Reaction extraction device for producing hydroxylamine sulfate

Abstract

The utility model relates to a reaction extraction device for producing hydroxylamine sulfate, which comprises a mixed solution feeding pipe and a sulfuric acid feeding pipe which are arranged on the outer wall of a reaction extraction tower, a crude product discharging pipe is arranged at the bottom of the reaction extraction tower, and a crude product conveying pump and a crude product refining device are sequentially arranged on the crude product discharging pipe; a stirring paddle is arranged in the reaction extraction tower and is powered by a driving motor, the outer wall of the reaction extraction tower is of a jacket structure, and a jacket layer is connected with a reboiler through a pipeline. The utility model has the beneficial effects that no extra catalyst is needed, and the production cost is low; extra reagents do not need to be introduced, the light components cyclohexanone and cyclohexane after reaction extraction are returned to the heterogeneous ammoximation device for cyclic utilization, and the technological process is simple; 0.1 MPa low-grade steam which is a byproduct of a factory is fully utilized as a heat source of the reboiler, so that comprehensive utilization of heat energy is achieved; the reaction temperature and pressure are mild, and safe and environment-friendly green production is achieved; no side reaction occurs in the reaction, and the subsequent hydroxylamine sulfate refining difficulty is reduced.

Description

Technical Field

[0001] The utility model belongs to the field of chemical production, in particular to a reaction extraction device for producing hydroxylamine sulfate. Background Art

[0002] Hydroxylamine sulfate is widely used in medicine, pesticides, analysis and other chemical fields. At present, the traditional methods for producing hydroxylamine sulfate mainly include catalytic reduction method, ion exchange method, double decomposition method, etc. The traditional production process of hydroxylamine sulfate has the disadvantages of complex process, need to use catalyst, high energy consumption, many side reactions, high production cost and low conversion rate.

[0003] Patent CN112591721B discloses a method for preparing solid hydroxylamine sulfate. The present invention discloses a method for preparing solid hydroxylamine sulfate, comprising the following steps: Step 1, synthesis of hydroxylamine sulfate: according to the mass fraction, ketoxime, concentrated sulfuric acid with a concentration of 60-80%, water, and a solid acid catalyst are added to a reactor, stirred at 100-300r / min, mixed evenly, heated to 70-90°C, reacted for 60-120min, to obtain a solution of ketone, water and hydroxylamine sulfate, and then vacuumed to -0.07 to -0.09MPa, separated and recovered ketone, and obtained hydroxylamine sulfate water. Solution; Step 2, refining of hydroxylamine sulfate: according to the mass fraction, add ammonia water to the obtained hydroxylamine sulfate aqueous solution, heat to 40-45°C while stirring, stir for 40-60 minutes, then add alcohol, stir, precipitate ammonium sulfate, reduce pressure and filter, obtain a methanol aqueous solution of hydroxylamine, then add sulfuric acid to the aqueous solution until the pH is 5-6, cool to 0-2°C, precipitate needle-shaped crystals, reduce pressure and filter, separate and reuse the filtrate by rectification, freeze-dry the needle-shaped crystals to fully remove volatiles, and obtain a solid hydroxylamine sulfate. The solid hydroxylamine sulfate obtained by the present invention has high yield and high purity. This patented technology requires the use of a solid catalyst, and the production cost is high.

[0004] Patent CN111285338A discloses a method for preparing solid hydroxylamine sulfate. The present invention relates to the field of chemical industry, and specifically to a method for preparing solid hydroxylamine sulfate; the method provides a method for preparing solid hydroxylamine sulfate by reacting sulfuric acid and butanone oxime, the method uses conventional reagents, does not contain any toxic raw materials, has mild reaction conditions, short process flow, low production cost, and can also produce byproduct butanone, which is economical and environmentally friendly; a recyclable metal-doped graphene adsorption material is used, and the strong complexation effect between metal ions and butanone oxime can be utilized to efficiently adsorb organic residues in hydroxylamine sulfate solution, which has the advantages of energy saving, environmental protection, and high utilization rate. The patented technology uses butanone oxime as raw material, requires the use of adsorption materials, and has high production costs.

