An amide intermediate processing device for hydrazine hydrate production

Abstract

The utility model belongs to a kind of for amide intermediate processing device of hydrazine hydrate production;Including concentration tank, water phase reaction liquid inlet pipeline and catalyst import are equipped on concentration tank, catalyst import is connected with quartz sand catalyst preparation unit, the outlet of concentration tank is connected with the concentrate material import of intermediate recovery kettle, intermediate recovery kettle is also connected with ammonia feed line, the ammoniation liquid outlet of intermediate recovery kettle is connected with separation recovery unit, and the liquid phase outlet of separation recovery unit is connected with hydrazine compound synthesis section;The top of concentration tank is equipped with steam exhaust pipeline;With the characteristics of being able to realize the water in water phase reaction liquid and ammonium formate is converted into formamide and reused simultaneously, avoid that ammoniation liquid contains metal ion, further, on the basis of energy saving and consumption reduction, reduce processing cost and realize continuous processing.

Description

Technical Field

[0001] This utility model belongs to the field of hydrazine hydrate production technology, and in particular relates to an amide intermediate processing device for hydrazine hydrate production. Background Technology

[0002] Hydrazine hydrate is an important fine chemical product with wide applications in the chemical industry. It is mainly used in foaming agents and pharmaceutical intermediates, and also as a deoxidizing and decarbonization cleaning agent for boilers and reactors. Furthermore, it can be used in the production of rocket fuel, diazo fuel, rubber additives, reducing agents, and certain organic pigments. Currently, the commonly used method for industrial production of hydrazine hydrate is the hydrogen peroxide process. This method uses hydrogen peroxide, ammonia, and alkyl ketones as raw materials, reacting them under catalytic conditions to generate a ketazine intermediate, which is further hydrolyzed to obtain hydrazine hydrate. Chinese Patent Publication No. CN114380708A discloses a method for recovering catalysts used in the synthesis of hydrated hydrazine intermediates. The method involves distilling the reaction liquid to remove excess water, then using metal oxides such as CuO as dehydrators to catalyze the dehydration of ammonium acid at 160°C to obtain the corresponding amide. However, in this process, some metal catalysts dissolve in the alkaline reaction liquid, resulting in residual metal ions. This hinders the further recycling of the amide, requiring further removal, which consumes energy. Furthermore, this method suffers from drawbacks such as the large amount of metal oxides used and difficulty in separation. Moreover, because metal ions need to be separated, subsequent processing requires an intermittent production mode, leading to low production efficiency. Utility Model Content

[0003] To overcome the above deficiencies, this utility model provides an amide intermediate processing device for the production of hydrazine hydrate, thereby solving the technical problems existing in the prior art.

[0004] To achieve the above objectives, the present invention provides the following technical solution:

[0005] An apparatus for producing amide intermediates for the production of hydrazine hydrate includes a concentration tank with an aqueous reaction liquid inlet and a catalyst inlet connected to a quartz sand catalyst preparation unit. The outlet of the concentration tank is connected to the concentrated material inlet of an intermediate recovery vessel, which is also connected to an ammonia feed line. The ammoniated liquid outlet of the intermediate recovery vessel is connected to a separation and recovery unit, and the liquid phase outlet of the separation and recovery unit is connected to a hydrazine compound synthesis section. A steam exhaust line is located at the top of the concentration tank.

[0006] The beneficial effects of this invention are as follows: This invention is designed for the synthesis of aqueous reaction liquid from hydrazine hydrate intermediates. As is well known, aqueous and oil-phase reaction liquids are generated in the hydrazine hydrate synthesis process. The oil-phase reaction liquid contains a large amount of hydrazine hydrate intermediates, while the aqueous reaction liquid contains a small amount of hydrazine hydrate intermediates, ammonium formate, and water. Therefore, the essence of the treatment device is how to remove water from the aqueous reaction liquid and convert ammonium formate into formamide for reuse. This invention uses quartz sand in the quartz sand catalyst preparation unit as a catalyst to dehydrate the aqueous reaction liquid. At the same time, the quartz sand catalyst can inhibit the decomposition of ammonium formate and, in conjunction with ammonia in the ammonia feed line, convert the ammonium formate compound into an amide compound, achieving the recovery and reuse of formamide. In the above process, water in the aqueous reaction liquid can be removed and ammonium formate can be converted into formamide for reuse, while avoiding the presence of metal ions in the ammoniation liquid. This reduces processing costs while saving energy and reducing consumption, and achieves continuous processing.

[0007] Preferably, the quartz sand catalyst preparation unit includes a quartz sand feed pipe, which is connected to the inlet of the regeneration reactor via a high-pressure roller mill. The outlet of the regeneration reactor is connected to the catalyst inlet via a diaphragm pump and a catalyst metering delivery unit. The regeneration reactor is also equipped with an acid delivery pipe.

