Synthetic method of liquid organic peroxide

Abstract

The invention relates to the related technical field of synthesis of materials, and particularly provides a synthesis method of liquid organic peroxide. The synthesis method comprises the following steps: S101, premixing an oxygen-containing organic compound and inorganic acid to obtain a reaction premix; s102, the reaction premix obtained in the step S101 and hydrogen peroxide are sequentially conveyed to a filling reactor and a delay pipeline, and the reaction premix and the hydrogen peroxide are subjected to a peroxidation reaction in the filling reactor and the delay pipeline; wherein an inner cavity of the filling reactor is filled with austenitic stainless steel; and step S103, carrying out oil-water separation on the reaction product obtained in the step 102 to obtain the liquid organic peroxide. By filling the austenitic stainless steel in the filling reactor, the yield and purity of the product, especially chromium-nickel type austenitic stainless steel, can be obviously improved.

Description

Technical Field

[0001] This application relates to the technical field of material synthesis, and specifically provides a method for synthesizing liquid organic peroxides. Background Art

[0002] Peroxides are a class of organic compounds with a peroxy chain (i.e., the —O—O— structure), which can be regarded as derivatives of hydrogen peroxide, and the presence of peroxo ions in the molecule is their characteristic. Due to the presence of peroxy bonds and a relatively high oxygen content in the molecular structure, they can be used as free radical initiators and participate in oxidation reactions, and can be used in fields such as organic synthesis and new material processing and manufacturing, as well as disinfectants, bactericides, and bleaching agents, etc. They are an important class of chemical products with a wide range of application fields and economic value.

[0003] Since the bond energy of the —O—O— structure is relatively small and the chemical properties are active, it is prone to decomposition under certain conditions, accompanied by energy release, resulting in the flammable and explosive properties of this type of compound. Some peroxides are extremely sensitive to factors such as temperature, metal ions, static electricity, and vibration, and have relatively high requirements for various links such as production, storage, transportation, and use.

[0004] Organic peroxides are currently produced using traditional batch processes. That is, raw materials, solvents, etc. are added to a reaction kettle, stirred evenly, then hydrogen peroxide is added dropwise, and the reaction is carried out under heat preservation. After the peroxidation reaction is completed, separation is carried out to obtain the organic peroxide. Usually, there is a very strong exothermic phenomenon during the feeding process, and it is necessary to control the temperature within a controllable range in a timely manner through a refrigerant medium. Due to the limitations of the batch reaction kettle, it is very difficult to effectively control the reaction temperature, and there is a risk of runaway, which can lead to serious accidents such as combustion or explosion. Even when using an automatic control system such as a distributed control system (DCS), relevant operators need to observe multiple operating parameters at any time and make adjustments at any time, which requires a very high professional level of the relevant operators and there are safety risk factors. Relevant accident cases caused by this have been reported in domestic and foreign literature. Therefore, the state has included the peroxidation process in one of the key supervised hazardous processes. How to safely scale up the production of peroxide synthesis process has also become an important problem to be solved. In order to reduce the safety risk and process scale-up risk of the peroxidation process, a lot of relevant research has been carried out at home and abroad. The focus is on how to effectively control the reaction heat effect during the peroxide synthesis process and how to effectively reduce the amount of materials in the synthesis process to reduce the hazards and thus reduce the safety risk, etc. Recently, it has been reported that process methods such as the microreactor method and the continuous flow method are used to conduct relevant process experiments, which can specifically solve some risk factors of the peroxidation process. The microreactor method is currently in the stage of theoretical improvement and process development. There is no report of stable industrial production yet, and there are many factors that need to be considered in the structural design of the microreactor, making the reactor structure relatively complex, with difficulties in processing and manufacturing, resulting in high processing and manufacturing costs, which limits its process research and development and practical application. The continuous flow method, due to the need for uniform mixing of various materials and a certain degree of mixing during the peroxide reaction process, especially when the solubility of some raw materials such as alcohols or aldehydes and ketones in the aqueous phase is poor, often leads to incomplete mixing of the raw materials and low raw material conversion rate, thus increasing the process flow and making the process flow complex. It is very difficult to obtain high-purity products, which limits its practical application. Summary of the Invention

[0005] In view of this, the present application provides a method for synthesizing a liquid organic peroxide, and the synthesis method includes the following steps: Step S101: Premix an oxygen-containing organic compound and an inorganic acid to obtain a reaction premix; Step S102: Sequentially transport the reaction premix obtained in step S101 and hydrogen peroxide to a packed reactor and a delay pipeline, and the reaction premix and the hydrogen peroxide undergo a peroxidation reaction in the packed reactor and the delay pipeline; wherein, the inner cavity of the packed reactor is filled with austenitic stainless steel, and the filling rate of the austenitic stainless steel in the packed reactor is (75-95)%; Step S103: The reaction product obtained in Step 102 undergoes oil-water separation to obtain the liquid organic peroxide. The oxygen-containing organic compound includes at least one of an alcohol organic compound, an aldehyde organic compound, or a ketone organic compound. The molar ratio of the oxygen-containing organic compound, the inorganic acid, and the hydrogen peroxide is 1:(0.1 - 10.0):(1.0 - 5.0).