[0005] Patent CN107539966B discloses a method for preparing hydroxylamine sulfate. The present invention discloses a method for preparing hydroxylamine sulfate, comprising the following steps: 1) the acid solution and oxime as raw materials are mixed evenly and then enter into a reaction distillation tower for distillation, and the bottom of the tower obtains a mixed solution of hydroxylamine sulfate and unreacted oxime and acid; 2) the mixed solution obtained in the bottom of the tower is partially transported to a stripping tower by a pump for stripping to remove organic matter and part of the water, and partially transported to a reactor equipped with a catalyst for further reaction; the liquid material obtained by the reaction is returned to the bottom of the distillation tower, and the gas phase is returned to the middle and upper part of the distillation tower; 3) the concentrated hydroxylamine sulfate solution flowing out of the bottom of the stripping tower is crystallized, liquid-solid separated, and dried to obtain hydroxylamine sulfate. This patented technology involves multi-step reactions, and the process flow is relatively complicated. Summary of the invention

[0006] The utility model aims to solve the shortcomings of the traditional hydroxylamine sulfate production process proposed in the above background, such as complex process, need to use catalyst, high energy consumption, many side reactions, high production cost, low conversion rate, etc. A reaction extraction device for producing hydroxylamine sulfate is provided, the reaction extraction device has mild reaction conditions, does not need to use catalyst, has low energy consumption, short process flow, no side reaction occurs, and high hydroxylamine sulfate conversion rate, and its technical scheme is: comprising a reaction extraction tower, the outer wall of the reaction extraction tower is provided with a mixed solution feed pipe and a sulfuric acid feed pipe, the bottom of the reaction extraction tower is provided with a crude product discharge pipe, and the crude product discharge pipe is provided with a crude product transport pump and a crude product refining device in sequence; a stirring paddle is provided inside the reaction extraction tower, the stirring paddle is powered by a driving motor, the outer wall of the reaction extraction tower is a jacket structure, and the jacket layer is connected to a reboiler through a pipeline.

[0007] The top of the reaction extraction tower is connected to a water cooler through a pipeline, the water cooler is connected to a collecting tank, the collecting tank is connected to a ketoxime delivery pump through a pipeline, the ketoxime delivery pump is connected to a heterogeneous ammoximation device, and a vacuum pump is also arranged on the top of the collecting tank, and the vacuum pump is connected to a tail gas treatment device.

[0008] The mixed solution feed pipe is at a lower height in the reaction extraction tower than the sulfuric acid feed pipe.

[0009] The upper inner wall of the reaction extraction tower is provided with X layers of fixed plates, wherein 5≤X≤7, and X is a positive integer.

[0010] A turntable is arranged between the two adjacent fixed plates, and the turntable is arranged on the rod of the stirring paddle.

[0011] In a preferred embodiment, the concentration of dilute sulfuric acid is 2-3 mol / L, and the molar ratio of cyclohexanone oxime to sulfuric acid is 1.5:1.

[0012] As a preferred embodiment, the vacuum pump controls the pressure in the reaction extraction tower at -0.04 MPa.

[0013] As a preferred solution, the reboiler uses 0.1 MPa steam as a heat source to control the temperature of the reaction extraction tower at 60-70°C.

[0014] As a preferred embodiment, in the mixed solution of cyclohexanone oxime and cyclohexane, the mass fraction of cyclohexanone oxime is 20-24%, the mass fraction of cyclohexane is 72-77%, and the rest of the solution is water and other impurities.