[0008] Preferably, the catalyst metering delivery unit includes a cylinder, with an acid hydrolysis material inlet at the top of the cylinder, which is connected to the outlet of the diaphragm pump. An acid overflow port is provided at the top of the cylinder, and a first filter cylinder made of a filter screen is provided inside the cylinder corresponding to the acid overflow port. A catalyst solid phase outlet is provided at the bottom of the cylinder, and a catalyst metering screw conveyor is installed on the catalyst solid phase outlet. The outlet of the metering screw conveyor is connected to the catalyst inlet.

[0009] Preferably, a static mixer is provided between the outlet of the concentration tank and the inlet of the concentrated material in the intermediate recovery vessel.

[0010] Preferably, the intermediate recovery vessel includes a tube side and a shell side. The tube side consists of several heat exchange tubes with tube sheets installed inside the intermediate recovery vessel. The bottom of the heat exchange tubes is connected to the lower part of the intermediate recovery vessel, and the top of the heat exchange tubes is connected to the upper part of the intermediate recovery vessel. The shell side is between the outer wall of the heat exchange tubes in the middle of the intermediate recovery vessel and the inner wall of the intermediate recovery vessel. The intermediate recovery vessel corresponding to the lower part of the shell side is provided with a heat exchange medium inlet pipe, and the intermediate recovery vessel corresponding to the upper part of the shell side is provided with a heat exchange medium outlet pipe. The bottom of the intermediate recovery vessel is provided with a concentrated material inlet, and the intermediate recovery vessel inside the intermediate recovery vessel above the concentrated material inlet is provided with a bubbler, the inlet of which is connected to the ammonia feed pipeline.

[0011] Preferably, the intermediate recovery vessel is provided with a gas phase outlet at the top and an ammonia liquid outlet on one side of the upper part of the intermediate recovery vessel.

[0012] Preferably, the separation and recovery unit includes a liquid-solid separator connected to the outlet of the ammonia liquid in the intermediate recovery vessel, the liquid phase outlet of the liquid-solid separator is connected to a gas-liquid separator, and the bottom liquid phase outlet of the gas-liquid separator is connected to the hydrazine compound synthesis section.

[0013] Preferably, the solid catalyst outlet of the liquid-solid separator is connected to the circulation inlet of the regeneration reactor via a catalyst storage tank, and the top gas phase outlet of the gas-liquid separator is connected to a vent pipe.

[0014] Preferably, the liquid-solid separator has an inlet on one side of the middle section, a solid catalyst outlet at the bottom, and a liquid outlet at the top; a second filter cylinder made of filter screen is provided in the liquid-solid separator below the liquid outlet.

[0015] An amide intermediate processing device for hydrazine hydrate production, manufactured according to the above scheme, uses quartz sand in a quartz sand catalyst preparation unit as a catalyst to mix and concentrate the aqueous reaction liquid in a concentration tank. This allows for concentration while ensuring thorough mixing. During this process, the catalyst inhibits the decomposition of ammonium formate and reduces the dehydration load on the subsequent intermediate recovery vessel. Furthermore, by setting up an intermediate recovery vessel, ammonium formate can be converted into formamide during the dehydration reaction, laying the foundation for reuse in the subsequent hydrazine compound synthesis section. This invention uses a quartz sand catalyst to achieve the dehydration reaction while preventing metal ions from entering the ammonia solution, thereby reducing processing costs while saving energy and achieving continuous processing. Simultaneously, this invention also enables the recycling and reuse of the quartz sand catalyst, further reducing processing costs. Attached Figure Description

[0016] Figure 1 This is a schematic diagram of the structure of this utility model.

[0017] Legend:

[0018] 1. Concentrator; 2. Aqueous phase reaction liquid inlet pipe; 3. Intermediate recovery vessel; 4. Ammonia feed pipe; 5. Hydrazine compound synthesis section; 6. Quartz sand feed pipe; 7. High-pressure roller mill; 8. Regeneration vessel; 9. Diaphragm pump; 10. Acid conveying pipe; 11. Cylinder; 12. Acid hydrolysis material inlet; 13. Acid overflow port; 14. First filter cylinder; 15. Quantitative conveying screw conveyor; 16. Static mixer; 17. Heat exchanger tube; 18. Heat exchange medium inlet pipe; 19. Heat exchange medium outlet pipe; 20. Bubble blower; 21. Liquid-solid separator; 22. Second filter cylinder; 23. Catalyst temporary storage tank; 24. Vent pipe; 25. Gas-liquid separator; 26. Steam exhaust pipe. Detailed Implementation

[0019] 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.

