CN115819471A - Preparation method of crystal ferrocene - Google Patents

Abstract

The invention belongs to the technical field of ferrocene production and preparation, and discloses a preparation method of crystal ferrocene, which comprises the steps of using methanol as a solvent, reacting ferrous chloride with sodium cyclopentadienyl to generate a crude product of ferrocene, washing, extracting, filtering, concentrating, cooling to obtain a crystal suspension, filtering, drying and screening to obtain crystal granular ferrocene, so that the problems of easy powder flying and poor environmental protection when the powder ferrocene is used are solved. The method has the advantages of simple operation, easy control of conditions, thorough dissolving effect, less residue, capability of effectively improving the performance of the product, omission of a granulation process, improvement of production efficiency, large granularity, reduction of impurity occlusion and entrainment, contribution to improvement of product purity, complete appearance of the obtained crystal granular ferrocene, purity of more than or equal to 99 percent, free iron of less than or equal to 100ppm, granularity of 20-120 meshes, yield of more than 85 percent, single solvent, convenience in recycling and application, and suitability for application of the ferrocene in the field of industrial production.

Description

Preparation method of crystal ferrocene

Technical Field

The invention relates to the technical field of ferrocene production and preparation, in particular to a preparation method of crystal ferrocene.

Background

Ferrocene, whose chemical name is cyclopentadienyl iron, is an organic transition metal compound having aromatic properties. The product is orange yellow powder at normal temperature, has camphor smell, is insoluble in water, and is easily soluble in organic solvents such as benzene, diethyl ether, gasoline, diesel oil, etc. Melting point 172-174 deg.C, boiling point 249 deg.C, sublimation temperature above 100 deg.C, chemical formula of C10H10Fe, and molecular weight 186.03. The ferrocene which is used as an important organic chemical raw material and intermediate does not react with acid, alkali and ultraviolet rays, has stable chemical property and is not decomposed within 400 ℃. The molecule of the compound has polarity, high thermal stability, chemical stability and radiation resistance, and can be widely applied to industries such as industry, agriculture, medicine, aerospace, energy conservation, environmental protection and the like. The appearance, purity and free iron index of the product directly have great influence on the application of the product and the quality of the subsequent synthesized product, and the industry has special requirements on the granularity besides high requirements on the content and free iron.

The crystal ferrocene is synthesized in the production process of the ferrocene, the ferrocene is effectively purified and separated by an extraction and filtration technology, a supersaturated solution is formed by concentration, and then the crystal ferrocene is polymerized with each other by cooling crystallization to form crystal particles; at present, ferrocene produced by a steam distillation method and a sublimation separation method which are commonly used in industry is often powdery, has small granularity and has higher index of free iron.

Disclosure of Invention

The invention mainly aims to provide a preparation method of crystal ferrocene, which can effectively solve the problems mentioned in the background technology.

In order to achieve the purpose, the invention adopts the technical scheme that:

a preparation method of crystal ferrocene mainly comprises the following steps:

(1) Putting dicyclopentadiene into a kettle, controlling the external temperature at 200-250 ℃, controlling the temperature in the kettle at 150-200 ℃, heating and depolymerizing under a stirring state, controlling the temperature at the top of the tower at 40-45 ℃, receiving monocyclopentadiene fraction, and storing at 0-20 ℃ for later use.

(2) Mixing iron powder and ferric trichloride according to a mass ratio of 1-6, adding the mixture into a reaction kettle, adding a solvent with a mass ratio of 1.

(3, mixing the monocyclopentadiene obtained in the step (1) with 30% of liquid sodium methoxide or sodium ethoxide, wherein the mass ratio of the monocyclopentadiene to the 30% of liquid sodium methoxide or sodium ethoxide to the iron powder is 8-10.

(4) And (3) heating and steaming to remove the solvent methanol in the ferrocene solid-liquid mixture obtained in the step (3), recovering the solvent methanol for recycling, evaporating to dryness, washing with water in a mass ratio of 1:8 to 15 of solvent extraction.

(5) And (3) evaporating 50-85% of solvent in the ferrocene solution obtained in the step (4) under the heating and stirring state, then gradually and gradiently cooling to-10-30 ℃ under the condition that the stirring speed is 60-100 rpm to obtain a crystal suspension, filtering out a mother solution for recycling, collecting crystals, drying and screening to obtain the orange crystal granular ferrocene.

Preferably, in the step (1), the tower top temperature is preferably controlled at 41-43 ℃, the content of the received monocyclopentadiene fraction is more than or equal to 98 percent, and the monocyclopentadiene fraction is stored at-15-20 ℃ and used within 24 hours.

