JPWO2014034500A1 - Acetonitrile purification method - Google Patents

Abstract

The method for purifying acetonitrile according to the present invention comprises a step of supplying a reaction tank with crude acetonitrile obtained by an ammoxidation reaction and an alkali, and a step of obtaining a distillate by distilling the reaction solution. And supplying acetamide and / or acetic acid to the reaction vessel.

Description

  The present invention relates to a method for purifying acetonitrile.

  At present, commercially available acetonitrile is mainly crude acetonitrile obtained as a by-product in the production of acrylonitrile or methacrylonitrile by catalytic ammoxidation reaction of propylene or isobutene, ammonia and oxygen. Collected and purified.

  Acetonitrile is used as a solvent for chemical reaction, particularly a solvent used for synthesis and purification of pharmaceutical intermediates, a moving bed solvent for high performance liquid chromatography, and the like. Recently, acetonitrile has also been used as a solvent for synthesizing and purifying DNA, a solvent for synthesizing organic EL materials, a cleaning solvent for electronic parts, and the like. In the case of the use as described above, acetonitrile purified to a particularly high purity is required.

  The crude acetonitrile obtained by the ammoxidation reaction contains various impurities. To date, a method of mixing crude acetonitrile and alkali has been proposed as a method for purifying crude acetonitrile.

  In Patent Document 1, when purifying crude acetonitrile containing impurities, an alkali is added to adjust the pH to be in the range of 10 to 13.5, heat treatment, and further treatment with a formaldehyde adjustment solution to acrylonitrile. And a method for decomposing hydrocyanic acid is disclosed. Examples of the alkali added to the crude acetonitrile include sodium hydroxide, potassium hydroxide, and ammonia.

  Patent Document 2 discloses a method for dehydrating and purifying acetonitrile in which an alkali is added to hydrous acetonitrile and stirred at 10 ° C. to 50 ° C. to separate and remove the aqueous phase. In addition to alkali and water, the separated aqueous phase contains hydrogen cyanide and acrylonitrile, and it is described that this aqueous phase can be used as an alkali source in the purification step of acetonitrile described in Patent Document 1. Yes.

  Patent Document 3 discloses a method in which acetonitrile by-produced by an ammoxidation reaction is alkali-treated at 60 ° C. to decompose hydrogen cyanide and acrylonitrile, and then further alkali is added in a dehydration tower to dehydrate acetonitrile. The aqueous alkali solution used for the treatment of acetonitrile is recovered by concentration by heating and reused as an alkali source supplied to the dehydration tower.

JP-A-48-81816 JP-A-55-153757 JP 2000-128847 A

  In the purification steps of acetonitrile disclosed in the above patent documents, metal hydroxides such as sodium hydroxide and potassium hydroxide and / or ammonia are used as alkali sources. However, as a result of investigations by the present inventors, it has been clarified that, in the conventional technique, acetonitrile is simultaneously hydrolyzed when impurities are decomposed using alkali. When acetonitrile is decomposed, the acetonitrile changes to an organic acid such as acetic acid, which causes a decrease in the production amount of high-purity acetonitrile. In addition, since the organic acid is generated as described above, the pH is lowered, so that more alkali is required for the decomposition of impurities. Since hydrolysis of acetonitrile is promoted by alkali, increasing the amount of alkali added is not a preferable method.

  In view of the problems of the above-described conventional technology, the present invention aims to provide a method for purifying acetonitrile that can suppress hydrolysis of acetonitrile when decomposing impurities and improve the production amount of high-purity acetonitrile. And

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention supplied acetonitrile and / or acetic acid to a reaction vessel for decomposing impurities such as acrylonitrile and hydrocyanic acid contained in crude acetonitrile. It was discovered that hydrolysis was suppressed and the present invention was reached. Furthermore, when attention was paid to acetamide and acetic acid generated during the purification process, and a method of using this was studied, hydrolysis of acetonitrile was suppressed even when an alkali containing the acetamide and / or acetic acid was used. I found.

That is, the present invention is as follows.
[1]
Supplying crude acetonitrile obtained by an ammoxidation reaction and alkali to a reaction vessel to obtain a reaction solution;
Distilling the reaction liquid to obtain a distillate;
Supplying acetamide and / or acetic acid to the reaction vessel;
A method for purifying acetonitrile, comprising:
[2]
In the step of distilling the reaction liquid to obtain a distillate, the reaction liquid is introduced into a distillation column to remove high boiling substances, and then the distillate obtained is supplied to a dehydration tower, The method for purifying acetonitrile according to the above [1], comprising a step of separating the aqueous phase in addition to the dehydration tower.
[3]
The method for purifying acetonitrile according to the above [2], wherein the alkali supplied to the reaction vessel contains a part of the aqueous phase.
[4]
The method for purifying acetonitrile according to the above [2] or [3], comprising adding the alkaline aqueous solution to the dehydration tower at 40 ° C. or higher and 90 ° C. or lower.
[5]
The manufacturing method of high purity acetonitrile including refine | purifying acetonitrile using the purification method of acetonitrile in any one of said [1]-[4].

  According to the method for purifying acetonitrile of the present invention, hydrolysis of acetonitrile in a reaction tank for decomposing impurities can be suppressed, and the production amount of high-purity acetonitrile can be improved.

FIG. 1 is an example of a schematic diagram of an acetonitrile production apparatus according to an embodiment of the present invention. FIG. 2 is another example of a schematic diagram of an acetonitrile production apparatus according to an embodiment of the present invention.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. The dimensional ratios of the devices and members are not limited to the illustrated ratios.

  The method for purifying acetonitrile in the present embodiment includes a step of supplying crude acetonitrile obtained by an ammoxidation reaction and an alkali to a reaction vessel to obtain a reaction solution, and distilling the reaction solution to obtain a distillate. And a step of supplying acetamide and / or acetic acid to the reaction vessel.