[0020] Reference Figure 1 This utility model is an amide intermediate processing device for the production of hydrazine hydrate, including a concentration tank 1. The concentration tank 1 is equipped with an aqueous reaction liquid inlet pipe 2 and a catalyst inlet. The catalyst inlet is connected to a quartz sand catalyst preparation unit. The outlet of the concentration tank 1 is connected to the concentrated material inlet of the intermediate recovery vessel 3. The intermediate recovery vessel 3 is also connected to an ammonia feed pipeline 4. The ammonia liquid outlet of the intermediate recovery vessel 3 is connected to a separation and recovery unit. The liquid phase outlet of the separation and recovery unit is connected to a hydrazine compound synthesis section 5. A steam exhaust pipeline 26 is provided on the top of the concentration tank 1. This invention innovatively uses quartz sand in a quartz sand catalyst preparation unit as a catalyst for the dehydration reaction of the aqueous phase reaction liquid in the synthesis of hydrazine hydrate intermediate. Simultaneously, it inhibits the decomposition of ammonium formate in the aqueous phase reaction liquid, laying the foundation for the conversion of ammonium formate into formamide. Compared with the traditional dehydration method using metal oxides, this technical solution avoids the defect of metal ion impurities in the subsequent liquid phase, thereby reducing subsequent processing costs and achieving continuous processing of the aqueous phase reaction liquid. Furthermore, this invention employs a two-stage dehydration method for the aqueous phase reaction liquid, consisting of concentration and dehydration in a concentration tank 1 and dehydration reaction in an intermediate recovery vessel 3. This two-stage dehydration method, in conjunction with the quartz sand catalyst, not only inhibits the decomposition of ammonium formate in the aqueous phase reaction liquid but also reduces the dehydration load in the intermediate recovery vessel 3.

[0021] Furthermore, the quartz sand catalyst preparation unit includes a quartz sand feed pipe 6, which is connected to the inlet of a regeneration reactor 8 via a high-pressure roller mill 7. The outlet of the regeneration reactor 8 is connected to the catalyst inlet via a diaphragm pump 9 and a catalyst metering delivery unit. An acid delivery pipe 10 is also provided on the regeneration reactor 8. As is well known, the essence of catalysis is that the catalyst provides "active sites" to interact with the reactants temporarily and weakly (such as through chemisorption), thereby changing the reaction pathway and reducing the energy required for the reaction (activation energy). The main component of quartz sand is silicon dioxide (SiO2). Silicon dioxide (SiO2) itself is not a good catalyst because it only has a tetrahedral structure that can form a huge three-dimensional network (mesh), meaning it lacks the necessary "active sites" to effectively adsorb reactants and reduce the activation energy of the reaction. Based on the above technical problems, this invention uses a high-pressure roller mill 7 to grind the quartz sand, increasing the specific surface area and reprocessing to increase the active sites, thus achieving the characteristic of dehydration reaction of the aqueous phase reaction liquid.

[0022] Furthermore, the catalyst metering delivery unit includes a cylinder 11. The upper part of the cylinder 11 has an acid hydrolysis material inlet 12, which is connected to the outlet of the diaphragm pump 9. The top of the cylinder 11 has an acid overflow port 13. A first filter cylinder 14 made of a filter screen is located inside the cylinder 11 corresponding to the acid overflow port 13. The lower part of the cylinder 11 has a catalyst solid phase outlet, on which a metering delivery screw conveyor 15 is installed. The outlet of the metering delivery screw conveyor 15 is connected to the catalyst inlet. This invention, by using the catalyst metering delivery unit, not only achieves solid-liquid separation but also uses the metering delivery screw conveyor 15 to quantitatively add the catalyst to the concentration tank 1, laying the foundation for subsequent full reaction. This invention filters the catalyst particles using the first filter cylinder 14 made of a filter screen, causing the filtered catalyst particles to deposit on the top of the cylinder 11. When the cylinder 11 reaches a certain solid content, the catalyst is delivered to the concentration tank 1 via the metering delivery screw conveyor 15. In the previous text, the density of the quartz sand catalyst was made uniform by crushing and grinding the quartz sand. Based on this, the purpose of quantitatively delivering the catalyst was achieved by adjusting the power and operating time of the screw conveyor 15.

[0023] Furthermore, a static mixer 16 is provided between the outlet of the concentration tank 1 and the inlet of the concentrated material in the intermediate recovery vessel 3. By setting up the static mixer 16, uniform mixing between materials can be achieved (i.e., thorough mixing between the catalyst and the aqueous reaction liquid).

[0024] Furthermore, the intermediate recovery vessel 3 includes a tube side and a shell side. The tube side consists of several heat exchange tubes 17 with tube sheets installed inside the intermediate recovery vessel 3. The bottom of the heat exchange tubes 17 is connected to the lower part of the intermediate recovery vessel 3, and the top of the heat exchange tubes 17 is connected to the upper part of the intermediate recovery vessel 3. The shell side is between the outer wall of the heat exchange tubes 17 in the middle of the intermediate recovery vessel 3 and the inner wall of the intermediate recovery vessel 3. The intermediate recovery vessel 3 corresponding to the lower part of the shell side is provided with a heat exchange medium inlet pipe 18, and the intermediate recovery vessel 3 corresponding to the upper part of the shell side is provided with a heat exchange medium outlet pipe 19. The bottom of the intermediate recovery vessel 3 is provided with a concentrated material inlet, and the intermediate recovery vessel 3 inside the intermediate recovery vessel 3 above the concentrated material inlet is provided with a bubbler 20. The inlet of the bubbler 20 is connected to the ammonia feed line 4. The material, after being fully mixed by the static mixer 16, enters the lower part of the intermediate recovery vessel 3. At the same time, liquid ammonia or gaseous ammonia in the ammonia feed line 4 enters the lower part of the intermediate recovery vessel 3 through the bubbler 20. After being mixed in the lower part of the intermediate recovery vessel 3, the material enters the tube side of the intermediate recovery vessel 3 for dehydration reaction, and at the same time, ammonium formate is converted into formamide.