Preferably, in the step (2), the solvent may be one or any combination of methanol, ethanol, chloroform, dichloromethane, dichloroethane, tetrahydrofuran, toluene and xylene, and when the boiling point of the solvent is high, the time for removing the solvent is long, the energy consumption is high, and when the boiling point is too low, the solvent is volatile, the reaction is not stable enough, and the single type of solvent is convenient for recycling. Preferably, the solvent is selected to be methanol, and iron powder and ferric trichloride are added: the mass ratio of methanol is 1.

Preferably, in the step (3), the solvent contained in the raw material 30% sodium methoxide and the methanol generated after the reaction are the same as the methanol solvent, and preferably 30% sodium methoxide is used, so that the raw material is convenient to recycle.

Preferably, in the step (4), the solvent may be one or any combination of methanol, ethanol, chloroform, dichloromethane, dichloroethane, tetrahydrofuran, toluene and xylene, and when the boiling point of the solvent is high, the time for removing the solvent is long, the energy consumption is high, when the boiling point is too low, the solvent is volatile, and when the solubility is too low, the amount used is too large, preferably dichloroethane.

Preferably, 50 to 85 percent of the solvent is distilled off in the S5, and the temperature is gradually reduced to-10 to 30 ℃ in a gradient manner under the condition that the stirring speed is 60 to 100rpm, so as to obtain the crystal suspension.

Compared with the prior art, the invention has the following beneficial effects:

(1) The screening of the solvent system is one of the important innovations of the invention, and a proper solvent system is selected through the determination and research of the polarity and the solubility of the solvent and is matched with the raw materials, so that the solvent is convenient to recycle and reuse.

(2) The proper raw material proportion and reaction temperature are favorable for improving the yield of the product and reducing the residual raw materials, and the generated ferrocene is separated and extracted by water washing, extraction and filtration, so that the purity is high and the impurities are few.

(3) The cooling crystallization mode is simple to operate in a stirring state after the solvent is removed, and the particle size of the crystal can be adjusted by controlling the cooling rate and the stirring speed, so that the obtained crystal has uniform particle size, high purity and complete crystal appearance.

(4) The mother liquor separated after crystallization can be recycled, the purity of the obtained crystal granular ferrocene is more than or equal to 99 percent, the free iron is less than or equal to 100ppm, the granularity is between 20 and 120 meshes, and the yield can reach more than 85 percent.

Drawings

FIG. 1 is a picture of the appearance of commercially available powdered ferrocene produced by a conventional process;

FIG. 2 is a picture of the appearance of crystalline ferrocene obtained according to an embodiment of the present invention.

Detailed Description

In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.

Example 1

(1) Weighing 10kg of iron powder and 50kg of ferric chloride, mixing, putting into a reactor, slowly adding 210kg of methanol, and reacting for 8 hours under the condition of 80-100 ℃ in a closed stirring manner to generate a ferrous chloride methanol solution for later use.

(2) Weighing 400kg of 30% liquid sodium methoxide, putting the liquid sodium methoxide into a reactor, stirring and adjusting the temperature to 10-20 ℃, slowly adding 90kg of the prepared monocyclopentadiene with the content of 98.3% into the reactor, and carrying out closed stirring reaction for 2h at the temperature of 0-20 ℃ to generate a sodium cyclopentadienide solution for later use.

(3) Slowly adding the sodium cyclopentadienyl solution generated in the step (2) into the ferrous chloride methanol solution in the step (1), carrying out closed stirring reaction for 4 hours at the temperature of 60-80 ℃ to generate a ferrocene crude methanol solid-liquid mixture, concentrating, removing the solvent and recovering methanol for later use. Then 1500kg of water is added, after stirring and water washing twice, the crude ferrocene with earthy yellow is obtained by centrifugal drying, 103.4kg of crude ferrocene with earthy yellow is obtained, 1000kg of dichloroethane is added into a reactor, the solution is stirred, and then the solution is filtered, thus obtaining 1056.2kg of ferrocene dichloroethane solution.

(4) Putting the crude ferrocene product into a reactor, adding 1000kg of dichloroethane, stirring the solution, filtering to obtain ferrocene dichloroethane filtrate, heating, stirring and concentrating until the weight of the received and recovered dichloroethane reaches 700kg, stopping heating, adjusting the stirring speed to 80rpm, gradually cooling, cooling the kettle to 10 ℃ after 3 hours, filtering the mother liquor, collecting crystallized solids to obtain 301.6kg of mother liquor for later use, and screening the dried crystallized solids to obtain 43.2kg of crystal granular ferrocene with purity: 99.5%, free iron: 46ppm, the granularity is 30-80 meshes.