  As shown in FIG. 1, as an example of the acetonitrile purification apparatus in the present embodiment, there is a concentration tower 1 into which crude acetonitrile is introduced, and the high-boiling separation tower 3 is connected to the concentration tower 1 via a reaction tank 2, The dehydration tower 4, the low-boiling separation tower 5, and the product tower 6 are connected in this order.

  Crude acetonitrile is obtained as a by-product when, for example, acrylonitrile or methacrylonitrile is produced from propylene, propane, isobutene, or isobutane by a catalytic ammoxidation reaction. In general, the product of the ammoxidation reaction is subjected to extractive distillation, and crude acetonitrile is recovered as a fraction separate from the fraction containing acrylonitrile or methacrylonitrile as a main component. Here, “crude acetonitrile” indicates a fraction having the highest content of acetonitrile among fractions obtained by extractive distillation of a product of an ammoxidation reaction. Crude acetonitrile is generally separated from a distillation column which recovers most of acrylonitrile or methacrylonitrile, and is usually 5 to 40% by mass of acetonitrile, 50 to 95% by mass of water, hydrogen cyanide, allyl alcohol, Many types such as oxazole, acrylonitrile, propionitrile, acetone, hydrocyanic acid, methacrylonitrile, cis- and trans-crotonnitrile, acrylic acid, methyl acrylate, methacrylic acid, methyl methacrylate, acrolein, methacrolein, ammonia Contains impurities.

  Crude acetonitrile is sent from line 7 to the middle stage of acetonitrile concentration tower 1. The acetonitrile concentration tower 1 is an upright distillation tower, and has a reboiler (not shown) at the bottom and a condenser (not shown) at the top. While removing hydrogen cyanide from the top of the column (line 8) and water from the bottom of the column (line 9), concentrated crude acetonitrile is withdrawn from the middle of the column (line 10). Hereinafter, the extracted crude acetonitrile is also referred to as “concentrated crude acetonitrile”. The line 10 is provided with a side cut condenser (not shown). The side cut condenser condenses gaseous concentrated crude acetonitrile. Liquid concentrated crude acetonitrile flowing out from the side cut condenser flows into the reaction vessel 2. The concentration of acetonitrile in the concentrated crude acetonitrile supplied from the concentrating tower 1 to the reaction vessel 2 is usually 50 to 70% by mass, and additionally contains 25 to 70% by mass of water, hydrogen cyanide, acrylonitrile, allyl alcohol and other impurities. It is out.

  In the reaction tank 2, the concentrated crude acetonitrile is treated with an alkali to convert acrylonitrile and hydrogen cyanide contained as impurities into a polymer such as succinonitrile and dimer. From the viewpoint of sufficiently proceeding the polymerization reaction, the temperature of the reaction vessel 2 is preferably 50 ° C. or higher and 80 ° C. or lower, more preferably 60 ° C. or higher and 75 ° C. or lower, and 3.0 hours or longer and 15 hours or shorter, still more preferably. The reaction is carried out at 60 ° C. or more and 75 ° C. or less for 4.0 hours or more and 10 hours or less.

  In the purification method in the present embodiment, acetamide and / or acetic acid can be added to the reaction vessel 2 from the line 11 or the like. Acetonitrile undergoes hydrolysis at a high temperature, and the hydrolysis becomes particularly remarkable at a temperature of 50 ° C. or higher. Therefore, under the reaction conditions in the reaction tank 2, it is normal that acetonitrile is easily decomposed into acetic acid and ammonia through acetamide by hydrolysis, and the recovered amount of acetonitrile is reduced. However, it was found that when acetamide and / or acetic acid was supplied to the reaction tank 2, hydrolysis of acetonitrile in the reaction tank 2 was suppressed, and the amount of acetonitrile recovered was improved. The concentration of acetamide and / or acetic acid supplied to the reaction tank 2 is not particularly limited, but the concentration of acetamide and / or acetic acid in the supply liquid such as the line 11 is 0.50% by mass or more and 25% by mass or less. More preferably, it is 1.0 mass% or more and 20 mass% or less, More preferably, it is 3.0 mass% or more and 15 mass% or less. Considering the amount of inflow from the concentrating tower 1 to the reaction tank 2 and the amount of liquid supplied to the line 11, etc., the concentration of acetamide and / or acetic acid in the reaction tank 2 is 0.050 mass% or more and 2.5 mass% or less. More preferably, it is 0.25 mass% or more and 1.5 mass% or less, More preferably, it is 0.5 mass% or more and 1.5 mass% or less. That is, when the concentration of acetamide and / or acetic acid contained in the supply liquid such as the line 11 is 0.5% by mass or more, the hydrolysis inhibition effect of acetonitrile tends to appear remarkably. Further, when the content is 25% by mass or less, not only can the above-mentioned effects be sufficiently ensured, but also the viscosity of the above-mentioned supply liquid can be reduced, and sufficient handleability tends to be ensured.

  The concentration of acetamide and / or acetic acid in the alkali supplied from the line 11 can be adjusted by adjusting the temperature and residence time of the aqueous alkali solution supplied to the dehydration tower 4.

  Acetonitrile is converted to acetamide under basicity, further liberating ammonia and sequentially hydrolyzed to acetic acid. From the study by the present inventors, it was found that the reaction rate at which acetonitrile is converted into acetamide is slower than the rate at which acetamide is converted into acetic acid. That is, the reaction in which acetonitrile is hydrolyzed to acetic acid is rate-limiting for the reaction in which acetonitrile is converted to acetamide.