[0025] Furthermore, the intermediate recovery vessel 3 is provided with a gas phase outlet at the top and an ammoniated liquid outlet on one side of the upper part of the intermediate recovery vessel 3. In this invention, the gas phase generated by the dehydration reaction in the intermediate recovery vessel 3 is discharged through the gas phase outlet at the top of the intermediate recovery vessel 3, and the ammoniated liquid after the dehydration reaction is discharged through the ammoniated liquid outlet in the form of overflow.

[0026] Furthermore, the separation and recovery unit includes a liquid-solid separator 21 connected to the outlet of the ammonia liquid in the intermediate recovery vessel 3. The liquid phase outlet of the liquid-solid separator 21 is connected to a gas-liquid separator 25, and the bottom liquid phase outlet of the gas-liquid separator 25 is connected to the hydrazine compound synthesis section 5. The ammonia liquid overflowing from the ammonia liquid outlet contains a catalyst. Based on this, the present invention achieves the separation of catalyst particles through the liquid-solid separator 21, and further separates the liquid phase after liquid-solid separation through the gas-liquid separator 25, so that the liquid phase after passing through the separation and recovery unit can directly enter the hydrazine compound synthesis section 5 for the production of hydrated hydrazine, thereby achieving the characteristics of continuous processing of aqueous reaction liquid and improving the processing efficiency of aqueous reaction liquid.

[0027] Furthermore, the solid catalyst outlet of the liquid-solid separator 21 is connected to the circulation inlet of the regeneration reactor 8 via the catalyst storage tank 23, and the top gas phase outlet of the gas-liquid separator 25 is connected to the vent pipe 24. This invention, through the above technical solution, enables the recycling of the quartz sand catalyst, thereby reducing the cost of treating the aqueous reaction liquid.

[0028] Furthermore, the liquid-solid separator 21 has an inlet on one side of its middle section, a solid catalyst outlet at its bottom, and a liquid outlet at its top. A second filter cylinder 22 made of a filter screen is located inside the liquid-solid separator 21 below the liquid outlet. The purpose of the liquid-solid separator 21 in this invention is to separate the solid catalyst using the second filter cylinder 22 made of a filter screen. The liquid phase overflows from the liquid outlet at the top of the liquid-solid separator 21 into the gas-liquid separator 25 for gas-liquid separation. When the solid content in the liquid-solid separator 21 reaches a certain threshold, it can enter the catalyst storage tank 23 by its own gravity and finally flow back to the regeneration reactor 8 for reuse. It should be noted that the first filter cylinder 14 and the second filter cylinder 22 have the same structure, i.e., a top-opening cylinder structure formed by the filter screen. In this cylinder structure, the liquid phase can overflow from the bottom and sides to the top, preventing the solid phase from passing through the filter screen.

[0029] This invention also provides a method for processing amide intermediates in the production of hydrazine hydrate, the method comprising the following steps:

[0030] Step 1: Natural quartz sand enters the high-pressure roller mill 7 through the quartz sand feed pipe 6 for grinding. The ground particles enter the regeneration kettle 8. The particles ground by the high-pressure roller mill 7 are 200-300 mesh.

[0031] Step 2: While the ground particles enter the regeneration reactor 8, the acid solution enters the regeneration reactor 8 through the acid solution delivery pipe 10; the aforementioned particles and acid solution are fully mixed and acid-hydrolyzed in the regeneration reactor 8, so that the tetrahedral structure is filled with active molecules; the acid solution is one or more of phosphoric acid, hydrochloric acid, sulfuric acid or sulfonic acid.

[0032] Step 3: The material in the regeneration kettle 8 enters the cylinder 11 through the outlet of the regeneration kettle 8, the diaphragm pump 9 and the acid hydrolysis material inlet 12. The liquid phase passes through the first filter cylinder 14 made of filter screen and is discharged through the acid overflow port 13. The catalyst particles with active substances attached are filtered through the first filter cylinder 14. After filtration, the 200-300 mesh catalyst particles are deposited at the bottom of the cylinder 11.