[0006] In some alternative embodiments, the austenitic stainless steel is uniformly filled in the inner cavity of the packed reactor. To achieve uniform filling of the austenitic stainless steel, the austenitic stainless steel can be made into a mesh shape, a honeycomb shape, etc.

[0007] In some alternative embodiments, the filling rate of the austenitic stainless steel in the packed reactor is (85 - 95)% (such as 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, or 95%, etc.).

[0008] In some specific embodiments, the filling rate of the austenitic stainless steel in the packed reactor is 90%.

[0009] In some alternative embodiments, the austenitic stainless steel includes at least one of austenitic chromium-nickel-manganese stainless steel or chromium-nickel stainless steel. In some specific embodiments, the austenitic stainless steel is selected from chromium-nickel stainless steel.

[0010] In some alternative embodiments, the chromium-nickel stainless steel includes at least one of 06Cr19Ni10 stainless steel (304 stainless steel), 06Cr25Ni20 stainless steel (310S stainless steel), 022Cr17Ni12Mo2 stainless steel (316 stainless steel), or 1Cr18Ni9Ti stainless steel (321 stainless steel). In some specific embodiments, the chromium-nickel stainless steel is selected from 022Cr17Ni12Mo2 steel.

[0011] In some alternative embodiments, the inner cavity volume of the packed reactor is (0.1 - 10) mL (such as 0.1 mL, 0.2 mL, 0.3 mL, 0.4 mL, 0.5 mL, 0.6 mL, 0.7 mL, 0.8 mL, 0.9 mL, 1 mL, 1.5 mL, 2 mL, 2.5 mL, 3 mL, 3.5 mL, 4 mL, 4.5 mL, 5 mL, 5.5 mL, 6 mL, 6.5 mL, 7 mL, 7.5 mL, 8 mL, 8.5 mL, 9 mL, 9.5 mL, or 10 mL, etc.). In some specific embodiments, the inner cavity volume of the packed reactor is 2 mL.

[0012] In some alternative embodiments, the inner diameter of the delay pipeline is selected from (0.1 - 3.0) mm (such as 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, 1.6 mm, 1.7 mm, 1.8 mm, 1.9 mm, 2.0 mm, 2.1 mm, 2.2 mm, 2.3 mm, 2.4 mm, 2.5 mm, 2.6 mm, 2.7 mm, 2.8 mm, 2.9 mm or 3.0 mm, etc.). In some specific embodiments, the inner diameter of the delay pipeline is selected from 2.0 mm.

[0013] In some alternative embodiments, the total flow rate of the reaction premix and the hydrogen peroxide in the filling reactor and the delay pipeline is (0.1 - 100) mL / min (such as 0.1 mL / min, 1 mL / min, 5 mL / min, 10 mL / min, 15 mL / min, 20 mL / min, 25 mL / min, 30 mL / min, 35 mL / min, 40 mL / min, 45 mL / min, 50 mL / min, 55 mL / min, 60 mL / min, 65 mL / min, 70 mL / min, 75 mL / min, 80 mL / min, 85 mL / min, 90 mL / min, 95 mL / min or 100 mL / min, etc.). In some specific embodiments, the total flow rate of the reaction premix and the hydrogen peroxide in the filling reactor and the delay pipeline is 6 mL / min.

[0014] In some alternative embodiments, the temperature of the peroxidation reaction is selected from (-10 - 75) °C (such as -10 °C, -5 °C, 0 °C, 5 °C, 10 °C, 15 °C, 20 °C, 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, etc.). In some specific embodiments, the temperature of the peroxidation reaction is selected from 45 °C.

[0015] In some alternative embodiments, the alcohol organic compound includes at least one of tert-butanol, isobutanol, tert-pentanol or cyclohexanol. In some specific embodiments, the alcohol organic compound is selected from tert-butanol.

[0016] In some alternative embodiments, the aldehyde organic compound includes at least one of butyraldehyde or valeraldehyde.

[0017] In some alternative embodiments, the ketone organic compound includes at least one of 2-butanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone or cyclohexanone. In some specific embodiments, the ketone organic compound is selected from 2-butanone.