  Acetamide and / or acetic acid has an effect of decreasing the rate of acetonitrile decomposition reaction, and is considered to suppress decomposition of acetonitrile. Industrial production of acetonitrile is often performed in a continuous process, and the supply of raw materials to the reaction vessel and the extraction of the reaction mixture are always adjusted to be balanced. Since it is almost impossible that only a specific component stays, supply of acetamide and / or acetic acid is required to reduce the rate of the decomposition reaction of acetonitrile. Further, when acetonitrile is produced by a discontinuous process, when the acetonitrile is decomposed into acetamide and acetic acid, and a certain amount of acetamide and / or acetic acid is produced, the decrease in the rate of the acetonitrile decomposition reaction may occur naturally. Conceivable. However, when acetonitrile is decomposed in the reaction tank, acetic acid is generated and the pH is lowered, so that decomposition of impurities such as acrylonitrile and hydrogen cyanide is delayed. In order to prevent this, a new alkali must be supplied to the reaction vessel, but the acetonitrile decomposition reaction is promoted by the alkali, so that the acetonitrile decomposition reaction further proceeds. Even in this case, increasing the relative amount of acetamide and / or acetic acid increases the effect of inhibiting the decomposition of acetonitrile, so it is effective to supply acetamide and / or acetic acid from outside the system.

  Therefore, in both the continuous process and the discontinuous process, by supplying acetamide and / or acetic acid to the reaction tank, it is possible to decompose impurities while suppressing decomposition of acetonitrile.

  The acetic acid fed to the reaction vessel need not be present purely as acetic acid. Acetic acid can suppress decomposition of acetonitrile without any problem in any form of acetate ion or acetate (such as sodium acetate or potassium acetate).

  The reaction solution in the reaction tank 2 is sent to the high boiling separation tower 3 through the line 12. From the viewpoint of separating high boiling substances, the high boiling separation tower 3 is preferably a vacuum distillation tower. Acetonitrile is recovered from the top of the high boiling separation tower 3 as an azeotropic composition mixture with water or a composition mixture close thereto, and liquefied with a condenser (not shown). A part of the condensate is refluxed to the high boiling separation tower 3 through a line (not shown), and the remainder is sent to the dehydration tower 4 through the line 14. Polymers such as succinonitrile and dimer, alkali, acetate, allyl alcohol, propionitrile, water and a small amount of acetonitrile produced in the reaction vessel 2 are separated from the line 13 at the bottom of the high boiling separation tower 3 to produce waste water. Send to processing equipment. A reboiler (not shown) that provides heat necessary for distillation is installed at the bottom of the column and supplies heat necessary for distillation.

  The pressure of the high boiling separation tower 3 is preferably 80 mmHg or more and 760 mmHg or less in terms of absolute pressure from the viewpoint of separation of high boilers and the suppression of decomposition of succinonitrile, dimer and the like generated in the reaction tank 2, More preferably, it is 100 mmHg or more and 300 mmHg or less. When the pressure is set in the above range, the tower bottom temperature is preferably 30 ° C. or higher and 80 ° C. or lower, more preferably 40 ° C. or higher and 60 ° C. or lower, and the tower top temperature is 20 ° C. or higher and 70 ° C. or lower. It is preferably 30 ° C. or higher and 50 ° C. or lower.

  In the dehydration tower 4, in addition to the distillate obtained from the top of the high boiling separation tower 3, a sufficient amount of alkali to extract water present in the distillate is an aqueous solution at 40 ° C. to 75 ° C. And added from line 15 and mixed. Subsequently, the acetonitrile phase can be obtained from the line 17 by removing the aqueous phase extracted and separated from 10 ° C. to 50 ° C. over 0.10 hours to 3.0 hours from the bottom of the dehydration tower 4. Although it does not specifically limit as aqueous alkali solution, It is preferable to use the aqueous solution of sodium hydroxide and / or potassium hydroxide.

  As shown in FIG. 2, another example of the schematic diagram of the purification apparatus for acetonitrile in the present embodiment is a diagram except that a part of the aqueous phase separated from the dehydration tower 4 is circulated in the reaction tank 2. 1 is the same device. That is, a part of the aqueous phase separated from the dehydration tower 4 is supplied to the reaction tank 2 from the line 11.

  In the purification method in the present embodiment, a part of the aqueous phase separated from the dehydration tower 4 can be circulated and used as an alkali source to be supplied to the reaction tank 2. By using the aqueous phase separated in the dehydration tower 4, it is not necessary to supply new alkali from outside the system, or the amount of alkali supplied from outside the system can be reduced, and the supply of alkali in the entire purification process Contributes to reducing the amount.

  Also in the dehydration tower 4, acetonitrile is slightly decomposed to produce acetamide and / or acetic acid. At this time, from the viewpoint of controlling the production of acetamide and / or acetic acid in the dehydration tower 4, it is preferable to warm the alkaline aqueous solution supplied to the dehydration tower 4. The temperature of the aqueous alkali solution supplied to the dehydration tower 4 is preferably 40 ° C. or higher and 90 ° C. or lower, more preferably 45 ° C. or higher and 75 ° C. or lower, and further preferably 45 ° C. or higher and 65 ° C. or lower. The residence time in the dehydration tower 4 is 0.10 hours to 3.0 hours, more preferably 0.20 hours to 2.8 hours. Since the aqueous phase extracted and separated from the dehydration tower 4 contains alkali, acetamide and / or acetic acid, introduction of this aqueous phase into the reaction tank 2 has an effect of suppressing hydrolysis of acetonitrile. On the other hand, the residence time of the reaction tank 2 is 3.0 hours or more and 15 hours or less, more preferably 4.0 hours or more and 10 hours or less, and is longer than the residence time of the dehydration tower 4. Therefore, the reaction tank 2 tends to facilitate the hydrolysis of acetonitrile. Even if the amount of acetonitrile hydrolyzed in the dehydration tower 4 is taken into account, the supply of acetamide and / or acetic acid greatly contributes to the effect of suppressing the decomposition of acetonitrile in the reaction tank 2, and the yield of high purity acetonitrile tends to increase rather. It is in. Therefore, by circulating a part of the aqueous phase separated from the dehydration tower 4 and using it as an alkali source to be supplied to the reaction tank 2, it is possible to reduce the alkali supply amount in the entire purification process and to suppress the decomposition of acetonitrile in the reaction tank 2. It is preferable from the viewpoint of achieving the two simultaneously.

