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WO1994026698A1 - Acetonitrile de grande purete et purification d'acetonitrile brut - Google Patents

Acetonitrile de grande purete et purification d'acetonitrile brut Download PDF

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Publication number
WO1994026698A1
WO1994026698A1 PCT/JP1993/000638 JP9300638W WO9426698A1 WO 1994026698 A1 WO1994026698 A1 WO 1994026698A1 JP 9300638 W JP9300638 W JP 9300638W WO 9426698 A1 WO9426698 A1 WO 9426698A1
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WO
WIPO (PCT)
Prior art keywords
acetonitrile
ozone
crude
absorbance
sodium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP1993/000638
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English (en)
Japanese (ja)
Inventor
Shigeo Nakamura
Shigeru Kurihara
Minoru Saitoh
Hideo Midorikawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Chemical Industry Co Ltd
Asahi Kasei Kogyo KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Chemical Industry Co Ltd, Asahi Kasei Kogyo KK filed Critical Asahi Chemical Industry Co Ltd
Priority to KR1019950700150A priority Critical patent/KR0171245B1/ko
Priority to DE4397378A priority patent/DE4397378B3/de
Priority to PCT/JP1993/000638 priority patent/WO1994026698A1/fr
Priority to GB9500707A priority patent/GB2285443B/en
Priority to DE4397378T priority patent/DE4397378T1/de
Priority to FR9306051A priority patent/FR2705342B1/fr
Publication of WO1994026698A1 publication Critical patent/WO1994026698A1/fr
Priority to US08/371,180 priority patent/US5629443A/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/32—Separation; Purification; Stabilisation; Use of additives
    • C07C253/34—Separation; Purification

Definitions

  • the present invention relates to a method for purifying high-purity acetonitrile and crude acetonitrile. Specifically, high-performance liquid chromatography with an ultraviolet absorbance of wavelengths of 200 to 400 nm of 0.05 or less--a simple method for high-purity acetonitrile and crude acetonitrile for mobile phase solvents. In addition to a method for purification, a high-purity purification is carried out and industrially used as a mobile phase solvent for liquid chromatography, especially for high performance liquid chromatography, a wavelength of 200 to 40 O nm is used. The present invention relates to a purification method for obtaining high-purity acetonitrile with low absorption in the ultraviolet region. Background art
  • acetonitrile is mainly produced as a by-product in the production of acrylonitrile or methacrylonitrile by the catalytic ammoxidation reaction of propylene or isobutene with ammonia and molecular oxygen.
  • the product obtained is recovered and purified. Since acetonitrile obtained as a by-product contains many impurities, various methods for purification have been proposed.
  • JP-A-5-143939-49 discloses a method of reacting with an aqueous solution of an alkali metal salt or an alkaline earth metal salt of hypochlorous acid.
  • JP-A-5-143939-49 discloses a method of reacting with an aqueous solution of an alkali metal salt or an alkaline earth metal salt of hypochlorous acid.
  • a method of separating after reaction with molecular chlorine is disclosed in Japanese Patent Application Laid-Open No. 59-105556, which discloses extraction and distillation in the presence of water.
  • a method for performing this is disclosed in Japanese Patent Application Laid-Open No. 55-143950.
  • a method for purifying acetonitrile a method of distilling after reacting with a basic compound is disclosed in JP-A-56-54949, and a method using three distillation columns is disclosed in JP-A-56-549. It is disclosed in Japanese Patent Application Publication No. Sho 58-124. That is, the main impurities contained in acetonitrile are aryl alcohol, oxazole, acrylonitrile, etc. In order to remove these, it is necessary to combine conventionally disclosed methods, and the process must be carried out. It becomes very complicated. In this method, it was not possible to obtain acetonitrile having the absorbance of ultraviolet light having a wavelength of 200 to 400 nm of 0.05 or less, which is the object of the present inventors.
  • East German Patent No. DD 2 172 212 A1 discloses a method of distilling after contact treatment with ozone, in which aryl alcohol, oxazole, lactone and the like are simultaneously decomposed and separated by distillation. A good way to get rid of it is disclosed. However, when the present inventors conducted additional tests, it was possible to reduce the absorbance of ultraviolet light having a wavelength of 200 to 400 nm of the acetate nitrile used as a raw material, but it was possible to reduce the absorbance of the wavelength of 200 to 400 nm. Acetonitrile having an ultraviolet absorbance of 0.05 or less could not be obtained.