[0033] Start the quantitative conveying screw auger 15. Determine the feed rate and conveying speed of the quantitative conveying screw auger 15 according to production needs. The catalyst particles at the bottom of the cylinder 11 are conveyed to the concentration tank 1 through the quantitative conveying screw auger 15. The aqueous phase reaction liquid for the synthesis of hydrazine hydrate intermediates enters the concentration tank 1 through the aqueous phase reaction liquid inlet pipe 2. The two are fully mixed and concentrated in the concentration tank 1. The aqueous phase reaction liquid for the synthesis of hydrazine hydrate intermediates includes hydrazine hydrate intermediates, ammonium formate, and water. The water content of the aqueous phase reaction liquid for the synthesis of hydrazine hydrate intermediates is 40-70%. The hydrazine hydrate intermediates contain acetone azide, butanone azide, cyclopropylmethyl ketone azide, cyclopentylmethyl ketone azide, and cyclohexanone azide. The catalyst entering the concentration tank 1 is 5-30% of the mass of ammonium formate. The temperature in the concentration tank 1 is 50-180°C. The concentration tank 1 is heated by steam, heat transfer oil, or electricity.

[0034] Step 4: The materials thoroughly mixed in the concentration tank 1 are further mixed in the static mixer 16 and then enter the tube side of the intermediate recovery vessel 3. Gaseous ammonia or liquid ammonia enters the tube side of the intermediate recovery vessel 3 through the ammonia feed line 4 and the bubbler 20, so that the reaction liquid undergoes a dehydration reaction under normal pressure, and the ammonium acid compound is converted into an amide compound, realizing the recovery of the intermediate; at the same time, the decomposition of the ammonium acid compound is inhibited by the catalyst.

[0035] In the above process, the heat source in the heat exchange medium inlet pipe 18 enters the shell side of the intermediate recovery vessel 3 and exchanges heat with the material in the heat exchange tube 17. After heat exchange, it is discharged through the heat exchange medium outlet pipe 19. The heat source is steam or heat transfer oil. The temperature of the dehydration reaction is 130-220℃ and the reaction time is 10-150min.

[0036] Step 6: The ammonified liquid after the reaction in Step 5 overflows into the liquid-solid separator 21 through the ammonified liquid outlet of the intermediate recovery vessel 3 for solid-liquid separation; the gas phase after the intermediate recovery vessel 3 is discharged through the gas phase outlet at the top of the intermediate recovery vessel 3; the pH of the ammonified liquid is 8-14.

[0037] Step 7: After the liquid phase enters the liquid-solid separator 21 in step 5, the liquid phase passes through the second filter cylinder 22 made of filter screen and is discharged through the liquid phase outlet at the top of the liquid-solid separator 21. The catalyst particles are filtered through the second filter cylinder 22, and the filtered catalyst particles are deposited inside the liquid-solid separator 21.

[0038] Step 8: The liquid phase enters the gas-liquid separator 25 through the liquid phase outlet at the top of the liquid-solid separator 21. After entering the gas-liquid separator 25, the liquid phase undergoes gas-liquid separation. The gas phase separated by gas-liquid separation enters the vent pipe 24 through the gas phase outlet at the top of the gas-liquid separator 25 for external discharge. The liquid phase separated by gas-liquid separation enters the hydrazine compound synthesis section 5.

[0039] Step 9: The catalyst particles deposited at the bottom of the liquid-solid separator 21 in step 7 enter the catalyst storage tank 23, and finally the catalyst particles in the catalyst storage tank 23 enter the regeneration tank 8 through the circulation inlet of the regeneration tank 8, so as to realize the recycling of the catalyst.

[0040] This invention addresses the shortcomings of existing technologies that use metal oxides as dehydration catalysts, resulting in the presence of metal ions in the liquid phase. It innovatively selects quartz sand as the catalyst, thus avoiding the introduction of metal ions while simultaneously dehydrating the aqueous reaction solution for the synthesis of hydrazine hydrate intermediates. This reduces the difficulty of subsequent processing and enables continuous processing of the aqueous reaction solution. Furthermore, to improve catalyst activity and ensure the smooth progress of the dehydration reaction, this invention involves grinding, acidolysis, and quantitative delivery of the quartz sand. Even further, this invention includes a liquid-solid separator 21 and a catalyst storage tank 23 to achieve catalyst recovery and reuse. In the above processes, this invention utilizes... The high-pressure roller mill 7 can crush and grind quartz sand into granules, which not only increases the specific surface area and active sites, but also ensures the particle size and strength, laying the foundation for subsequent quantitative feeding and catalyst recovery. Furthermore, in order to achieve continuous processing of the aqueous reaction liquid, this invention also includes a catalyst quantitative feeding unit and a liquid-solid separator 21. Specifically, by setting up the catalyst quantitative feeding unit, continuous, stable and quantitative feeding of the catalyst can be achieved, thereby ensuring the continuous feeding of the aqueous reaction liquid. In addition, by setting up the liquid-solid separator 21, the ammonia liquid can be continuously and stably fed to the subsequent process. Thus, the entire system achieves the advantage of continuous and stable processing of the aqueous reaction liquid. Using quartz sand as a catalyst has the advantages of low cost and high yield, thereby improving the company's profit margin. The production process can reduce the loss of amide during the synthesis of hydrazine hydrate intermediates and reduce wastewater discharge. Catalytic dehydration can achieve extremely high recovery efficiency of amide catalyst and can be directly recycled without introducing metal ions. At the same time, it reduces the amount of catalyst used, and the recovery rate of amide catalyst reaches more than 99%. Furthermore, continuous process can reduce the difficulty and cost of production operation and increase product consistency.