  The extraction temperature in the dehydration tower 4 is preferably 5 ° C. or more and 40 ° C. or less from the viewpoint of lowering the moisture in acetonitrile flowing out from the line 17 and suppressing the hydrolysis of acetonitrile more than necessary. More preferably, it is 35 ° C. or lower. In order to maintain the extraction temperature, the liquid from the line 14 may be cooled in advance and supplied to the dehydration tower 4 or the main body of the dehydration tower 4 may be cooled. Here, the extraction temperature indicates the temperature in the dehydration tower 4, and more specifically, the internal liquid at the alkali feed position from the top liquid feed position of the high boiling separation tower 3 in the dehydration tower 4. Indicates temperature.

  The amount of alkali used in the dehydration tower 4 varies depending on the water content in acetonitrile, but is usually in the range of 10% by mass to 90% by mass, preferably 30% by mass to 60% by mass with respect to the water content in acetonitrile. It is. The amount of water in acetonitrile is preferably 10% by mass or less, more preferably 3% by mass or less by the method of extracting water with alkali.

  When at least a part of the bottom liquid (aqueous phase) of the dehydration tower 4 is sent to the reaction tank 2 through the line 11, the excess bottom liquid of the dehydration tower 4 is sent to the wastewater treatment facility through the line 16 and processed. The bottom liquid of the dehydration tower 4 mainly contains acetamide, acetic acid (including alkali salt), a small amount of acetonitrile, and the like in addition to sodium hydroxide and / or potassium hydroxide and water as alkalis.

  From the viewpoint of removing acrylonitrile and hydrogen cyanide from acetonitrile and suppressing hydrolysis of acetonitrile, the amount of liquid sent to the reaction tank 2 of the bottom liquid of the dehydration tower 4 is 1 per 1 mole of hydrogen cyanide in the internal liquid of the reaction tank 2. It is preferable to adjust the concentration to be 0.0 mol or more and 3.5 mol or less of sodium hydroxide and / or potassium hydroxide. In this case, the pH of the mixed solution in the reaction tank 2 is 12.0 ± 1.5. By recycling the bottom liquid of the dehydration tower 4 to the reaction tank 2, it is possible to eliminate or reduce the alkali added to the reaction tank 2 and reduce the amount of wastewater treatment of the bottom liquid of the dehydration tower 4. Furthermore, there is an advantage that acetonitrile contained in a small amount in the bottom liquid of the dehydration tower 4 can be recovered.

  Decreasing the amount of acetonitrile decomposed in the reaction tank 2 increases the mass of acetonitrile recovered from the top line 21 of the product column 6 which is the final distillation column. When the mass of high-purity acetonitrile to be produced is the same, the mass of crude acetonitrile supplied to the acetonitrile purification apparatus can be reduced, and downsizing of the acetonitrile purification apparatus can be achieved. Moreover, since acetonitrile to decompose | disassemble decreases, the amount of waste water which must be processed can be reduced, the size reduction of a waste water treatment facility and environmental load can be reduced.

  After dehydration in the dehydration tower 4, it is preferable to use two or more distillation towers in order to separate and remove a compound having a lower boiling point and a compound having a higher boiling point than acetonitrile. Specifically, the low boiling point compound is first separated and removed from the top of the low boiling separation tower 5 through the line 18, and the bottom liquid of the low boiling separation tower 5 is sent to the product tower 6 through the line 19. Thereafter, it is preferable to separate high-boiling compounds from the bottom of the product column 6 through a line 20 to obtain purified acetonitrile from the line 21 at the top of the column.

  In the low-boiling separation column 5 and the product column 6, the reflux ratio and the amount of low-boiling compounds and high-boiling compounds extracted can be appropriately determined so as to achieve a purification degree suitable for the purpose. Depending on the desired degree of purification, the reflux ratio of the low boiling separation column 5 and the product column 6 is preferably 1 or more and 50 or less, more preferably 2 or more and 30 or less. The reflux ratio is defined as a value obtained by dividing the mass refluxed to the distillation column by the mass discharged outside the distillation column. From the viewpoint of efficiently separating and removing impurities by distillation, it is preferable that the reflux ratio is stably maintained at a predetermined value during operation in purifying high-purity acetonitrile. The lower limit of the pressure in the low-boiling separation column 5 and the product column 6 is set so that components to be separated in the distillation column each have an appropriate boiling point, and is preferably 0.05 MPa or more in absolute pressure, more preferably Is 0.08 MPa or more, more preferably 0.09 MPa or more. The upper limit of the pressure is preferably 0.27 MPa or less in absolute pressure, more preferably 0.20 MPa or less, still more preferably 0.15 MPa or less. When set to the above preferable pressure, the bottom temperature of the low boiling separation column 5 and the product column 6 is preferably 80 ° C. or more and 95 ° C. or less, more preferably 80 ° C. or more and 88 ° C. or less, and the column top temperature is It is preferable that it is 70 degreeC or more and 90 degrees C or less, More preferably, it is 75 degreeC or more and 85 degrees C or less.

  The low boiling separation column 5 and the product column 6 are preferably a plate column or a packed column each having a condenser at the top and a reboiler at the bottom. Examples of the plate tower include a cross flow contact type having a downcomer and a countercurrent contact type having no downcomer. Further, a bubble bell type, a perforated plate type, a valve type, or the like can be used as the opening of the tray. The number of stages of the distillation column is not particularly limited as long as it is 10 or more, but is preferably 30 or more and 80 or less. As an example of the packed column, a column packed with an irregular packing and / or a regular packing can be used as the packing. As the irregular filling, for example, Raschig ring, Lessing ring, Pole ring, Berle saddle, Interlock saddle, Terrarette packing, Dixon ring or McMahon packing can be used. As the regular packing, a mesh-structured packing can be used. As materials for these irregular and regular packing materials, those made of magnetism, metal, plastic or carbon can be used. In addition, the packed tower can be provided with a liquid redistribution plate at an appropriate height to improve the gas-liquid contact efficiency.