  • Crude acetonitrile contains impurities derived from its manufacturing method, and therefore has absorption in the ultraviolet region of wavelength 200 to 400 nm, but the ultraviolet absorption in this region is mainly due to the double impurities. This is due to bonding.
  • C C double bond
  • C 0 group, COOH carboxyl group, CHO aldehyde group
  • You Compounds have absorption in this region, specifically, allylic alcohol, oxazole, acrylonitrile, methacrylonitrile, cis and trans crocrotritolyl, acrylic acid, acrylic acid Methyl, methacrylic acid, methyl methacrylate, acetic acid, acrolein, methacrolein, and acetone are applicable.
  • acetonitrile having an absorbance at a wavelength of 200 to 400 nm of 0.05 or less For example, in order to reduce the absorbance of acetonitrile at a wavelength of 200 nm to 0.05 or less, acrylonitrile in acetonitrile is 1.5 ppm or less, and oxazole is 0.8 ppm or less. Acrylonitrile is less than 0.2 ppm, methacrylonitrile is less than 0.2 ppm, cis-crotonitrile is less than 0.2 ppm, acrylic acid is less than 0.2 ppm, and methyl acrylate is 0.
  • acetic acid must be 30 ppm or less, and the same applies to other impurities.
  • acetonitrile most of these compounds coexist in acetonitrile, so the limit value of each compound is even smaller, so that high-purity acetonitril can be obtained. Requires advanced separation and purification technology.
  • a first object of the present invention is to disclose a high-purity acetate nitrile for high-performance liquid chromatography and a mobile phase solvent having an absorbance of ultraviolet light having a wavelength of 200 to 400 nm of 0.05 or less.
  • a second object of the present invention is to provide a simple method for purifying crude acetonitrile and a more advanced purification to industrially carry out liquid chromatography-mobile phase solvents, especially high-performance liquid-mouth chromatography-mobile phase solvents.
  • the present invention discloses a purification method for producing acetonitrile having an absorbance of ultraviolet rays having a wavelength of from 200 to 400 nm and having a wavelength of not more than 0.05.
  • the present inventors have conducted a detailed study on a method of contact treatment with ozone, and found that acid and permanganate reducing substances are generated by the contact treatment with ozone, and these are basic substances and / or They grasped that they were removed by contact with the adsorbent, and found a simple purification method that was the object of the present invention. Even more surprisingly, the liquid treated with ozone was brought into contact with one or more basic substances and adsorbents. By removing the low-boiling compounds and high-boiling compounds contained in the acetonitrile later, an acetonitrile having an ultraviolet absorbance of 0.05 to 400 nm or less of ultraviolet light having a wavelength of 0.05 or less can be obtained. Thus, the present invention has been completed. Disclosure of the invention
  • the present invention provides a method for purifying crude acetonitrile.
  • the crude acetonitrile as a raw material in the present invention includes acetonitrile having a light absorbance of ultraviolet light having a wavelength of 200 nm of 0.1 or more, propylene, isobutene or tertiary butanol, and ammonium nitrate.
  • Crude acetonitril which is obtained as a by-product when acrylonitrile or methacrylonitrile is produced by catalytic ammoxidation reaction with oxygen, can be used.
  • a crude acetonitril having an absorbance of 0.1 or more for ultraviolet light having a wavelength of 200 nm can be used, and preferably, a crude acetonitrile having a wavelength of 200 nm is used.
  • the present invention does not particularly limit crude acetonitrile as a raw material, and crude acetonitrile produced by another production method can also be used as a raw material.
  • crude acetonitrile produced by another production method can also be used as a raw material.
  • the crude acetonitrile having an absorbance of ultraviolet light having a wavelength of 200 nm of 0.1 or more is used as a raw material, and the absorbance of ultraviolet light having a wavelength of 200 to 400 nm is 0.05 or less.
  • Acetonitrile can be obtained.
  • crude acetonitrile having an absorbance of ultraviolet light having a wavelength of 200 nm less than 0.1 can be used as a raw material.
