Environment-friendly green ferrocene purification method

Abstract

The invention discloses an environment-friendly green ferrocene purification method, and belongs to the technical field of environment-friendly green ferrocene purification methods. According to the method, a steam distillation sublimation and plasma stirring synergistic method is adopted, a steam distillation technology is adopted, the characteristic that ferrocene sublimates at the temperature of 100 DEG C is utilized, an inert environment is provided through steam, the system partial pressure is reduced, high-temperature decomposition is avoided, water diffusion steam distillation is adopted, the condensation blocking risk is reduced, the mass transfer efficiency is improved, and non-thermal plasma is introduced; and uniform stirring is realized through active particles such as high-energy electrons and free radicals, so that the retention time of ferrocene is shortened, and the generation of caking is reduced. Light component impurities in ferrocene are reduced through desolvation treatment, high-purity ferrocene is obtained, the caking problem is solved, solid waste discharge is reduced, the solvent can be recycled, the method has the advantages of being simple in process, environmentally friendly and high in product purity, operation convenience and efficiency are effectively improved, and the method is suitable for industrial production. The industrial continuous automatic production of the ferrocene is favorably realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of chemical materials, and particularly relates to an environmentally friendly and green purification method for ferrocene. Background Art

[0002] Ferrocene, also known as cyclopentadienyl iron, has an orange needle-like crystal appearance. It is soluble in ether, tetrahydrofuran, concentrated sulfuric acid, benzene, dilute nitric acid, and petroleum ether. Ferrocene is widely used in industries such as energy conservation, industry, aerospace, medicine, agriculture, and environmental protection. It can be used as a photosensitizer, fuel-saving and anti-knock agent, antibiotic, blood supplement, special enzyme inhibitor, additive, and various tracers. It can also be used as an analytical reagent, lubricating oil additive, radiation absorber, catalyst, polymer additive for plastics and rubbers, heat stabilizer, light stabilizer, flame retardant, wear-resistant material promoter, antistatic agent, biochemical and tracer material. The purity of ferrocene products and the differences in crystal forms directly have a greater impact on the application of products and the quality of subsequent synthetic products. The crude solid product of ferrocene separated from the synthesis reaction contains unreacted raw materials, by-products, and impurities, etc., and must be separated and purified. Currently, recrystallization method, steam distillation method, and sublimation separation method are commonly used in the industry for ferrocene.

[0003] Most of the organic solvents used in the purification of ferrocene by the recrystallization method are flammable solvents. There is a certain amount of volatile organic solvents during hot filtration, with low safety performance. Moreover, due to the complex process, strict operation requirements, and relatively serious pollution, it has been gradually phased out.

[0004] The advantage of the sublimation method is that no chemical solvents are required during the purification process, and no waste liquid is generated. However, it has high requirements for equipment performance. The temperature is high during the sublimation process, and the material is prone to forming lumps. It is very easy to cause equipment blockage during the condensation process. The entire sublimation process needs to be carried out in a closed system, and strict attention should be paid to preventing fire during operation, with high safety risks, which greatly inhibits its promotion and application in industrial continuous production.

[0005] The steam method for purifying ferrocene is the method commonly used in the industry at present. In this purification method, a large amount of steam is used to sublimate ferrocene in the mixture, and after condensation, a solid product is obtained through liquid-solid separation and drying. However, this method still has many problems such as easy blockage of materials in the condenser, low thermal efficiency, high energy consumption, and a large amount of three wastes. Summary of the Invention

[0006] In view of the above situation, the present invention provides an environmentally friendly and green purification method for ferrocene, which can effectively solve the problems of low purification purity and high energy consumption in the prior art for ferrocene.

[0007] In order to achieve the above object, the following technical solutions are adopted: The present invention provides an environmentally friendly and green purification method for ferrocene, including the following steps:

[0008] (1) Pretreatment: Pretreating the crude ferrocene and crushing the crude ferrocene into uniform particles;

[0009] (2) Plasma activation: Inert nitrogen is introduced into a closed reactor to generate low-temperature plasma through electrodes to treat the crude product, decompose macromolecular impurities and activate ferrocene molecules;

[0010] (3) High-pressure steam injection: high-pressure steam is introduced, combined with mechanical stirring to prevent agglomeration;

[0011] (4) Temperature-controlled sublimation: The jacket of the purifier is heated to maintain efficient sublimation of ferrocene;

[0012] (5) Plasma assistance: A plasma generator is added to the steam injection area to use high-energy electron flow to promote the separation of ferrocene and impurities and reduce side reactions;

[0013] (6) Condensation and separation: Provide water spray cooling, the mixed gas enters the spray tower, and the cooling water temperature is controlled to condense ferrocene into microcrystalline particles, which enter the solid-liquid separator with the water flow;

[0014] (7) Plasma anti-blocking design: Plasma activation layer is coated on the inner wall of the condensation pipe to reduce ferrocene sticking to the wall;

[0015] (8) Circulation and environmental protection treatment: The separated water is treated by activated carbon adsorption and plasma oxidation to remove residual organic matter and then circulated to the spray system.