  The pressure of the vapor supplied to the reboiler of the low boiling separation column 5 and the product column 6 is preferably 1.0 MPaG or less, more preferably 0.6 MPaG or less, from the viewpoint of making the temperature difference with the liquid to be heated appropriate. And

  As described above, in the present embodiment, the method for purifying acetonitrile is a first step of obtaining a reaction liquid by supplying crude acetonitrile obtained by an ammoxidation reaction, an alkali, and acetamide and / or acetic acid to a reaction vessel. And a second step of distilling a mixed solution of the reaction solution and the acetamide and / or acetic acid to obtain a distillate.

  The manufacturing method of high purity acetonitrile in this embodiment is a manufacturing method including refine | purifying acetonitrile using the purification method mentioned above. Here, in the production of high-purity acetonitrile, a conventionally known method can be used except that the purification method in the present embodiment is used. Here, “high purity” of high purity acetonitrile means a purity of 99.9% by mass or more.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

  Gas chromatography was used to measure the concentrations of acetonitrile, acrylonitrile, allyl alcohol, oxazole, propionitrile, and acetamide, and the conditions at that time were as follows.

  HP-6890 made by Hured Packard was used for gas chromatography, and DB-624 made by Agilent Technologies was used for the column. That is, the column had a length of 60 m, an inner diameter of 0.32 mm, and a film thickness of 5.0 μm. FID was used as the detector, and helium was used as the carrier gas.

The column temperature conditions were as follows.
Initial temperature: 70 ° C
Initial time: 10 minutes Temperature rising rate: 5.0 ° C / min Intermediate temperature: 120 ° C
Post time: 10 minutes Final temperature: 250 ° C

  The hydrogen cyanide concentration was measured by silver nitrate titration, the ammonia concentration was measured by ion chromatography, and the water concentration was measured by the Karl Fischer method.

  At the time of measuring the acetic acid concentration, it is considered that a part thereof is an alkali salt. Therefore, the pH was adjusted to 6 with sulfuric acid to be dissociated as acetic acid and analyzed by the gas chromatography.

  The sodium hydroxide concentration was measured by converting the hydroxide ion concentration by neutralization titration with acetic acid. Furthermore, the concentration of sodium ions was determined by ion chromatography, and converted and confirmed.

  Considering that the acetamide concentration and the acetic acid concentration are affected by the liquid temperature and the time required for the analysis, the liquid was cooled and analyzed quickly after sampling. In some cases, it was expressed as the total concentration of acetamide and acetic acid.

  Substances other than the above were not identified and quantified, but were balanced as other substances. In particular, in the reaction tank 2, acrylonitrile and hydrogen cyanide disappeared by reaction and polymerization, both alone and in combination, so these products were counted.

  The analysis sample was collected in an amount necessary for the analysis from the nozzle installed in the designated line in FIG. 1 or 2 so as to be a representative sample at the site, and analyzed by the above method.

[Experiment 1]
In a mixer, 500 g of concentrated crude acetonitrile composed of 65% by mass of acetonitrile (MeCN) and 35% by mass of water and 53.4 g of an alkaline liquid composed of water, sodium hydroxide and acetamide were added to prepare a mixed solution. The mixture was held for 5 hours while stirring at 70 ° C. The concentration of sodium hydroxide in the alkaline solution was 25% by mass, and the concentration of acetamide was 1% by mass.

Table 1 shows the composition of each solution and the decomposition rate of acetonitrile (MeCN). The acetonitrile decomposition rate was a value defined by the following formula.
Acetonitrile decomposition rate (%) = (1-acetonitrile mass in reaction solution / acetonitrile mass in concentrated crude acetonitrile) × 100

[Experiment 2]
Stirring was carried out at 70 ° C. for 5 hours in the same manner as in Experimental Example 1 except that the acetic acid concentration in the alkaline solution was changed to 3% by mass. Table 2 shows the composition of each solution and the decomposition rate of acetonitrile.

[Experiment 3]
Stirring was carried out at 70 ° C. for 5 hours in the same manner as in Experimental Example 1, except that the concentrations of acetamide and acetic acid in the alkaline solution were 5.0% by mass and 4.0% by mass, respectively. The composition of each solution and the acetonitrile decomposition rate are shown in Table 3.

[Experimental Example 4]
Stirring was performed at 70 ° C. for 5 hours in the same manner as in Experimental Example 1, except that the concentrations of acetamide and acetic acid in the alkaline solution were 7.0% by mass and 8.0% by mass, respectively. Table 4 shows the composition of each solution and the acetonitrile decomposition rate.

[Example 1]
Acetonitrile was purified using the purification apparatus shown in FIG. Crude acetonitrile containing 15% by mass of acetonitrile, which is a by-product of the ammoxidation reaction of propylene, was supplied from the line 7 to the acetonitrile concentration tower 1. Hydrogen cyanide was separated from line 8 and a part of water was separated from line 9. Vapor was extracted from the line 10 and condensed with a condenser (not shown) installed in the line 10 to obtain concentrated crude acetonitrile containing 65% by mass of acetonitrile. Other compositions of the concentrated crude acetonitrile were water 32% by mass, hydrogen cyanide 1.1% by mass, acrylonitrile 360% by mass, ammonia 100% by mass, and allyl alcohol, oxazole, propionitrile and the like.

  Concentrated crude acetonitrile 2580 kg / h was fed to the reactor 2 through the line 10. To the reaction tank 2, 230 kg / h of the bottom liquid of the dehydration tower 4 described later was added from the line 11 and reacted at 73 ° C. for 8 hours.