  • the use of these raw materials is not an attractive method, mainly because of the small effect from an economic point of view.
  • the absorbance of acetonitrile for ultraviolet light is a value measured using an Iseki cell having an optical path length of 10 mm and distilled water at the detection wavelength as a control.
  • the first step of the present invention is a step of contacting crude acetonitrile with nascent oxygen. The purpose of this step is to decompose impurities having double bonds, especially aryl alcohol, oxazole, acrylonitrile, etc., which are difficult to remove by methods such as distillation, adsorption or reaction, by contact with nascent oxygen. It is to convert the compound into a compound that can be easily separated and removed in the subsequent steps.
  • Compounds that generate nascent oxygen include permanganic acid or salts thereof, such as permanganate potassium lime, peroxides such as hydrogen peroxide, sodium peroxide, barium peroxide, oxyacid or salts thereof.
  • permanganic acid or salts thereof such as permanganate potassium lime
  • peroxides such as hydrogen peroxide, sodium peroxide, barium peroxide, oxyacid or salts thereof.
  • the ozone-containing gas used in the present invention is obtained by supplying air or oxygen or an oxygen-containing gas to an ozone generator, and is used for contact with crude acetate. It can also be used after diluting it with a gas such as nitrogen, carbon dioxide or air.
  • the concentration of ozone in the ozone-containing gas is from 0.01 to 5.0 V, preferably from 0.1 to 2.0 V. If the ozone concentration is too low, the time required for contact with the crude acetonitril increases, and the efficiency increases due to the increase in the size of the reactor and the accompanying loss of acetonitril due to the supplied gas. Not.
  • the temperature at which the crude acetonitrile is brought into contact with the ozone-containing gas is 140 to 80 ° C, preferably 10 to 40 ° C. If the temperature is too low, there are problems such as a slow reaction rate and precipitation of trace components. If the temperature is too high, an excessive reaction proceeds and the yield of acetonitrile decreases.
  • the pressure at which the crude acetonitrile is brought into contact with the ozone-containing gas may be reduced pressure, normal pressure, or pressurized pressure, but is preferably in the range of normal pressure to 10 atm.
  • the contact between the crude acetonitrile and the ozone-containing gas can be performed in a batch system or a continuous system.
  • the batch method can be carried out in a single-stage or multi-stage contact tank having a stirring device or a bubble tower, but is preferably performed in a contact tank having a stirring device to improve gas-liquid contact.
  • the ozone-containing gas is preferably supplied as small bubbles from one or more nozzles into the acetonitrile. .
  • the ozone-containing gas is preferably supplied to a position below or beside the stirring blade, and the optimum position is determined by observing the stirring state of the acetonitrile depending on the structure of the tank and the blade. And the number can be determined.
  • the contact between the crude acetonitrile and the ozone-containing gas in the batch method depends on the amount of impurities contained in the crude acetonitrile, but the volume of the acetonitrile contacted with the ozone-containing gas is different. It is preferable to supply a gas volume of 1 to 1000 times, preferably 100 to 1000 times, for 1 to 300 minutes, preferably 10 to 120 minutes. . If the supply time is too short, the reaction between the ozone and the impurities will be insufficient, and the loss due to the entrainment of acetonitril due to the high gas flow rate will occur. If the supply time is too long, there is no advantage from the viewpoint of productivity, and an excessive oxidation reaction proceeds.
  • the supply time of the ozone-containing gas can also be determined by analyzing the ozone concentration in the exhaust gas. Specifically, it is preferable to supply the ozone-containing gas until the ozone concentration in the exhaust gas becomes 80% or more, preferably 90% or more of the ozone concentration of the supplied gas.
  • a continuous analyzer using an iodine titration method, an ultraviolet absorption method, a chemiluminescence method, or the like can be used.
  • the reaction can be carried out in a packed tower, a wet wall tower, a bubble tower, or the like, but it is preferably carried out in a packed tower.
  • a packing material for the packed tower Raschig ring, wrestling ring, Berlassador, interlock saddle, teralet packing, pole ring, McMahon packing, Dixon ring, etc. can be used. .
  • These fillers can be made of a material such as porcelain, metal, plastic, or carbon.
