mass of 25% concentrated ammonia was added to the reactor, and the mixture was premixed and stirred for 10 minutes. NH3 was then introduced from the bottom of the reactor to maintain a pressure of 0.5 MPa. After maintaining this pressure for 10 minutes, N2 was introduced to adjust the pressure to 5.0 MPa. The high-low temperature circulating heating module was then turned on to raise the temperature to 125°C, and the reaction was initiated for 4 hours. The slurry after the amination reaction was analyzed by HPLC. At this point, the imine content of benzophenone in the slurry was 45.67%, and the single-step amination conversion rate was 45.67%.

[0076] Open the ammonia inlet and outlet controllers to drain excess ammonia. Then add 1% cuprous chloride catalyst, maintain the reactor temperature at 125℃, circulate high-pressure gas, adjust the oxygen concentration to 20%, maintain the reactor pressure at 4.0 MPa, and continue the reaction for 1 hour. Perform HPLC analysis on the slurry after the oxidation reaction. At this point, the benzophenone imine content in the slurry is 1.37%, the benzophenone azide content is 19.88%, and the single-step conversion rate is 89.75%.

[0077] After the slurry is cooled to 80℃, the cooled absorbent is pumped back into the reactor from the absorption tank (recovery tank) to continue the reaction. After five cycles of reaction, the oxidized slurry is taken for HPLC analysis. At this time, the benzophenone content in the slurry is 8.76%. After the slurry is cooled to room temperature, it is washed with methanol multiple times and the solid product mass is calculated. The total benzophenone nitrogen conversion rate is 91.67%.

[0078] Example 2:

[0079] 4 kg of benzophenone and glacial acetic acid were added to the reactor through the solid feed port at a mass ratio of 100:1. An equal mass of 25% concentrated ammonia was added to the reactor, and the mixture was premixed and stirred for 10 minutes. NH3 was then introduced from the bottom of the reactor to maintain a pressure of 0.7 MPa. After maintaining this pressure for 10 minutes, N2 was introduced to adjust the pressure to 7.0 MPa. The high-low temperature circulating heating module was then turned on to raise the temperature to 150°C, and the reaction was initiated for 2 hours. The slurry after the amination reaction was analyzed by HPLC. At this point, the benzophenone imine content in the slurry was 52.08%, and the single-step amination conversion rate was 52.08%.

[0080] Open the ammonia inlet and outlet controllers to drain excess ammonia. Then add 0.5% cuprous chloride catalyst, maintain the reactor temperature at 125℃, circulate high-pressure gas, adjust the oxygen concentration to 35%, maintain the reactor pressure at 5.0 MPa, and continue the reaction for 1 hour. Perform HPLC analysis on the slurry after the oxidation reaction. At this point, the benzophenone imine content in the slurry is 1.69%, the benzophenone azide content is 22.41%, and the single-step conversion rate is 88.95%.

[0081] After the slurry is cooled to 65°C, the cooled absorbent is pumped back into the reactor from the recovery tank to continue the reaction. After three cycles of reaction, the oxidized slurry is taken for HPLC analysis. At this time, the benzophenone content in the slurry is 4.09%. After the slurry is cooled to room temperature, it is washed with methanol multiple times and the solid product mass is calculated. The benzophenone nitrogen conversion rate of the whole process is 95.17%.

[0082] The above description is merely a specific embodiment of this utility model, but the protection scope of this utility model is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope disclosed in this utility model should be included within the protection scope of this utility model. Therefore, the protection scope of this utility model should be determined by the protection scope of the claims.

Claims

1. An apparatus for producing benzophenone azide in the same reactor, characterized in that: include A reaction vessel (1) is used to carry out amination and oxidation reactions in the same reaction vessel; The feeding port (1-1) is located at the top of the reactor and is used to feed benzophenone raw material in the amination reaction and cuprous chloride in the oxidation reaction. A self-priming stirrer (2) is installed inside the reactor to perform self-priming stirring and draw ammonia gas from the gas phase at the top of the reactor back into the liquid phase for reuse. Ammonia water inlet valve (5) is located on the side of the reactor and is used to feed ammonia water into the reactor. Ammonia water discharge valve (6) is installed on the side of the reactor and is used to automatically drain water after the amination reaction is completed. Ammonia cylinder (13) is connected to the reaction vessel through pipeline, gas flow control valve and gas inlet valve, and is used to introduce ammonia gas in the amination reaction; Nitrogen cylinder (14) is connected to the reactor via pipeline, gas flow control valve and gas inlet valve. It is used to introduce nitrogen after the amination reaction to convert the gas in the reactor. Oxygen cylinder (12) is connected to the reaction vessel through pipeline, gas flow control valve and gas inlet valve, and is used to introduce oxygen in the oxidation reaction; The discharge port (1-2) is located at the bottom of the reactor and is used to discharge the benzophenone azo solid obtained after the oxidation reaction. The console (4) is used to collect data and generate control signals; The reactor (1) is connected to the high and low temperature circulation tank (10) on the left side via a pipeline. The reactor (1) is connected to the oil pump, ammonia water inlet valve (5), ammonia water outlet valve (6) and absorption tank (3) in series via a pipeline on the right side. The reactor (1) is equipped with a gas outlet valve at the top, which is connected to the absorption tank (3) via a pipeline.

2. The apparatus for producing benzophenone azide in the same reactor according to claim 1, characterized in that: The bottom of the reactor (1) is equipped with a weighing module (11) for weighing the metered benzophenone raw material and ammonia water in the amination reaction and comparing the dosage.

3. The apparatus for producing benzophenone azide in the same reactor according to claim 2, characterized in that: The reactor (1) is equipped with a temperature detector (7), a pressure detector (8), and a liquid level detector (9).

4. The apparatus for producing benzophenone azide in the same reactor according to claim 3, characterized in that: A filter screen is installed at the ammonia inlet and outlet, and the filter screen is used to filter benzophenone azo.

5. The apparatus for producing benzophenone azide in the same reactor according to claim 4, characterized in that: The ammonia water inlet valve (5), ammonia water outlet valve (6), oil pump, liquid level detector (9), and weighing module (11) of the material in the reactor are coordinated and controlled by the control console (4). The weighing module (11) and liquid level detector (9) detect changes in the material in the reactor, generate adjustment signals, and transmit them to the control console. The control console (4) generates control signals based on the adjustment signal information and transmits them to the ammonia water inlet valve (5), ammonia water outlet valve (6), and oil pump, so as to realize the automatic feeding and discharging of ammonia water into the reactor to cooperate with the different stages of the reaction.

6. The apparatus for producing benzophenone azide in the same reactor according to claim 5, characterized in that: The gas inlet valve, gas outlet valve, pressure detector (8), self-priming stirrer (2), and gas flow regulating valve are coordinated and controlled by the control console (4). The pressure detector (8) detects the pressure change in the reactor (1), generates a pressure signal, and transmits it to the control console (4). The control console (4) generates a control signal based on the pressure signal and transmits it to the gas inlet valve, gas flow regulating valve, self-priming stirrer, and gas outlet valve.

Images