  The reaction liquid 2810 kg / h in the reaction tank 2 was sent to the high boiling separation tower 3 through the line 12. Distillation was performed by flowing 0.4 MPaG of steam 2.8 t / h through a reboiler installed at the bottom of the tower. The tower top pressure and tower bottom pressure were 235 mmHg and 255 mmHg in absolute pressure, respectively, and the tower top temperature and tower bottom temperature were 41.5 ° C. and 58.9 ° C., respectively. A liquid 770 kg / h containing allyl alcohol, propionitrile, sodium hydroxide, water and the like was extracted from the bottom of the column and treated with waste water. Vapor distilled from the top of the column was condensed with a condenser. The condensate 3940 kg / h was refluxed to the high boiling separation tower 3, and the distillate 2040 kg / h was cooled from the line 14 by a heat exchanger (not shown) and supplied to the lower part of the dehydration tower 4.

  300 kg / h of a 48 mass% sodium hydroxide aqueous solution at a temperature of 80 ° C. was supplied from the line 15 at the top of the dehydration tower 4, and was brought into liquid-liquid contact with the distillate having a temperature of 7.1 ° C. supplied from the line 14. The dehydrating tower 4 has a jacket on its outer side and can be cooled. The aqueous phase was extracted from the bottom of the dehydration tower 4, and 230 kg / h of the water phase was supplied from the line 11 to the reaction tank 2. The remainder of the bottom liquid was sent from the line 16 to a wastewater treatment facility (not shown) and processed. The amount extracted from the line 16 was balanced at 260 kg / h. From the line 17, 1850 kg / h of the acetonitrile phase at 25.9 ° C. was extracted.

  When the material balance of the reaction vessel 2 was collected, it was as shown in Table 5.

[Example 2]
The operation was performed under the same conditions as in Example 1 except that the temperature of the 48 mass% sodium hydroxide aqueous solution supplied from the line 15 was 65 ° C. When the material balance of the reaction vessel 2 was collected, it was as shown in Table 6.

[Example 3]
The operation was performed under the same conditions as in Example 1 except that the temperature of the 48 mass% sodium hydroxide aqueous solution supplied from the line 15 was 45 ° C. When the material balance of the reaction vessel 2 was collected, it was as shown in Table 7.

[Example 4]
The acetonitrile phase extracted from the line 17 in Example 1 was supplied to the low boiling point separation tower 5. The reboiler of the low boiling separation column 5 was subjected to distillation by flowing a steam of 0.4 MPaG at 2.6 t / h. The tower top pressure and tower bottom pressure were 0.1172 MPa and 0.1181 MPa in absolute pressure, respectively, and the tower top temperature and tower bottom temperature were 78.8 ° C. and 86.4 ° C., respectively. Vapor distilled from the top of the column was condensed with a condenser. Water at 28 ° C. was used as the condenser refrigerant. 4150 kg / h of the condensate was refluxed to the low boiling separation column 5, 300 kg / h was withdrawn from the line 18, and oxazole and low boiling point substances were removed. The liquid in the line 18 was treated with waste water. A liquid of 1550 kg / h extracted from the line 19 was sent to the product tower 6.

  Distillation was performed by flowing 1.6 t / h of 0.4 MPaG of steam through the reboiler of the product tower 6. The tower top pressure and the tower bottom pressure were respectively 0.1100 MPa and 0.1112 MPa in absolute pressure, and the tower top temperature and the tower bottom temperature were 81.2 ° C. and 82.2 ° C., respectively. A 70 kg / h liquid containing propionitrile and a high boiling point substance was extracted from the line 20 and treated with waste water. Steam distilled from the top of the column was condensed by a condenser and allowed to flow down to a reflux drum. Water at 28 ° C. was used as the condenser refrigerant. The condensate 4380 kg / h in the reflux drum was refluxed to the product column 6 using a pump, and 1480 kg / h was withdrawn from the line 21 to obtain purified high purity acetonitrile.

  When impurities in high purity acetonitrile were analyzed, the results shown in Table 8 were obtained.

[Example 5]
The operation was performed under the same conditions as in Example 4 except that the acetonitrile phase extracted from the line 17 in Example 2 was supplied to the low boiling point separation column 5.

  From the line 21, 1484 kg / h of highly purified acetonitrile was extracted. When impurities in high purity acetonitrile were analyzed, the results shown in Table 9 were obtained.

[Example 6]
The operation was performed under the same conditions as in Example 4 except that the acetonitrile phase extracted from the line 17 in Example 3 was supplied to the low boiling point separation column 5.

  1485 kg / h of high purity acetonitrile purified from the line 21 was extracted. When impurities in high purity acetonitrile were analyzed, the results shown in Table 10 were obtained.

[Comparative Experiment Example 1]
In a mixer, 500 g of concentrated crude acetonitrile composed of 65% by mass of acetonitrile and 35% by mass of water and 53.4 g of an alkaline solution composed of water and sodium hydroxide were added to prepare a mixed solution. The mixture was held for 5 hours while stirring at 70 ° C. Table 11 shows the composition of each solution and the decomposition rate of acetonitrile.

[Comparative Experiment Example 2]
500 g of concentrated crude acetonitrile composed of 65% by mass of acetonitrile and 35% by mass of water and 53.4 g of an alkaline solution composed of water, sodium hydroxide and ammonia were put into a mixer to prepare a mixed solution. The mixture was held for 5 hours while stirring at 70 ° C. Table 12 shows the composition of each solution and the decomposition rate of acetonitrile.

[Comparative Example 1]
Acetonitrile was purified using the purification apparatus shown in FIG. All the bottom liquid of the dehydration tower 4 was extracted from the line 16 and sent to a wastewater treatment facility, and an aqueous sodium hydroxide solution was added to the reaction tank 2 from the line 11. Except for these, acetonitrile was purified using the same equipment as in Example 1.

  A liquid containing 15% by mass of crude acetonitrile, which is a by-product of the ammoxidation reaction of propylene, was supplied from the line 7 to the acetonitrile concentration tower 1. Hydrogen cyanide was separated from line 8 and a part of water was separated from line 9. Vapor was extracted from the line 10 and condensed with a condenser (not shown) installed in the line 10 to obtain concentrated crude acetonitrile containing 65% by mass of acetonitrile. Other compositions of the concentrated crude acetonitrile were water 32% by mass, hydrogen cyanide 1.1% by mass, acrylonitrile 360% by mass, ammonia 100% by mass, and allyl alcohol, oxazole and propionitrile were included. .