[0041] Experimental Example: In the embodiments of this utility model, the aqueous reaction solution for the synthesis of hydrazine hydrate intermediate was the reaction solution after the synthesis of ketazine using amide as a catalyst. After the reaction, the aqueous reaction solution was obtained after removing the organic phase. Generally, the aqueous reaction solution contains 25-50% ammonium formate and 1-5% formamide. In the embodiments, the formate in the aqueous reaction solution was titrated by titration. The recovery rate of formamide was determined by determining the change in the content of formate before and after the recovery reaction.

[0042] The processing method used includes the following steps:

[0043] Step 1: Natural quartz sand enters the high-pressure roller mill 7 through the quartz sand feed pipe 6 for grinding. The ground particles enter the regeneration kettle 8. The particles ground by the high-pressure roller mill 7 are 200-300 mesh.

[0044] Step 2: While the ground particles enter the regeneration reactor 8, the acid solution enters the regeneration reactor 8 through the acid solution delivery pipe 10; the aforementioned particles and acid solution are fully mixed and acid-hydrolyzed in the regeneration reactor 8, so that the tetrahedral structure is filled with active molecules; the acid solution is a mixture of sulfuric acid and sulfonic acid;

[0045] Step 3: The material in the regeneration kettle 8 enters the cylinder 11 through the outlet of the regeneration kettle 8, the diaphragm pump 9 and the acid hydrolysis material inlet 12. The liquid phase passes through the first filter cylinder 14 made of filter screen and is discharged through the acid overflow port 13. The catalyst particles with active substances attached are filtered through the first filter cylinder 14. After filtration, the 200-300 mesh catalyst particles are deposited at the bottom of the cylinder 11.

[0046] The quantitative conveying screw auger 15 is started, and the feed rate and conveying speed of the quantitative conveying screw auger 15 are determined according to production needs. The catalyst particles at the bottom of the cylinder 11 are conveyed to the concentration tank 1 through the quantitative conveying screw auger 15. The aqueous phase reaction liquid for the synthesis of hydrazine hydrate intermediates enters the concentration tank 1 through the aqueous phase reaction liquid inlet pipe 2. The two are fully mixed and concentrated in the concentration tank 1. The aqueous phase reaction liquid for the synthesis of hydrazine hydrate intermediates includes hydrazine hydrate intermediates, ammonium formate, and water. The water content of the aqueous phase reaction liquid for the synthesis of hydrazine hydrate intermediates is 40-70%. The hydrazine hydrate intermediates contain acetone azide, butanone azide, cyclopropylmethyl ketone azide, cyclopentylmethyl ketone azide, and cyclohexanone azide. The catalyst entering the concentration tank 1 is 10% of the mass of ammonium formate. The temperature in the concentration tank 1 is 100°C, and the concentration tank 1 is heated by steam.

[0047] Step 4: The materials thoroughly mixed in the concentration tank 1 are further mixed in the static mixer 16 and then enter the tube side of the intermediate recovery vessel 3. Gaseous ammonia or liquid ammonia enters the tube side of the intermediate recovery vessel 3 through the ammonia feed line 4 and the bubbler 20, so that the reaction liquid undergoes a dehydration reaction under normal pressure, and the ammonium acid compound is converted into an amide compound, realizing the recovery of the intermediate; at the same time, the decomposition of the ammonium acid compound is inhibited by the catalyst.

[0048] In the above process, the heat source in the heat exchange medium inlet pipe 18 enters the shell side of the intermediate recovery vessel 3 and exchanges heat with the material in the heat exchange tube 17. After heat exchange, it is discharged through the heat exchange medium outlet pipe 19. The heat source is heat transfer oil. The temperature of the dehydration reaction is 160°C and the reaction time is 50 min.

[0049] Step 6: The ammonified liquid after the reaction in Step 5 overflows into the liquid-solid separator 21 through the ammonified liquid outlet of the intermediate recovery vessel 3 for solid-liquid separation; the gas phase after the intermediate recovery vessel 3 is discharged through the gas phase outlet at the top of the intermediate recovery vessel 3; the pH of the ammonified liquid is 8-14.

[0050] Step 7: After the liquid phase enters the liquid-solid separator 21 in step 5, the liquid phase passes through the second filter cylinder 22 made of filter screen and is discharged through the liquid phase outlet at the top of the liquid-solid separator 21. The catalyst particles are filtered through the second filter cylinder 22, and the filtered catalyst particles are deposited inside the liquid-solid separator 21.