[0016] (9) Exhaust gas purification: The uncondensed gas is decomposed into volatile organic compounds through a plasma catalytic oxidation device to achieve emission standards.

[0017] In the above purification method, a synergistic method of steam distillation sublimation and plasma stirring is adopted. The characteristic of ferrocene sublimating at 100°C is utilized, and water vapor is used to provide an inert environment and reduce the partial pressure of the system to avoid high-temperature decomposition. Water diffusion steam distillation is utilized, and the steam penetrates the material layer from top to bottom to reduce the risk of condensation blockage and improve the mass transfer efficiency. Non-thermal plasma is introduced during the distillation process to achieve uniform stirring through active particles such as high-energy electrons and free radicals.

[0018] Furthermore, in step (2), the power of the electrode to generate low-temperature plasma is 50-200W.

[0019] Furthermore, the duration of treating the crude product in step (2) is 10-30 min.

[0020] Furthermore, in step (3), the pressure of the high-pressure water vapor is 0.4-0.8 MPa.

[0021] Furthermore, in the step (4), the jacket of the purifier is heated to 100-160°C.

[0022] Further, the rotation speed of the mechanical stirring in step (3) is 50 - 100 r / min.

[0023] Further, the temperature of the cooling water in step (6) is controlled at 0 - 20°C.

[0024] Further, in the present invention, through an integrated reactor, a steam injection port, a magnetic stirring paddle and a plasma electrode are integrated in the purifier to achieve multi - technology cooperation.

[0025] Further, in the purification method, the reactor material is made of high - temperature - resistant and corrosion - resistant 316L stainless steel or quartz glass. By combining a quartz purification column with a high - temperature reactor, it is corrosion - resistant and avoids metal contamination.

[0026] Further, the present invention integrates an on - line monitoring system (infrared spectroscopy + melting point instrument) to real - time regulate process parameters, inhibit side reactions and reduce impurity generation.

[0027] The beneficial effects of the present invention are as follows:

[0028] (1) The present invention adopts a method of synergistically combining steam distillation sublimation and plasma stirring. Using the steam distillation technology, taking advantage of the property that ferrocene sublimes at 100°C, the steam provides an inert environment and reduces the system partial pressure to avoid high - temperature decomposition. Using water - diffusion steam distillation, the steam penetrates the material layer from top to bottom, reducing the risk of condensation blockage and improving the mass transfer efficiency. Introducing the plasma stirring technology, non - thermal plasma is introduced during the distillation process, and uniform stirring is achieved through active particles such as high - energy electrons and free radicals, shortening the residence time of ferrocene in the sublimator and reducing the formation of lumps.

[0029] (2) Compared with the traditional sublimation technology, the ferrocene purification method of the present invention can reduce the light - component impurities in ferrocene through desolvation treatment, thereby obtaining high - purity ferrocene. It also shortens the residence time of ferrocene in the sublimator, avoiding the formation of lumps of materials in the sublimator. Compared with the traditional sublimation method, it improves the purity of ferrocene, solves the problem of lumping, reduces the discharge of solid waste, and realizes the recycling of solvents. The ferrocene purification method of the present invention has the characteristics of simple process, environmental protection and high product purity, effectively improving the operation convenience and efficiency, and is conducive to realizing the industrial continuous and automated production of ferrocene. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 It is the process flow diagram of the environment - friendly and green ferrocene purification method of the present invention.

[0031] The accompanying drawings are used to provide a further understanding of the present invention and form a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention and do not constitute a limitation to the present invention. Detailed implementation manners

[0032] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the scope of protection of the present invention.

[0033] Unless otherwise defined, all professional and scientific terms used herein have the same meaning as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to the described content can be applied to the present invention. The preferred implementation methods and materials described herein are only for illustrative purposes and do not limit the content of this application.

[0034] The experimental methods in the following embodiments are all conventional methods unless otherwise specified. The test materials used in the following embodiments are all obtained from commercial channels unless otherwise specified.