  Concentrated crude acetonitrile 2580 kg / h was fed to the reactor 2 through the line 10. To the reaction tank 2, 180 kg / h of 48 mass% sodium hydroxide aqueous solution was added from the line 11 and reacted at 73 ° C. for 8 hours.

  The reaction liquid 2760 kg / h in the reaction tank 2 was sent to the high boiling separation tower 3 through the line 12. Distillation was performed by flowing 0.4 MPaG of steam 2.8 t / h through a reboiler installed at the bottom of the tower. The tower top pressure and tower bottom pressure were 235 mmHg and 255 mmHg in absolute pressure, respectively, and the tower top temperature and tower bottom temperature were 41.5 ° C. and 58.9 ° C., respectively. A liquid containing 790 kg / h containing allyl alcohol, propionitrile, sodium hydroxide and water was extracted from the bottom of the column and treated with waste water. The vapor distilled from the top of the column is condensed by a condenser, 3940 kg / h of the condensed liquid is refluxed to the high boiling separation tower 3, and 1970 kg / h of the distillate is cooled by a heat exchanger (not shown) from the line 14. The lower part of the dehydration tower 4 was supplied.

  300 kg / h of a 48 mass% aqueous sodium hydroxide solution at a temperature of 50 ° C. was supplied from the line 15 at the top of the dehydration tower 4, and the distillate at a temperature of 7.3 ° C. supplied from the line 14 was brought into liquid-liquid contact. The dehydrating tower 4 has a jacket on its outer side and can be cooled. A water phase of 475 kg / h was extracted from the bottom of the dehydration tower 4 and sent from the line 16 to a wastewater treatment facility (not shown) for treatment. The temperature of the aqueous phase was 15.5 ° C.

  An acetonitrile phase of 1795 kg / h was extracted from the line 17 and supplied to the low boiling point separation tower 5. The temperature of the acetonitrile phase was 25.7 ° C.

  When the material balance of the reaction vessel 2 was collected, it was as shown in Table 13.

[Comparative Example 2]
The acetonitrile phase extracted from the line 17 in Comparative Example 1 was supplied to the low boiling point separation tower 5. The reboiler of the low boiling separation column 5 was subjected to distillation by flowing a steam of 0.4 MPaG at 2.5 t / h. The tower top pressure and tower bottom pressure were 0.1172 MPa and 0.1181 MPa in absolute pressure, respectively, and the tower top temperature and tower bottom temperature were 78.8 ° C. and 86.4 ° C., respectively. Vapor distilled from the top of the column was condensed with a condenser. Water at 28 ° C. was used as the condenser refrigerant. 4150 kg / h of the condensate was refluxed to the low boiling separation column 5, 300 kg / h was withdrawn from the line 18, and oxazole and low boiling point substances were removed. The liquid in the line 18 was treated with waste water. 1495 kg / h of liquid extracted from the line 19 was sent to the product tower 6.

  Distillation was performed by flowing 1.6 t / h of 0.4 MPaG of steam through the reboiler of the product tower 6. The tower top pressure and the tower bottom pressure were respectively 0.1100 MPa and 0.1112 MPa in absolute pressure, and the tower top temperature and the tower bottom temperature were 81.2 ° C. and 82.2 ° C., respectively. A 70 kg / h liquid containing propionitrile and a high boiling point substance was extracted from the line 20 and treated with waste water. Steam distilled from the top of the column was condensed by a condenser and allowed to flow down to a reflux drum. Water at 28 ° C. was used as the condenser refrigerant. Condensate 4380 kg / h in the reflux drum was refluxed to the product column 6 using a pump, and 1425 kg / h was extracted from the line 21 to obtain purified high-purity acetonitrile.

  When impurities of high purity acetonitrile were analyzed, the results shown in Table 14 were obtained.

[Example 7]
Crude acetonitrile containing 12% by mass of acetonitrile, which is a byproduct of the propane ammoxidation reaction, was supplied to the same equipment as in Example 1 to purify acetonitrile.

  Crude acetonitrile was supplied from the line 7 to the acetonitrile concentration tower 1. Hydrogen cyanide was separated from line 8 and a part of water was separated from line 9. Vapor was extracted from the line 10 and condensed with a condenser (not shown) installed in the line 10 to obtain concentrated crude acetonitrile containing 65% by mass of acetonitrile. Other compositions of the concentrated crude acetonitrile were 32% by mass of water, 1.3% by mass of hydrogen cyanide, 350% by mass of acrylonitrile, 100% by mass of ammonia, and allyl alcohol, propionitrile and the like.

  Concentrated crude acetonitrile 2580 kg / h was fed to the reactor 2 through the line 10. To the reaction tank 2, 230 kg / h of the bottom liquid of the dehydration tower 4 described later was added from the line 11 and reacted at 73 ° C. for 8 hours.

  The reaction liquid 2810 kg / h in the reaction tank 2 was sent to the high boiling separation tower 3 through the line 12. Distillation was performed by flowing 0.4 MPaG of steam 2.8 t / h through a reboiler installed at the bottom of the tower. The tower top pressure and tower bottom pressure were 235 mmHg and 255 mmHg in absolute pressure, respectively, and the tower top temperature and tower bottom temperature were 41.5 ° C. and 58.9 ° C., respectively. A liquid 770 kg / h containing allyl alcohol, propionitrile, sodium hydroxide, water and the like was extracted from the bottom of the column and treated with waste water. The vapor distilled from the top of the column is condensed by a condenser, the condensed liquid 3940 kg / h is refluxed to the high-boiling separation tower 3, and the distillate 2040 kg / h is cooled by a heat exchanger (not shown) from the line 14 to dehydrate. Feeded to the bottom of column 4.