[0018] In some alternative embodiments, the inorganic acid includes at least one of sulfuric acid, phosphoric acid, nitric acid or perchloric acid. In some specific embodiments, the inorganic acid is selected from sulfuric acid. In some other alternative embodiments, the sulfuric acid is selected from sulfuric acid aqueous solutions with a concentration of (70-80)%(m / v) (such as 70%(m / v), 71%(m / v), 72%(m / v), 73%(m / v), 74%(m / v), 75%(m / v), 76%(m / v), 77%(m / v), 78%(m / v), 79%(m / v) or 80%(m / v), etc.). In some other specific embodiments, the sulfuric acid is selected from sulfuric acid aqueous solutions with a concentration of 75%(m / v).

[0019] In some alternative embodiments, the hydrogen peroxide is selected from hydrogen peroxide aqueous solutions with a concentration of (45-55)%(m / v) (such as 45%(m / v), 46%(m / v), 47%(m / v), 48%(m / v), 49%(m / v), 50%(m / v), 51%(m / v), 52%(m / v), 53%(m / v), 54%(m / v) or 55%(m / v), etc.). In some specific embodiments, the hydrogen peroxide is selected from hydrogen peroxide aqueous solutions with a concentration of 55%(m / v).

[0020] In some specific embodiments, the oxygen-containing organic compound is selected from alcohol organic compounds. In some other specific embodiments, the oxygen-containing organic compound is selected from tert-butanol, and the liquid organic peroxide is selected from di-tert-butyl peroxide. In some alternative embodiments, the tert-butanol is selected from tert-butanol aqueous solutions with a concentration of (70-90)%(m / v) (such as 70%(m / v), 75%(m / v), 80%(m / v), 85%(m / v) or 90%(m / v), etc.). In some specific embodiments, the tert-butanol is selected from tert-butanol aqueous solutions with a concentration of 85%(m / v).

[0021] The present application has the following beneficial effects: First, filling the reactor with austenitic stainless steel in the present application can significantly improve the yield and purity of the product, especially chromium-nickel type austenitic stainless steel, and more particularly 022Cr17Ni12Mo2.

[0022] Second, as the filling rate of the present application in the filling reactor increases, the yield and purity of the product "first increase and then decrease". Description of the Drawings

[0023] To more clearly illustrate the specific embodiments of the present disclosure or the technical solutions in the prior art, the following will briefly introduce the drawings required for use in the description of the specific embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present disclosure. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0024] Figure 1 It is a device flowchart for implementing a method for synthesizing a liquid organic peroxide of the present application. Specific Embodiments

[0025] The present application discloses a method for synthesizing a liquid organic peroxide. Those skilled in the art can draw on the content of this article and appropriately modify the process parameters to achieve it. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art, and they are all considered to be included in the present application. The method and application of the present application have been described through preferred embodiments. Relevant personnel can obviously make changes or appropriate alterations and combinations to the methods and applications described herein without departing from the content, spirit, and scope of the present application to implement and apply the technology of the present application.

[0026] To make the objectives, technical solutions, and advantages of the present application clearer, the following will further describe the implementation schemes of the present application in detail in combination with embodiments.

[0027] Example: Synthesis of Liquid Organic Peroxide In the example, the device flowchart for implementing a method for synthesizing a liquid organic peroxide of the present application is as Figure 1 shown. Among them, an oxygen-containing organic compound and an inorganic acid are premixed and placed in Container 1, and hydrogen peroxide is placed in Container 2; the reaction premix flows through the packed reactor and the delay pipeline synchronously under the action of a constant flow pump 1, and hydrogen peroxide flows through the packed reactor and the delay pipeline synchronously under the action of a constant flow pump 2. The reaction premix and the hydrogen peroxide undergo an oxidation reaction in the packed reactor and the delay pipeline; the reaction product passes through an oil-water separator to obtain an oil phase and a water phase, and the oil phase is the liquid organic peroxide.

[0028] Before the experiment, the flow rate of the constant pressure infusion pump was calibrated with pure water and the system pipeline was leak-tested. The inner cavity volume of the packed reactor is 2 mL; the inner diameter of the delay pipeline is 2 mm, and the installed length of the delay pipeline is calculated according to the flow rate as a delay time of 0.5 h.

[0029] Taking di-tert-butyl peroxide as an example, the synthesis route of di-tert-butyl peroxide is as follows: .