Example 2

(1) Weighing 10kg of iron powder and 50kg of ferric chloride, mixing, putting into a reactor, slowly adding 210kg of the recovered methanol obtained in the step (3) in the example 1, and reacting for 8 hours under the condition of 80-100 ℃ in a closed stirring manner to generate a ferrous chloride methanol solution for later use.

(2) Weighing 400kg of 30% liquid sodium methoxide, putting the liquid sodium methoxide into a reactor, stirring and adjusting the temperature to 10-20 ℃, slowly adding 90kg of the prepared monocyclopentadiene with the content of 98.6% into the reactor, and carrying out closed stirring reaction for 2h at the temperature of 0-20 ℃ to generate a sodium cyclopentadienide solution for later use.

(3) Slowly adding the sodium cyclopentadienyl solution generated in the step (2) into the ferrous chloride methanol solution in the step (1), carrying out closed stirring reaction for 4 hours at the temperature of 60-80 ℃ to generate a ferrocene crude methanol solid-liquid mixture, concentrating, removing the solvent and recovering methanol for later use. Then 1500kg of water is added, after stirring and water washing twice, the crude product of the khaki ferrocene is obtained by centrifugal drying, 105.3kg of crude product of the khaki ferrocene is obtained by throwing the crude product into a reactor, 1000kg of dichloroethane is added, and after stirring the solution, the solution is filtered to obtain 1055.3kg of ferrocene dichloroethane solution.

(4) Putting ferrocene dichloroethane solution into a reactor, adding 301.6kg of mother liquor obtained in the step (4) in the embodiment 1, heating, stirring and concentrating until the weight of the received and recovered dichloroethane reaches 970kg, stopping heating, adjusting the stirring speed to 80rpm, gradually cooling, reducing the temperature in the kettle to 10 ℃ after 3 hours, filtering the mother liquor, collecting crystallized solid to obtain 302.8kg of mother liquor for later use, and screening the dried crystallized solid to obtain 74.3kg of crystal ferrocene with purity: 99.3%, free iron: 39ppm, the granularity is 30-80 meshes, and the yield is 86.4%.

Example 3

(1) Weighing 10kg of iron powder and 50kg of ferric chloride, mixing, putting into a reactor, slowly adding 210kg of the recovered methanol obtained in the step (3) in the example 2, and reacting for 8 hours under the condition of 80-100 ℃ in a closed stirring manner to generate a ferrous chloride methanol solution for later use.

(2) Weighing 400kg of 30% liquid sodium methoxide, putting the liquid sodium methoxide into a reactor, stirring and adjusting the temperature to 10-20 ℃, slowly adding 90kg of the prepared monocyclopentadiene with the content of 98.8% into the reactor, and carrying out closed stirring reaction for 2h at the temperature of 0-20 ℃ to generate a sodium cyclopentadienide solution for later use.

(3) Slowly adding the sodium cyclopentadienyl solution generated in the step (2) into the ferrous chloride methanol solution in the step (1), carrying out closed stirring reaction for 4 hours at the temperature of 60-80 ℃ to generate a ferrocene crude methanol solid-liquid mixture, concentrating, removing the solvent and recovering methanol for later use. Then 1500kg of water is added, after stirring and water washing twice, the crude ferrocene with the earthy yellow color is obtained by centrifugal drying, 104.1kg of crude ferrocene with the earthy yellow color is obtained, 1000kg of dichloroethane is added into a reactor, the solution is stirred, and then the solution is filtered, thus obtaining 1053.9kg of ferrocene dichloroethane solution.

(4) Putting ferrocene dichloroethane solution into a reactor, adding 302.8kg of mother liquor obtained in the step (4) in the embodiment 1, heating, stirring and concentrating until the weight of the received and recovered dichloroethane reaches 970kg, stopping heating, adjusting the stirring speed to 80rpm, gradually cooling, reducing the temperature in the kettle to 10 ℃ after 3 hours, filtering the mother liquor, collecting crystallized solid to obtain 300.3kg of mother liquor for later use, and screening the dried crystallized solid to obtain 75.1kg of crystal ferrocene with purity: 99.6%, free iron: 46ppm, 30-80 mesh granularity and 87.3 percent yield.

Example 4

(1) Weighing 10kg of iron powder and 50kg of ferric chloride, mixing, putting into a reactor, slowly adding 210kg of the recovered methanol obtained in the step (3) in the example 3, and reacting for 8 hours under the condition of 80-100 ℃ in a closed stirring manner to generate a ferrous chloride methanol solution for later use.