  • the contact between the crude acetonitrile and the ozone-containing gas can be carried out in countercurrent or cocurrent, but it is preferable to make contact in countercurrent.
  • a liquid redistribution plate can be provided at an appropriate height to increase the gas-liquid contact efficiency.
  • the ratio of the ozone-containing gas to the crude acetonitrile is preferably 1 to 1000, preferably 10 to 100, by volume, and flooding occurs according to the characteristics of the packed tower. No value is chosen.
  • the second step of the present invention is a step of bringing the acetonitrile that has passed through the first step into contact with at least one substance selected from a basic substance and an adsorbent.
  • the purpose of this step is to convert impurities contained in the acetonitrile that has passed through the first step into compounds that can be easily separated, or to perform adsorption separation.
  • the contact of the acetonitrile with the basic substance and the adsorbent in the second step of the present invention is at a temperature of 140 to 80 ° C, preferably at a temperature of 5 to 60 ° C. More preferably, it is carried out at a temperature of 10 to 40.
  • the basic substance in the present invention a liquid or solid basic substance is used.
  • Liquid basic substances include Li, Na, K, Rb and Alkali metals. Is a compound selected from the group consisting of hydroxides of Cs, carbonates or bicarbonates, hydroxides of Mg, Ca, Sr or Ba as alkaline earth metals, ammonia or amine, or The aqueous solution or the solution can be used.
  • the amine used here has a boiling point of at least 5 ° C, preferably 1 ° C, compared to the boiling point of acetonitrile in order to facilitate separation and removal in the subsequent distillation step. It is preferable to use an amine separated by 0 ° C or more, specifically, methylamine, dimethylamine, trimethylamine, ethylamine, getylamine, triethylamine, Propylamine, isopropylamine, dipropylamine, tripropylamine, s-butylamine, t-butylamine, dibutylamine, triptylamine, pentylamine, t 1-Pentylamine, hexylamine, heptylamine, octylamine, ethylenediamine, 1,2—pan mouth, 1,3—propanediamine, ethanolamine, Aliphatic amines such as ethanolamine and triethanolamine, or aromatics such as aniline, pyridine, quinoline, 0-toluid
  • the solvent used for the solution used here has a boiling point of 5 ° C or more compared to the boiling point of acetonitrile in order to facilitate separation and removal in the next distillation step. It is preferable to use a solvent which is separated by 10 or more.
  • methanol, 1-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3 Pennol, ethylene glycol, 1,3—dioxane, 1,4-dioxane, 1,2—propanediol, 1,3—aliphatic alcohols such as propanediol, or pentane, hexane, octane And saturated aliphatic hydrocarbons such as nonane and decane.
  • acetonitrile itself as a solvent.
  • the concentration of the basic substance in these aqueous solutions or solutions can be arbitrarily set at a concentration equal to or lower than the saturation solubility, but may be a slurry.
  • the amount of addition of these liquid basic substances may be such that the pH value of an aqueous solution obtained by diluting the acetate to 1/10 with water becomes 5 or more, but it is preferable. Is 5-9, more preferred It is better to control it to be 6-8.
  • the contact between the acetonitrile and the liquid basic substance is carried out by injecting into a pipe with a line mixer or a single- or multi-stage contact tank with a stirring device to promote the reaction. It is preferable to add the compound.
  • the added liquid basic substance forms a salt with an acid such as carboxylic acid and precipitates as a sticky precipitate.Therefore, in order to prevent troubles due to clogging in the next distillation step, filtration and sedimentation are performed. An operation of separating these precipitates by separation or the like is required. If water is contained in the basic substance added as a liquid, the water must be removed to form an azeotropic composition with acetonitril when the water is separated and removed in the next distillation step. At the same time, acetonitrile is also removed, resulting in a problem that the recovery rate of acetonitrile is reduced.
  • an ammonia gas or an ammonia-containing gas as a basic substance can be supplied into the acetonitril to cause a reaction.
  • small bubbles are supplied from one or more nozzles into the acetonitrile, or stirring is performed. It is good to use the method.