[0030] Set the temperature of the reaction bath (water bath) to 45 °C, set the first constant flow pump to 5 mL / min, and set the second constant flow pump to 1 mL / min. Premix 50 g of an aqueous solution of tert-butanol with a concentration of 85% (m / v) and 37 g of an aqueous solution of sulfuric acid with a concentration of 75% (m / v) and load them into Container 1. Load 20 g of an aqueous hydrogen peroxide solution with a concentration of 50% (m / v) into Container 2; simultaneously start the first constant pressure and constant flow pump and the second constant pressure and constant flow pump, observe the change in reaction temperature through a temperature sensor, and separate the upper oil phase through an oil-water separation device, which is the product di-tert-butyl peroxide. And use gas chromatography GC analysis method (in accordance with HG / T 5794-2021) to determine the purity of the product di-tert-butyl peroxide.

[0031] Among them, different materials are filled in the packed reactor for the above reaction, and the reaction results are shown in Table 1.

[0032] Table 1:

[0033] As can be seen from Table 1, filling the packed reactor with austenitic stainless steel in this application can significantly improve the yield and purity of the product.

[0034] By comparing Examples 3, 6-9 and Comparative Examples 1-3, it can be seen that compared with non-filling, filling the packed reactor with austenitic stainless steel in this application can significantly improve the yield and purity of the product, especially chromium-nickel type austenitic stainless steel, and more particularly 022Cr17Ni12Mo2; on the contrary, filling the packed reactor with martensitic stainless steel not only cannot improve the yield of the product, but also reduces the purity of the product.

[0035] By comparing Examples 1-5, it can be seen that as the filling rate of this application in the packed reactor increases, the yield and purity of the product "first increase and then decrease".

[0036] The above has introduced in detail a method for synthesizing a liquid organic peroxide provided by this application. Specific examples are used in this article to elaborate on the principle and implementation manner of this application. The description of the above examples is only used to help understand the method and its core idea of this application. It should be pointed out that for those skilled in the art of this technology, without departing from the principle of this application, several improvements and modifications can still be made to this application, and these improvements and modifications also fall within the protection scope of the claims of this application.

Claims

1. A method for synthesizing a liquid organic peroxide, characterized in that, The synthesis method comprises the following steps: Step S101: Premix an oxygen-containing organic compound and an inorganic acid to obtain a reaction premix; Step S102: Sequentially transport the reaction premix obtained in Step S101 and hydrogen peroxide to a packed reactor and a delay pipeline, and the reaction premix and the hydrogen peroxide undergo a peroxidation reaction in the packed reactor and the delay pipeline; wherein, the inner cavity of the packed reactor is filled with austenitic stainless steel, and the filling rate of the austenitic stainless steel in the packed reactor is (75-95)%; Step S103: Separate oil and water from the reaction product obtained in Step 102 to obtain the liquid organic peroxide; The oxygen-containing organic compound includes at least one of an alcohol organic compound, an aldehyde organic compound or a ketone organic compound; The molar ratio of the oxygen-containing organic compound, the inorganic acid and the hydrogen peroxide is 1:(0.1-10.0):(1.0-5.0).

2. The synthesis method according to claim 1, characterized in that, The filling rate of the austenitic stainless steel in the packed reactor is (85-95)%.

3. The synthesis method according to claim 2, wherein The filling rate of the austenitic stainless steel in the packed reactor is 90%.

4. The synthesis method according to any one of claims 1 to 3, characterized in that, The austenitic stainless steel includes at least one of austenitic chromium-nickel-manganese stainless steel or chromium-nickel stainless steel; 5. The synthesis method according to claim 4, characterized in that, The austenitic stainless steel is selected from chromium-nickel stainless steel; 6. The synthesis method according to claim 5, characterized in that, The chromium-nickel stainless steel includes at least one of 06Cr19Ni10 stainless steel, 06Cr25Ni20 stainless steel, 022Cr17Ni12Mo2 stainless steel or 1Cr18Ni9Ti stainless steel; 7. The synthesis method according to claim 6, characterized in that, The chromium-nickel stainless steel is selected from 022Cr17Ni12Mo2 stainless steel; 8. The synthesis method according to claim 1, wherein, The inner cavity volume of the packed reactor is (0.1-10) mL; and / or, the inner diameter of the delay pipeline is (0.1-3.0) mm; and / or, the total flow rate of the reaction premix and the hydrogen peroxide in the packed reactor and the delay pipeline is (0.1-100) mL / min; 9. The method according to claim 1, characterized in that, The temperature of the peroxidation reaction is selected from (-10-75) °C; 10. The synthesis method according to claim 1, characterized in that, The alcohol organic compound includes at least one of tert-butanol, isobutanol, tert-amyl alcohol or cyclohexanol; and / or, the aldehyde organic compound includes at least one of butyraldehyde or valeraldehyde; and / or, the ketone organic compound includes at least one of 2-butanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone or cyclohexanone; and / or, the inorganic acid includes at least one of sulfuric acid, phosphoric acid, nitric acid or perchloric acid.

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