[0015] The technical principle adopted by this utility model:

[0016] Cyclohexanone oxime undergoes hydrolysis in a dilute sulfuric acid aqueous solution to generate hydroxylamine sulfate and cyclohexanone. This reaction is a reversible reaction. The mixed solution of the existing heterogeneous ammoximation product cyclohexanone oxime and cyclohexane is used as a raw material to react with a dilute sulfuric acid aqueous solution. At the same time, cyclohexane extracts the cyclohexanone generated by the reaction, so that the reaction equilibrium proceeds in the positive reaction direction. The reaction formula is as follows:

[0017] .

[0018] Beneficial effects of the utility model:

[0019] (1) Hydrolysis reaction is used to produce hydroxylamine sulfate, which does not require the use of additional catalysts and has low production costs;

[0020] (2) Hydrolysis reaction is used to produce hydroxylamine sulfate, with heterogeneous ammoximation product cyclohexanone oxime, solvent cyclohexane and dilute sulfuric acid as raw materials. No additional chemical reagents are required. The light components cyclohexanone and cyclohexane after reaction extraction are returned to the heterogeneous ammoximation device for recycling, and the process flow is simple.

[0021] (3) Make full use of the 0.1MPa low-grade steam produced as a by-product of the factory as the heat source of the reboiler to achieve comprehensive utilization of thermal energy;

[0022] (4) The reaction temperature and pressure are relatively mild, truly achieving safe and environmentally friendly green production;

[0023] (5) This reaction has no side effects, which greatly reduces the difficulty of subsequent purification of hydroxylamine sulfate. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a schematic diagram of the overall structure of the utility model.

[0025] In the figure: 1. reaction extraction tower; 2. water cooler; 3. vacuum pump; 4. collecting tank; 5. ketoxime delivery pump; 6. heterogeneous ammoximation device; 7. reboiler; 8. crude product transport pump; 9. crude product refining device; 10. tail gas treatment device; 11. drive motor; 12. mixed solution feed pipe; 13. sulfuric acid feed pipe; 14. crude product discharge pipe; 15. stirring paddle; 16. fixed plate; 17. turntable. DETAILED DESCRIPTION

[0026] The utility model is further described in detail below based on the accompanying drawings and specific embodiments.

[0027] Example 1

[0028] A reaction extraction device for producing hydroxylamine sulfate comprises a reaction extraction tower 1, wherein a mixed solution feed pipe 12 and a sulfuric acid feed pipe 13 are arranged on the outer wall of the reaction extraction tower 1, a crude product discharge pipe 14 is arranged at the bottom of the reaction extraction tower 1, and a crude product transport pump 8 and a crude product refining device 9 are arranged on the crude product discharge pipe 14 in sequence; a stirring paddle 15 is arranged inside the reaction extraction tower 1, and the stirring paddle 15 is powered by a driving motor 11; the outer wall of the reaction extraction tower 1 is a jacket structure, and the jacket layer is connected to a reboiler 7 through a pipeline.

[0029] The top of the reaction extraction tower 1 is connected to a water cooler 2 through a pipeline, the water cooler 2 is connected to a collecting tank 4, the collecting tank 4 is connected to a ketoxime delivery pump 5 through a pipeline, the ketoxime delivery pump 5 is connected to a heterogeneous ammoximation device 6, and a vacuum pump 3 is also provided on the top of the collecting tank 4, and the vacuum pump 3 is connected to a tail gas treatment device 10.

[0030] The mixed solution feed pipe 12 is located at a lower height than the sulfuric acid feed pipe 13 in the reaction extraction tower 1 .

[0031] The upper inner wall of the reaction extraction tower 1 is provided with five layers of fixed plates 16 .

[0032] A turntable 17 is disposed between the two adjacent fixed plates 16 , and the turntable 17 is disposed on the rod of the stirring paddle 15 .

[0033] Furthermore, the concentration of dilute sulfuric acid is 2-3 mol / L, and the molar ratio of cyclohexanone oxime to sulfuric acid is 1.5:1.

[0034] Furthermore, the vacuum pump controls the pressure in the reaction extraction tower at -0.04 MPa.

[0035] Furthermore, the reboiler uses 0.1 MPa steam as a heat source to control the temperature of the reaction extraction tower at 60-70°C.

