CN114014762B - Crystallization refining method of tetrabutylammonium bromide - Google Patents
Crystallization refining method of tetrabutylammonium bromide Download PDFInfo
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- CN114014762B CN114014762B CN202111369007.7A CN202111369007A CN114014762B CN 114014762 B CN114014762 B CN 114014762B CN 202111369007 A CN202111369007 A CN 202111369007A CN 114014762 B CN114014762 B CN 114014762B
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
Abstract
The invention discloses a crystallization refining method of tetrabutylammonium bromide, which comprises the steps of adding a molten tetrabutylammonium bromide crude product into preheated solvent ethyl acetate, and then adopting a method of staged heating and cooling and ultrasonic coupling to perform continuous crystallization. The invention can greatly shorten the time required by the crystallization refining of tetrabutylammonium bromide, and has high yield and one-time crystallization rate of more than 99 percent.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a crystallization refining method of tetrabutylammonium bromide.
Background
Tetrabutylammonium bromide has a molecular formula of C 16 H 36 BrN is a common organic synthesis intermediate and phase transfer catalyst, and has extremely wide application in the aspects of chemical industry, new energy, epidemic prevention and the like. At present, the synthesis method of tetrabutylammonium bromide mainly takes tributylamine and bromobutane as raw materials and is prepared by quaternization reaction, the crystallization refining process mainly comprises the steps of removing solvent from tetrabutylammonium bromide obtained by the reaction, melting the obtained crude tetrabutylammonium bromide, and then adding the crude tetrabutylammonium bromide into solvent ethyl acetate for natural crystallization. The method has high concentration of the crystallization stock solution, and the solid-liquid ratio can be as high as (0.8-1): 1, the primary crystallization rate can reach 90-95%, and the process is simple. However, this method is too long, the crystallization time is as long as 3 days or more, and the production efficiency is extremely low.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a crystallization refining method of tetrabutylammonium bromide.
The invention provides a crystallization refining method of tetrabutylammonium bromide, which comprises the following steps:
s1, adding ethyl acetate into a reaction kettle, preheating to 30-35 ℃, then adding a molten tetrabutylammonium bromide crude product under the stirring condition, and carrying out ultrasonic treatment for 3-5min to obtain a crystallization stock solution;
s2, cooling the crystallization stock solution to 8-10 ℃, crystallizing for 2-3 hours under the stirring condition, then heating to 12-15 ℃, and carrying out ultrasonic treatment for 5-10min;
s3, cooling to 5-6 ℃, crystallizing for 4-5 hours under the stirring condition, then heating to 8-10 ℃, and carrying out ultrasonic treatment for 10-15 minutes;
s4, cooling to 4-5 ℃, adding a proper amount of ethyl acetate precooled to 4-5 ℃, crystallizing for 1-2h under the stirring condition, then heating to 6-7 ℃, and carrying out ultrasonic treatment for 10-15min;
s5, cooling to 3-4 ℃, crystallizing for 1-2h under the stirring condition, then carrying out solid-liquid separation, and removing the solvent from the collected crystals to obtain the refined tetrabutylammonium bromide crystals.
Preferably, in S1, the mass ratio of the tetrabutylammonium bromide crude product to the ethyl acetate is (0.8-1): 1.
preferably, in S4, the addition amount of the ethyl acetate is 10-20% of the mass of the crude tetrabutylammonium bromide product.
Preferably, in S1 and S2, the ultrasonic treatment has a frequency of 30-40kHZ and a power of 100-200W; wherein, the ultrasonic processing frequency and the power in S1 and S2 can be the same or different.
Preferably, in S3 and S4, the ultrasonic treatment has a frequency of 30-40kHZ and a power of 500-600W; wherein, the ultrasonic processing frequency and power in S3 and S4 can be the same or different.
Preferably, in S2-S4, the temperature rising rate is 3-5 ℃/h; wherein the rate of temperature rise in S2-S4 may be the same or different.
Preferably, in S2, the cooling rate is 10-15 ℃/h; s3, the cooling rate is 3-5 ℃/h; in S4-S5, the cooling rate is 1-2 ℃/h; wherein the cooling rates in S4-S5 may be the same or different.
Preferably, in S1-S5, the stirring speed is 50-150rpm; wherein the stirring speeds in S1-S5 may be the same or different.