  • the supply amount of ammonia or ammonia-containing gas may be any amount as long as the pH value of an aqueous solution obtained by diluting the acetonitrile to 110 with water is 5 or more, preferably 5 to 9, more preferably 5 to 9. Should be controlled to be 6 to 8.
  • Solid basic substances include anion exchange resins, alkali metal hydroxides, carbonates or bicarbonates, alkaline earth metal oxides, hydroxides, or carbonates, and mixtures of different metal oxides.
  • a solid base a substance in which an alkali metal or alkaline earth metal compound is supported on a carrier, activated carbon, and the like.
  • the anion exchange resin of the present invention a porous or gel type strongly basic anion exchange resin or a weakly basic anion exchange resin can be used. Either an ion exchange resin for an aqueous solution or an ion exchange resin for a non-aqueous solution can be used. Strongly basic anion exchange resin regenerates exchange groups such as trimethylammonium group and dimethylethanol group by regeneration treatment.
  • the Jakushio group anion exchange resin arbitrariness preferred to use after performing a reproduction process 1-3 Kyua Mi Bruno exchange group such as N a OH, with NH 4 0 H like. After performing an exchange group regeneration treatment, these anion exchange resins are brought into contact with a sufficient amount of acetonitrile and washed to remove water and impurities contained in the ion exchange resin before use. Good to use.
  • the solid basic substance of the present invention include hydroxides, carbonates or bicarbonates of alkali metals Li, Na, K, Rb, and Cs, and alkaline earths.
  • the carrier include oxides, hydroxides, carbonates, or bicarbonates, which are compounds of barium oxide, an alkali metal, or an alkaline earth metal.
  • Activated carbon, silica, alumina, titania or zirconia is used, and the loading amount is 0.01 to 50 wt%, preferably 0.1 to 10 wt%.
  • N 20 As solid basic substances, N 20 ,? ⁇ 1 ⁇ or 211_Rei 1 2 - 1 ⁇ 1 4 C 1 - C 0 2 in is activated can also be used activated carbon was expressed basified.
  • activated carbon As the adsorbent, activated carbon, activated alumina, silica gel, synthetic zeolite, natural zeolite, adsorption resin, natural clay mineral, silica alumina, silica magnesia, silica polia and the like are used.
  • Solid basic substances and Z or adsorbents can be handled as powders or granules, the size of which is between 0.01 and 100 mm, preferably between 0.01 and 2 A thing of 0 mm is good. Further, the powder can be used as a cylindrical or spherical molded body by tableting or the like.
  • the contact between the basic substance and Z or the adsorbent with the acetonitril can be carried out in a continuous manner or in a batch manner. However, for industrial use, the continuous manner is preferred.
  • a solid basic substance is filled in a part of a packed tower or pipe. Then, it can be supplied and contacted with the acetonitrile. Further, the space velocity SV is preferably operated at 0.001 to 100 (lZmin), preferably at 0.01 to 100 (1 / in).
  • the batch method can be carried out in a contact tank equipped with a stirring device or a shaking device.
  • the contact time is between 0.1 and 1000 minutes, preferably between 1 and 120 minutes.
  • the separation of the solid base and / or the adsorbent from acetonitrile becomes unnecessary, and the present invention can be carried out without the separation and removal step in the third step.
  • the first purpose simple acetonitrile purification, can be performed. That is, a simple method of purifying acetonitrile by simply passing through a packed bed composed of a solid base or an adsorbent without using a distillation column disclosed in East German Patent No.DD 2172 212 A1 is disclosed. Things.
  • the first step and the second step are continued. Processing by the third step is required.
  • the third step of the present invention is a step of separating and removing low-boiling compounds and high-boiling compounds in acetonitrile that have passed through the first step or the second step.
  • the purpose of this step is to separate and remove impurities such as compounds that cause ultraviolet absorption contained in acetonitrile, and that the absorbance of ultraviolet light at a wavelength of 200 to 400 nm is less than 0.05. Is to get acetonitrile.
  • the method of separation and removal is selected from a distillation method and a membrane separation method, and a distillation method is particularly preferable as an industrial separation method.
  • a tray column or a packed column is used as the distillation column of the present invention.
  • the tray tower include a cross-flow contact type with a downcomer and a countercurrent contact type without a downcomer.