[0051] Step 8: The liquid phase enters the gas-liquid separator 25 through the liquid phase outlet at the top of the liquid-solid separator 21. After entering the gas-liquid separator 25, the liquid phase undergoes gas-liquid separation. The gas phase separated by gas-liquid separation enters the vent pipe 24 through the gas phase outlet at the top of the gas-liquid separator 25 for external discharge. The liquid phase separated by gas-liquid separation enters the hydrazine compound synthesis section 5.

[0052] Step 9: The catalyst particles deposited at the bottom of the liquid-solid separator 21 in step 7 enter the catalyst storage tank 23, and finally the catalyst particles in the catalyst storage tank 23 enter the regeneration tank 8 through the circulation inlet of the regeneration tank 8, so as to realize the recycling of the catalyst.

[0053] Experimental Example 1

[0054] Take 2.5 kg of the above reaction solution (the content of ammonium formate is determined to be 27.6% and the content of formamide is 1.63%) and 70 g of quartz sand particle catalyst (10% of the mass of ammonium formate) and add them to the concentration tank 1. The specific treatment process adopts the above treatment method. In step 8, the liquid phase enters the gas-liquid separator 25 through the liquid phase outlet at the top of the liquid-solid separator 21. The liquid phase entering the gas-liquid separator 25 is collected (the liquid phase is colorless and transparent). The weight of the liquid phase is 561.32 g. After titration, it is found that the liquid phase contains 3.45 g of ammonium formate, and the recovery rate is about 99.5%.

[0055] Experimental Example 2

[0056] Take 2.5 kg of the above reaction solution (the content of ammonium formate is determined to be 27.6% and the content of formamide is 1.63%) and 100 g of copper oxide catalyst (10% of the mass of ammonium formate) and add them to the concentration tank 1. The specific treatment process adopts the technical solution of the above treatment method (the difference from the above treatment method is that the quartz sand catalyst preparation unit is in a shutdown state). In step 8, the liquid phase enters the gas-liquid separator 25 through the liquid phase outlet at the top of the liquid-solid separator 21. The liquid phase entering the gas-liquid separator 25 is collected (the liquid phase is blue, which is analyzed to be caused by the dissolution of some copper oxide under alkaline conditions). The weight of the liquid phase is 536.48 g. After titration, it is found that the liquid phase contains 31.74 g of ammonium formate, and the recovery rate is about 95.4%.

[0057] A comparison between Experiment 2 and Experiment 1 shows that a large amount of copper oxide catalyst is used, and the recovered amide catalyst solution is blue and contains copper ions, which will affect subsequent cycles, promote the decomposition of hydrogen peroxide, and have a significant impact on the stability and safety of the synthesis system.

[0058] Experimental Example 3

[0059] Take 2.5 kg of the above reaction solution (the content of ammonium formate is determined to be 27.6% and the content of formamide is 1.63%) and 100 g of alumina catalyst (10% of the mass of ammonium formate) and add them to the concentration tank 1. The specific treatment process adopts the technical solution of the above treatment method (the difference from the above treatment method is that the quartz sand catalyst preparation unit is in a shutdown state). In step 8, the liquid phase enters the gas-liquid separator 25 through the liquid phase outlet at the top of the liquid-solid separator 21. The liquid phase entering the gas-liquid separator 25 is collected (the liquid phase is brownish-yellow, which is caused by the reaction of part of the alumina under alkaline conditions to form metal salt, resulting in a side reaction). The weight of the liquid phase is 568.54 g. After titration, it is found that the liquid phase contains 53.13 g of ammonium formate, and the recovery rate is about 92.3%.

[0060] A comparison between Experiment 3 and Experiment 1 shows that the alkaline environment of the ionic components in the reaction solution leads to the consumption of metal oxides. The recovered amide catalyst solution is brownish-yellow and contains metal ions, which will affect subsequent cycles and promote the decomposition of hydrogen peroxide, thus having a significant impact on the stability and safety of the synthesis system.

[0061] Test Example 4

[0062] Take 2.5 kg of the above reaction solution (the content of ammonium formate is determined to be 27.6% and the content of formamide is 1.63%) and add it to the concentration tank 1; the specific treatment process adopts the technical solution of the above treatment method (the difference from the above treatment method is that the quartz sand catalyst preparation unit is in a shutdown state). In step 8, the liquid phase enters the gas-liquid separator 25 through the liquid phase outlet at the top of the liquid-solid separator 21. The liquid phase entering the gas-liquid separator 25 is collected (the liquid phase is colorless and transparent). The weight of the liquid phase is 585.13 g. After titration, it is found that the liquid phase contains 82.8 g of ammonium formate, and the recovery rate is about 88.0%.

[0063] A comparison between Experiment 4 and Experiment 1 shows that the treated quartz sand catalyst can effectively promote intramolecular dehydration of ammonium formate, and does not contain metal ions, does not introduce safety risk factors, and significantly improves product yield.