The beneficial effects of the invention are as follows:
the invention provides a crystallization refining method of tetrabutylammonium bromide, which is characterized in that tetrabutylammonium bromide obtained by reaction is continuously crystallized in ethyl acetate by adopting a method of coupling staged heating, cooling and ultrasonic wave, wherein the growth of crystallization crystal nucleus can be promoted by proper ultrasonic treatment, the crystallization speed can be accelerated, the system can be regulated by coupling staged heating, cooling and ultrasonic wave treatment and adding a small amount of solvent at proper time, the formation process of crystallization crystal grains can be regulated and controlled, the uniformity of a crystallization system in the crystallization refining process can be improved, the phenomenon of stirring and locking caused by uneven precipitation of crystals can be avoided, the primary crystallization rate and the crystallization purity can be improved, and the crystallization refining process can be accelerated. The invention can greatly shorten the time required by the crystallization and refining of tetrabutylammonium bromide, and has high yield, low impurity content, high purity and more than 99 percent of primary crystallization rate.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
A crystallization refining method of tetrabutylammonium bromide comprises the following steps:
s1, adding ethyl acetate into a reaction kettle, preheating to 33 ℃, then adding a molten tetrabutylammonium bromide crude product under the stirring condition of 100rpm, and carrying out ultrasonic treatment for 4min under the conditions of the frequency of 40kHZ and the power of 150W to obtain a crystal stock solution, wherein the mass ratio of the tetrabutylammonium bromide crude product to the ethyl acetate is 0.9:1, a step of;
s2, cooling the crystallization stock solution to 9 ℃ at a cooling rate of 12 ℃/h, crystallizing for 2.5h under a stirring condition of 100rpm, then heating to 13 ℃ at a heating rate of 4 ℃/h, and performing ultrasonic treatment for 8min under a condition that the frequency is 40kHZ and the power is 150W;
s3, cooling to 5 ℃ at a cooling rate of 4 ℃/h, crystallizing for 4.5h under a stirring condition of 100rpm, then heating to 9 ℃ at a heating rate of 4 ℃/h, and performing ultrasonic treatment for 12min under a condition that the frequency is 40kHZ and the power is 550W;
s4, cooling to 4.5 ℃ at a cooling rate of 1.5 ℃/h, adding ethyl acetate which is equivalent to 15% of the mass of the tetrabutylammonium bromide crude product and precooled to 4.5 ℃, crystallizing for 1.5h under the stirring condition of 100rpm, then heating to 6.5 ℃ at a heating rate of 4 ℃/h, and carrying out ultrasonic treatment for 12min under the conditions of 40kHZ and 550W of power;
s5, cooling to 3.5 ℃ at a cooling rate of 1.5 ℃/h, crystallizing for 1.5h under the stirring condition of 100rpm, then carrying out solid-liquid separation, and removing the solvent from the collected crystals to obtain the refined tetrabutylammonium bromide crystals.
The total crystallization refining time of the method is less than 24 hours, the primary crystallization rate is 99.5%, and the technical indexes of the obtained product are shown in the following table:
as can be seen from the table, the tetrabutylammonium bromide obtained by the crystallization refining method has high purity and low impurity content, and can meet the requirement of standardization.
Example 2
A crystallization refining method of tetrabutylammonium bromide comprises the following steps:
s1, adding ethyl acetate into a reaction kettle, preheating to 30 ℃, then adding a molten tetrabutylammonium bromide crude product under the stirring condition of 50rpm, and carrying out ultrasonic treatment for 3min under the conditions of the frequency of 30kHZ and the power of 100W to obtain a crystal stock solution, wherein the mass ratio of the tetrabutylammonium bromide crude product to the ethyl acetate is 0.8:1, a step of;
s2, cooling the crystallization stock solution to 10 ℃ at a cooling rate of 10 ℃/h, crystallizing for 2h under a stirring condition of 50rpm, then heating to 12 ℃ at a heating rate of 3 ℃/h, and carrying out ultrasonic treatment for 5min under a condition that the frequency is 30kHZ and the power is 100W;
s3, cooling to 5 ℃ at a cooling rate of 3 ℃/h, crystallizing for 4h under a stirring condition of 50rpm, then heating to 8 ℃ at a heating rate of 3 ℃/h, and performing ultrasonic treatment for 10min under a condition that the frequency is 30kHZ and the power is 500W;
s4, cooling to 4 ℃ at a cooling rate of 1 ℃/h, adding ethyl acetate which is equivalent to the mass of the tetrabutylammonium bromide crude product and is precooled to 4 ℃ and is crystallized for 1h under the stirring condition of 50rpm, then heating to 6 ℃ at a heating rate of 3 ℃/h, and carrying out ultrasonic treatment for 10min under the conditions of 30kHZ frequency and 500W power;
s5, cooling to 3 ℃ at a cooling rate of 1 ℃/h, crystallizing for 1h under a stirring condition of 50rpm, then carrying out solid-liquid separation, and removing the solvent from the collected crystals to obtain refined tetrabutylammonium bromide crystals.