(2) Weighing 400kg of 30% liquid sodium methoxide, putting the liquid sodium methoxide into a reactor, stirring and adjusting the temperature to 10-20 ℃, slowly adding 90kg of the prepared monocyclopentadiene with the content of 98.5% into the reactor, and carrying out closed stirring reaction for 2h at the temperature of 0-20 ℃ to generate a sodium cyclopentadienide solution for later use.

(3) Slowly adding the sodium cyclopentadienyl solution generated in the step (2) into the ferrous chloride methanol solution in the step (1), carrying out closed stirring reaction for 4 hours at the temperature of 60-80 ℃ to generate a ferrocene crude methanol solid-liquid mixture, concentrating, removing the solvent and recovering methanol for later use. Then 1500kg of water is added, after stirring and water washing are carried out twice, 102.9kg of crude khaki ferrocene product is obtained by centrifugal drying, 1000kg of dichloroethane is added into a reactor, after the solution is stirred, the solution is filtered, and 1055.1kg of ferrocene dichloroethane solution is obtained.

(4) Putting ferrocene dichloroethane solution into a reactor, adding 300.3kg of mother liquor obtained in the step (4) in the embodiment 1, heating, stirring and concentrating until the weight of the received and recovered dichloroethane reaches 970kg, stopping heating, adjusting the stirring speed to 80rpm, gradually cooling, reducing the temperature in the kettle to 10 ℃ after 3 hours, filtering the mother liquor, collecting crystallized solid to obtain 301.8kg of mother liquor for later use, and screening the dried crystallized solid to obtain 74.9kg of crystal ferrocene with purity: 99.5%, free iron: 39ppm, the granularity is 30-80 meshes, and the yield is 87.1%.

The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (5)

1. A preparation method of crystal ferrocene is characterized by comprising the following steps: the method mainly comprises the following steps:

s1, putting dicyclopentadiene into a kettle, controlling the external temperature at 200-250 ℃, controlling the temperature in the kettle at 150-200 ℃, heating and depolymerizing under a stirring state, controlling the temperature at the top of the tower at 40-45 ℃, receiving monocyclopentadiene fraction, and storing at 0-20 ℃ for later use;

s2, mixing iron powder and ferric trichloride according to a mass ratio of 1;

and S3, mixing the monocyclopentadiene obtained in the S1 with 30% of liquid sodium methoxide or sodium ethoxide, wherein the mass ratio of the monocyclopentadiene: 30% liquid sodium methoxide or sodium ethoxide: the iron powder is 8-10: 1, carrying out heat preservation reaction for 0.5-3 h under the stirring state at the temperature of 0-20 ℃ to generate a sodium cyclopentadienyl solution, then mixing the sodium cyclopentadienyl solution with a ferrous chloride solution generated by S2, and carrying out heat preservation reaction for 2-6 h under the stirring state at the temperature of 60-100 ℃ to generate a ferrocene crude methanol solid-liquid mixture;

s4, heating and steaming to remove the solvent methanol in the ferrocene solid-liquid mixture obtained in the S3, and recovering for recycling;

s5, distilling and removing 50-85% of solvent in the ferrocene solution obtained in the S4 under the heating and stirring state, then gradually and gradiently cooling to-10-30 ℃ under the condition that the stirring speed is 60-100 rpm to obtain crystal suspension, filtering the mother solution for recycling, collecting crystals, drying and screening to obtain orange crystal granular ferrocene.

2. A process for preparing crystalline ferrocene according to claim 1, wherein: the solvent used in S2 is methanol.

3. A process for preparing crystalline ferrocene according to claim 1, wherein: and (2) mixing the monocyclopentadiene in the S3 with 30% of liquid sodium methoxide according to the mass ratio of 8-10 to 30-45, stirring and reacting for 0.5-3 hours at the temperature of 0-20 ℃, then mixing the monocyclopentadiene with a ferrous chloride methanol solution generated in the S2, and stirring and reacting for 2-6 hours at the temperature of 60-100 ℃ to generate the ferrocene.

4. A process for preparing crystalline ferrocene according to claim 1, wherein: and after evaporation to dryness in the S4, washing the mixture for 1 to 2 hours with water in a mass ratio of 1 to 5 under the condition of 20 to 40 ℃ in a stirring state, collecting solids, and then adding the mixture into the mixture in a mass ratio of 1: 8-15, wherein the solvent used for extraction can be one or any combination of methanol, ethanol, chloroform, dichloromethane, dichloroethane, tetrahydrofuran, toluene and xylene.

5. A process for preparing crystalline ferrocene according to claim 1, wherein: and (5) evaporating 50-85% of the solvent in the S5, and gradually reducing the temperature to-10-30 ℃ in a gradient manner under the condition that the stirring speed is 60-100 rpm to obtain a crystal suspension.

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