[0064] Finally, it should be noted that the above description is only a preferred embodiment of the present utility model and is not intended to limit the present utility model. Although the present utility model has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present utility model should be included within the protection scope of the present utility model.

Claims

1. An apparatus for processing amide intermediates in the production of hydrazine hydrate, characterized in that: The device includes a concentration tank (1), which is equipped with an aqueous reaction liquid inlet pipe (2) and a catalyst inlet. The catalyst inlet is connected to the quartz sand catalyst preparation unit. The outlet of the concentration tank (1) is connected to the concentrated material inlet of the intermediate recovery vessel (3). The intermediate recovery vessel (3) is also connected to the ammonia feed line (4). The ammonia liquid outlet of the intermediate recovery vessel (3) is connected to the separation and recovery unit. The liquid phase outlet of the separation and recovery unit is connected to the hydrazine compound synthesis section (5). A steam exhaust line (26) is provided on the top of the concentration tank (1).

2. The apparatus for processing amide intermediates in the production of hydrazine hydrate according to claim 1, characterized in that: The quartz sand catalyst preparation unit includes a quartz sand feed pipe (6), which is connected to the inlet of the regeneration kettle (8) via a high-pressure roller mill (7). The outlet of the regeneration kettle (8) is connected to the catalyst inlet via a diaphragm pump (9) and a catalyst metering delivery unit. The regeneration reactor (8) is also equipped with an acid delivery pipeline (10).

3. The apparatus for processing amide intermediates in the production of hydrazine hydrate according to claim 2, characterized in that: The catalyst metering delivery unit includes a cylinder (11), an acid hydrolysis material inlet (12) at the top of the cylinder (11), the acid hydrolysis material inlet (12) being connected to the outlet of the diaphragm pump (9), an acid overflow port (13) at the top of the cylinder (11), a first filter cylinder (14) made of filter screen corresponding to the acid overflow port (13) inside the cylinder (11), a catalyst solid phase outlet at the bottom of the cylinder (11), a catalyst metering delivery screw conveyor (15) installed on the catalyst solid phase outlet, and the outlet of the metering delivery screw conveyor (15) being connected to the catalyst inlet.

4. The apparatus for processing amide intermediates in the production of hydrazine hydrate according to claim 1, characterized in that: A static mixer (16) is provided between the outlet of the concentration tank (1) and the inlet of the concentrated material of the intermediate recovery vessel (3).

5. An apparatus for processing amide intermediates in the production of hydrazine hydrate according to claim 1 or 4, characterized in that: The intermediate recovery vessel (3) contains a tube side and a shell side. The tube side consists of several heat exchange tubes (17) with tube sheets installed inside the intermediate recovery vessel (3). The bottom of the heat exchange tubes (17) is connected to the lower part of the intermediate recovery vessel (3), and the top of the heat exchange tubes (17) is connected to the upper part of the intermediate recovery vessel (3). The shell side is between the outer wall of the heat exchange tube (17) in the middle of the intermediate recovery vessel (3) and the inner wall of the intermediate recovery vessel (3); The intermediate recovery vessel (3) at the lower shell side is provided with a heat exchange medium inlet pipe (18), and the intermediate recovery vessel (3) at the upper shell side is provided with a heat exchange medium outlet pipe (19). The bottom of the intermediate recovery vessel (3) is provided with a concentrated material inlet. Inside the intermediate recovery vessel (3) above the concentrated material inlet, there is a bubbler (20). The inlet of the bubbler (20) is connected to the ammonia feed line (4).

6. The apparatus for processing amide intermediates in the production of hydrazine hydrate according to claim 5, characterized in that: The intermediate recovery vessel (3) is provided with a gas phase outlet at the top and an ammonia liquid outlet on one side of the upper part of the intermediate recovery vessel (3).

7. An apparatus for processing amide intermediates in the production of hydrazine hydrate according to claim 1 or 6, characterized in that: The separation and recovery unit includes a liquid-solid separator (21) connected to the ammonia liquid outlet of the intermediate recovery vessel (3). The liquid phase outlet of the liquid-solid separator (21) is connected to a gas-liquid separator (25), and the bottom liquid phase outlet of the gas-liquid separator (25) is connected to the hydrazine compound synthesis section (5).

8. The apparatus for processing amide intermediates in the production of hydrazine hydrate according to claim 7, characterized in that: The solid catalyst outlet of the liquid-solid separator (21) is connected to the circulation inlet of the regeneration vessel (8) through the catalyst storage tank (23), and the top gas phase outlet of the gas-liquid separator (25) is connected to the vent pipe (24).

9. A device for processing amide intermediates in the production of hydrazine hydrate according to claim 8, characterized in that: The liquid-solid separator (21) has an inlet on one side of the middle section, a solid catalyst outlet at the bottom, and a liquid outlet at the top. A second filter cylinder (22) made of filter screen is provided in the liquid-solid separator (21) below the liquid outlet.

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