[0035] Embodiment

[0036] An environmentally friendly and green ferrocene purification method includes the following steps:

[0037] (1) Pretreatment: Pretreat the crude ferrocene by crushing the crude ferrocene into uniform particles;

[0038] (2) Plasma activation: Introduce the inert gas nitrogen into a closed reactor, generate low-temperature plasma through the electrode, with a power of 100 W, treat the crude product for 20 min to decompose macromolecular impurities and activate ferrocene molecules;

[0039] (3) High-pressure steam injection: Inject high-pressure steam at 0.5 MPa, and combine mechanical stirring to prevent caking. The rotational speed of the mechanical stirring is 80 r / min;

[0040] (4) Temperature-controlled sublimation: Heat the jacket of the purifier to 150 °C to maintain the efficient sublimation of ferrocene;

[0041] (5) Plasma assistance: Add a plasma generator in the steam injection area to use high-energy electron flow to promote the separation of ferrocene from impurities and reduce side reactions;

[0042] (6) Condensation and separation: Provide water spray cooling. The mixed gas enters the spray tower, and the temperature of the cooling water is controlled at 10 °C to sublimate ferrocene into microcrystalline particles, which enter the solid-liquid separator with the water flow;

[0043] (7) Plasma anti-blocking design: Coat the inner wall of the condensation pipe with a plasma activation layer to reduce the hanging of ferrocene on the wall;

[0044] (8) Circulation and environmental protection treatment: The separated water is treated by activated carbon adsorption and plasma oxidation to remove residual organic matter and then recycled to the spraying system.

[0045] (9) Tail gas purification: Pass the uncondensed gas through a plasma catalytic oxidation device to decompose volatile organic compounds and discharge them up to standard.

[0046] In the above method, the reactor material is made of heat-resistant and corrosion-resistant 316L stainless steel. A quartz purification column is combined with a heat-resistant 316L stainless steel reactor, which is corrosion-resistant and avoids metal contamination.

[0047] Result analysis

[0048] Compared with the traditional method, the present invention has the following advantages:

[0049] 1. Environmental protection: Plasma degradation of pollutants reduces wastewater discharge, the water circulation rate is increased by more than 30%, the energy consumption of ferrocene production is reduced by 25%, and the COD value of wastewater is decreased by 80%, meeting the green chemical industry standards.

[0050] 2. High efficiency: The purification time is shortened to 2 - 3 hours, while the traditional method requires 4 - 6 hours. The product purity reaches 99.5% and the yield is over 80%.

[0051] Although the embodiments of the present invention have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principle and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

[0052] The above describes the present invention and its implementation manners. This description is not restrictive. What is shown in the drawings is only one of the implementation manners of the present invention, and the actual application is not limited thereto. Generally speaking, if those of ordinary skill in the art are inspired by it and design similar ways and embodiments without creative efforts without departing from the purpose of the present invention, they shall fall within the protection scope of the present invention.

Claims

1. An environmentally friendly and green purification method for ferrocene, characterized in that: It includes the following steps: (1) Pretreatment: Pretreat the crude ferrocene by crushing it into uniform particles; (2) Plasma activation: Introduce the inert gas nitrogen into a closed reactor, generate low-temperature plasma through electrodes, treat the crude product, decompose macromolecular impurities and activate ferrocene molecules; (3) High-pressure steam injection: Inject high-pressure steam and combine with mechanical stirring to prevent caking; (4) Temperature-controlled sublimation: Heat the jacket of the purifier to maintain efficient sublimation of ferrocene; (5) Plasma assistance: Add a plasma generator in the steam injection area, use high-energy electron flow to promote the separation of ferrocene from impurities and reduce side reactions; (6) Condensation and separation: Provide water spray cooling, the mixed gas enters the spray tower, control the temperature of the cooling water, make ferrocene sublime into microcrystalline particles, and enter the solid-liquid separator with the water flow; (7) Plasma anti-blocking design: Coat the inner wall of the condensation pipeline with a plasma activation layer to reduce the wall sticking of ferrocene; (8) Recycling and environmental protection treatment: The separated water is treated by activated carbon adsorption and plasma oxidation to remove residual organic matter and then recycled to the spray system; (9) Tail gas purification: Decompose volatile organic compounds in the uncondensed gas through a plasma catalytic oxidation device and discharge it up to standard.

2. The environmentally friendly and green ferrocene purification method according to claim 1, wherein: In step (2), the power for generating low-temperature plasma by the electrodes is 50 - 200 W.

3. The environmentally friendly and green ferrocene purification method according to claim 2, characterized in that: In step (2), the treatment duration of the crude product is 10 - 30 min.

4. The environmentally friendly and green ferrocene purification method according to claim 3, characterized in that: In step (3), the pressure of the high-pressure steam is 0.4 - 0.8 MPa.

5. The environmentally friendly and green ferrocene purification method according to claim 4, characterized in that: In step (4), the jacket of the purifier is heated to 100 - 160 °C.

6. The environmentally friendly and green ferrocene purification method according to claim 5, characterized in that: In step (3), the rotation speed of the mechanical stirring is 50 - 100 r / min.

7. The environmentally friendly and green ferrocene purification method according to claim 6, characterized in that: In step (6), the temperature of the cooling water is controlled at 0 - 20 °C.

8. The environmentally friendly and green ferrocene purification method according to claim 7, characterized in that: In the purification method, the reactor material is made of heat-resistant and corrosion-resistant 316L stainless steel or quartz glass, and a quartz purification column is combined with the reactor.

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