The total crystallization refining time of the method is less than 24 hours, and the primary crystallization rate is 99.1 percent.
Example 3
A crystallization refining method of tetrabutylammonium bromide comprises the following steps:
s1, adding ethyl acetate into a reaction kettle, preheating to 35 ℃, then adding a molten tetrabutylammonium bromide crude product under the stirring condition of 150rpm, and carrying out ultrasonic treatment for 5min under the conditions of the frequency of 40kHZ and the power of 200W to obtain a crystallization stock solution, wherein the mass ratio of the tetrabutylammonium bromide crude product to the ethyl acetate is 1:1, a step of;
s2, cooling the crystallization stock solution to 8 ℃ at a cooling rate of 15 ℃/h, crystallizing for 3h under a stirring condition of 150rpm, then heating to 15 ℃ at a heating rate of 5 ℃/h, and performing ultrasonic treatment for 10min under a condition that the frequency is 40kHZ and the power is 200W;
s3, cooling to 6 ℃ at a cooling rate of 5 ℃/h, crystallizing for 5h under a stirring condition of 150rpm, heating to 10 ℃ at a heating rate of 5 ℃/h, and performing ultrasonic treatment for 15min under a condition that the frequency is 40kHZ and the power is 600W;
s4, cooling to 5 ℃ at a cooling rate of 2 ℃/h, adding ethyl acetate which is equivalent to 20% of the mass of the tetrabutylammonium bromide crude product and precooled to 5 ℃, crystallizing for 2h under the stirring condition of 150rpm, then heating to 7 ℃ at a heating rate of 5 ℃/h, and carrying out ultrasonic treatment for 15min under the conditions of 40kHZ frequency and 600W power;
s5, cooling to 4 ℃ at a cooling rate of 2 ℃/h, crystallizing for 2h under a stirring condition of 150rpm, then carrying out solid-liquid separation, and removing the solvent from the collected crystals to obtain refined tetrabutylammonium bromide crystals.
The total crystallization refining time of the method is less than 24 hours, and the primary crystallization rate is 99.2 percent.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (5)
1. The crystallization refining method of tetrabutylammonium bromide is characterized by comprising the following steps:
s1, adding ethyl acetate into a reaction kettle, preheating to 30-35 ℃, then adding a molten tetrabutylammonium bromide crude product under the stirring condition, and carrying out ultrasonic treatment for 3-5min to obtain a crystallization stock solution;
s2, cooling the crystallization stock solution to 8-10 ℃, crystallizing for 2-3 hours under the stirring condition, then heating to 12-15 ℃, and carrying out ultrasonic treatment for 5-10min;
s3, cooling to 5-6 ℃, crystallizing for 4-5 hours under the stirring condition, then heating to 8-10 ℃, and carrying out ultrasonic treatment for 10-15 minutes;
s4, cooling to 4-5 ℃, adding a proper amount of ethyl acetate precooled to 4-5 ℃, crystallizing for 1-2h under the stirring condition, then heating to 6-7 ℃, and carrying out ultrasonic treatment for 10-15min;
s5, cooling to 3-4 ℃, crystallizing for 1-2 hours under the stirring condition, then carrying out solid-liquid separation, and removing the solvent from the collected crystals to obtain refined tetrabutylammonium bromide crystals;
in S1 and S2, the ultrasonic treatment frequency is 30-40kHZ, and the power is 100-200W;
in S3 and S4, the ultrasonic treatment frequency is 30-40kHZ, and the power is 500-600W;
in S4, the addition amount of the ethyl acetate is 10-20% of the mass of the crude product of tetrabutylammonium bromide.
2. The method for purifying tetrabutylammonium bromide crystals according to claim 1, wherein in S1, the mass ratio of tetrabutylammonium bromide to ethyl acetate is (0.8-1): 1.
3. the method for purifying tetrabutylammonium bromide crystals according to claim 1, wherein the temperature rising rate is 3 to 5 ℃/h in S2 to S4.
4. The crystalline purification method of tetrabutylammonium bromide according to claim 1, wherein in S2, the cooling rate is 10-15 ℃/h; s3, the cooling rate is 3-5 ℃/h; in S4-S5, the cooling rate is 1-2 ℃/h.
5. The method for purifying tetrabutylammonium bromide crystals according to claim 1, wherein the stirring speed is 50 to 150rpm in S1 to S5.
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| US3965178A (en) * | 1973-08-19 | 1976-06-22 | Continental Oil Company | Method for preparing tetrabutylammonium bromide |
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