  300 kg / h of a 48 mass% aqueous sodium hydroxide solution at a temperature of 50 ° C. was supplied from the line 15 at the top of the dehydration tower 4, and brought into liquid-liquid contact with the distillate at a temperature of 7.1 ° C. supplied from the line 14. The dehydrating tower 4 has a jacket on its outer side and can be cooled. The aqueous phase was extracted from the bottom of the dehydration tower 4, and 230 kg / h of the water phase was supplied from the line 11 to the reaction tank 2. The remainder of the bottom liquid was sent from the line 16 to a wastewater treatment facility (not shown) and processed. The amount extracted from the line 16 was balanced at 260 kg / h.

  From the line 17, 1850 kg / h of the acetonitrile phase at 25.9 ° C. was extracted. When the material balance of the reaction vessel 2 was collected, it was as shown in Table 15.

[Example 8]
The acetonitrile phase extracted from the line 17 in Example 7 was supplied to the low boiling point separation column 5. The reboiler of the low boiling separation column 5 was subjected to distillation by flowing a steam of 0.4 MPaG at 2.6 t / h. The tower top pressure and tower bottom pressure were 0.1172 MPa and 0.1181 MPa in absolute pressure, respectively, and the tower top temperature and tower bottom temperature were 78.8 ° C. and 86.4 ° C., respectively. Vapor distilled from the top of the column was condensed with a condenser. Water at 28 ° C. was used as the condenser refrigerant. 4150 kg / h of the condensate was refluxed to the low-boiling separation tower 5, 300 kg / h was extracted from the line 18, and low-boiling substances were removed. The liquid in the line 18 was treated with waste water. A liquid of 1550 kg / h extracted from the line 19 was sent to the product tower 6.

  Distillation was performed by flowing 1.6 t / h of 0.4 MPaG of steam through the reboiler of the product tower 6. The tower top pressure and the tower bottom pressure were respectively 0.1100 MPa and 0.1112 MPa in absolute pressure, and the tower top temperature and the tower bottom temperature were 81.2 ° C. and 82.2 ° C., respectively. A 70 kg / h liquid containing propionitrile and a high boiling point substance was extracted from the line 20 and treated with waste water. Steam distilled from the top of the column was condensed by a condenser and allowed to flow down to a reflux drum. Water at 28 ° C. was used as the condenser refrigerant. The condensate 4380 kg / h in the reflux drum was refluxed to the product column 6 using a pump, and 1486 kg / h was withdrawn from the line 21 to obtain purified high purity acetonitrile.

  When impurities in high purity acetonitrile were analyzed, the results shown in Table 16 were obtained.

  From the results of the above examples and comparative examples, in the process of purifying high-purity acetonitrile, by supplying acetamide and / or acetic acid to the reaction tank 2, the acetonitrile recovery rate can be improved without affecting the quality of the high-purity acetonitrile. It can be seen that it can be improved. Furthermore, it can be seen that the amount of alkali used can be reduced by using the bottom liquid of the dehydration tower 4 as the alkali source of the reaction tank 2.

  This application is based on a Japanese patent application filed on August 31, 2012 (Japanese Patent Application No. 2012-192215), the contents of which are incorporated herein by reference.

  The method for purifying acetonitrile according to the present invention is a process in which the amount of wastewater treated and the amount of chemical used for purification are small, and the purification equipment and steps are simple. In addition, according to the method of the present invention, high-purity acetonitrile that can be used for applications such as pharmaceutical intermediate synthesis / purification solvents, DNA synthesis / purification solvents, organic EL material synthesis solvents, and electronic component cleaning solvents is prepared. It can be purified efficiently.

DESCRIPTION OF SYMBOLS 1 Acetonitrile concentration tower 2 Reaction tank 3 High boiling separation tower 4 Dehydration tower 5 Low boiling separation tower 6 Product tower 7-21 line

That is, the present invention is as follows.
[1]
Supplying crude acetonitrile obtained by an ammoxidation reaction and alkali to a reaction vessel to obtain a reaction solution;
Distilling the reaction liquid to obtain a distillate;
Supplying acetamide and / or acetic acid to the reaction vessel;
Only including,
In the step of distilling the reaction liquid to obtain a distillate, the reaction liquid is introduced into a distillation column to remove high boiling substances, and then the distillate obtained is supplied to a dehydration tower, Including the step of separating the aqueous phase in addition to the dehydration tower,
The method for purifying acetonitrile , wherein the alkali supplied to the reaction vessel contains a part of the aqueous phase .
[2]
The method for purifying acetonitrile according to claim 1, wherein the concentration of acetamide and / or acetic acid in the aqueous phase is 0.50% by mass or more and 25% by mass or less.
[3]
The method for purifying acetonitrile according to the above [1] or [2] , comprising adding the alkaline aqueous solution to the dehydration tower at 40 ° C. or higher and 90 ° C. or lower.
[4]
The manufacturing method of high purity acetonitrile including refine | purifying acetonitrile using the purification method of acetonitrile in any one of said [1]- [3] .

Claims (5)

Supplying crude acetonitrile obtained by an ammoxidation reaction and alkali to a reaction vessel to obtain a reaction solution;
Distilling the reaction liquid to obtain a distillate;
Supplying acetamide and / or acetic acid to the reaction vessel;
A method for purifying acetonitrile, comprising:   In the step of distilling the reaction liquid to obtain a distillate, the reaction liquid is introduced into a distillation column to remove high boiling substances, and then the distillate obtained is supplied to a dehydration tower, The method for purifying acetonitrile according to claim 1, comprising a step of separating the aqueous phase in addition to the dehydration tower.   The method for purifying acetonitrile according to claim 2, wherein the alkali supplied to the reaction vessel contains a part of the aqueous phase.   The method for purifying acetonitrile according to claim 2 or 3, comprising adding the alkaline aqueous solution to the dehydration tower at 40 ° C or higher and 90 ° C or lower.   The manufacturing method of high purity acetonitrile including refine | purifying acetonitrile using the purification method of acetonitrile of any one of Claims 1-4.

Images