[0036] Furthermore, in the mixed solution of cyclohexanone oxime and cyclohexane, the mass fraction of cyclohexanone oxime is 20-24%, the mass fraction of cyclohexane is 72-77%, and the rest of the solution is water and other impurities.

[0037] Example 2

[0038] The device in Example 1 is used, and the mixed solution of cyclohexanone oxime, the product of the heterogeneous ammonia oximation reaction, and the solvent cyclohexane are continuously introduced into the kettle of the reaction extraction tower 1 through a pump and a pipeline, and the pre-configured dilute sulfuric acid is continuously introduced into the kettle of the reaction extraction tower 1 through a pump and a pipeline, and 0.1MPa steam is connected to the shell side of the reboiler 7 through a pipeline, and the mixed solution of cyclohexanone oxime and cyclohexane and the dilute sulfuric acid are indirectly heated by steam in the tube layer of the reboiler 7; a vacuum pump 3 is provided at the top of the reaction extraction tower to maintain the reaction extraction tower 1 at a negative pressure, and cyclohexanone oxime and sulfuric acid are hydrolyzed to generate cyclohexanone and hydroxylamine sulfate under the action of the stirring paddle 15 in the reaction extraction tower 1. After the generated cyclohexanone is extracted by the solvent cyclohexane, the cyclohexane is heated to a gaseous state, and the entrained cyclohexanone continuously rises along the tower plate and is finally extracted from the top of the tower, and after being cooled into a liquid phase by a water cooler 2, it flows into a collection tank 4 by gravity, and is transported to the heterogeneous ammonia oximation device 6 for recycling through a pump and a pipeline. The hydrolysis product hydroxylamine sulfate produced by the reaction extraction tower 1 and part of the reacted cyclohexanone oxime and dilute sulfuric acid are transported to the crude product refining device 9 through a pump and a pipeline to separate a solid hydroxylamine sulfate product with a purity of 99.9%.

Claims

1. A reaction extraction device for producing hydroxylamine sulfate, characterized in that: The invention comprises a reaction extraction tower (1), wherein a mixed solution feed pipe (12) and a sulfuric acid feed pipe (13) are arranged on the outer wall of the reaction extraction tower (1), a crude product discharge pipe (14) is arranged at the bottom of the reaction extraction tower (1), and a crude product transport pump (8) and a crude product refining device (9) are arranged on the crude product discharge pipe (14) in sequence; a stirring paddle (15) is arranged inside the reaction extraction tower (1), and the stirring paddle (15) is powered by a driving motor (11); the outer wall of the reaction extraction tower (1) is a jacket structure, and the jacket layer is connected to a reboiler (7) through a pipeline.

2. A reaction extraction device for producing hydroxylamine sulfate according to claim 1, characterized in that: The top of the reaction extraction tower (1) is connected to a water cooler (2) via a pipeline, the water cooler (2) is connected to a collecting tank (4), the collecting tank (4) is connected to a ketoxime delivery pump (5) via a pipeline, the ketoxime delivery pump (5) is connected to a heterogeneous ammoximation device (6), and a vacuum pump (3) is also provided on the top of the collecting tank (4), and the vacuum pump (3) is connected to a tail gas treatment device (10).

3. A reaction extraction device for producing hydroxylamine sulfate according to claim 1, characterized in that: The mixed solution feed pipe (12) is located at a lower height in the reaction extraction tower (1) than the sulfuric acid feed pipe (13).

4. A reaction extraction device for producing hydroxylamine sulfate according to claim 1, characterized in that: The upper inner wall of the reaction extraction tower (1) is provided with X layers of fixed plates (16), wherein 5≤X≤7, and X is a positive integer.

5. A reaction extraction device for producing hydroxylamine sulfate according to claim 4, characterized in that: A turntable (17) is disposed between the two adjacent fixed plates (16), and the turntable (17) is disposed on the rod of the stirring paddle (15).

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