  • a bubble bell type, a perforated plate type, a valve type, or the like can be used as the tray opening.
  • the number of stages in this distillation column is not particularly limited as long as it is at least 10 stages, but preferably 30 to 80 stages.
  • packed towers examples include lashing rings, dressing rings, and polish
  • a tower filled with a wool ring, berl saddle, interlock saddle, teralet hacking, dixon ring or McMahon packing can be used.
  • the material of the filler it is possible to use those made of porcelain, metal, plastic or carbon.
  • the packing tower may be provided with a liquid redistribution plate at an appropriate height to enhance the gas-liquid contact efficiency.
  • a method for separating and removing a compound having a low boiling point and a compound having a high boiling point as compared with acetonitrile a method using two distillation columns may be mentioned. Specifically, a method in which low-boiling compounds are separated and removed from the top in the column I, and high-boiling compounds are separated and removed in the second column from the bottom to obtain purified acetonitrile from the top, or There is a method in which a high-boiling compound is separated and removed from the bottom in one column, and a low-boiling compound is separated and removed from the top in a second column to obtain purified acetonitrile from the bottom or the upper part.
  • the low-boiling compound and the high-boiling compound can be separated and removed in a single distillation column.
  • the acetonitrile is supplied to an intermediate portion of the distillation column, a low-boiling compound is extracted from the top of the distillation column, and a high-boiling compound is extracted from the bottom of the distillation column.
  • This is a method of obtaining purified acetonitrile from above or below the supply position, and preferably a method of obtaining purified acetonitrile from above the supply position of the acetonitrile.
  • the reflux ratio and the amount of low-boiling compounds and high-boiling compounds withdrawn can be determined as conditions for obtaining purified acetonitrile that meets the purpose.
  • the withdrawal amount of the top containing the low-boiling compound and the withdrawal amount of the bottom containing the high-boiling compound are each 1% or more, preferably 5% or more, based on the supplied acetonitrile. Extraction amount from top and bottom If the amount is small, the absorbance of ultraviolet light having a wavelength of 200 to 400 nm may not be less than 0.05 due to a trace amount of impurities contained in the extracted acetonitrile.
  • the low-boiling compound and the high-boiling compound can be separated and removed, but this is not an economically effective method.
  • distillation operations can be performed at any of reduced pressure, normal pressure, and increased pressure, but usually the range of normal pressure to 10 atm is preferable.
  • FIG. 1 is a diagram showing an ultraviolet absorption spectrum of purified acetonitrile.
  • FIG. 2 is a view showing an ultraviolet absorption spectrum of acetonitrile as a raw material.
  • the absorbance of ultraviolet light at 200 nm is 1.560, acrylonitrile as impurities 2.8 ppm, allylic alcohol 5.0111, acid 1.5 ppm, The following operation was performed using acetonitrile having a permanganic acid fading rate of 29%, which is an index of the amount of permanganate reducing substances. I got it.
  • a 30 mm diameter ozone contact tower was filled with a porcelain lashing ring with an outer diameter of 5 mm, an inner diameter of 2 mm and a height of 5 mm to a height of 41 mm.
  • Acetonitrile contacted with ozone was extracted from the bottom of the ozone contact tower. Acrylonitrile and aryl alcohol in the extracted acetonitrile were not detected, but the acid concentration increased to 105 ppm and the permanganate discoloration rate was 100%. Had risen.
  • a column having a diameter of 20 mm filled with 50 m ⁇ filled with a non-aqueous porous weakly basic anion exchange resin (trade name Amberlist A—21) was prepared. The acetonitril that had passed through the step 1 was continuously supplied, and brought into contact at a temperature of 20.
  • the absorbance of the finally obtained acetonitrile in ultraviolet light at 200 nm is 1.620.
  • acrylonitrile and acryl alcohol are below the detection limit. there were.
  • the acid content was 0.9 ppm, and the permanganic acid fading rate was 0%.
  • the treatment in the first step decomposes acrylonitrile and aryl alcohol, but increases acid and permanganate reducing substances. It is clear that the acid and permanganate reducing substances have been removed by the treatment in the second step. Although this operation was performed continuously for 200 hours, the operation was simple and the operation was stable.
  • the ultraviolet absorption spectrum was measured using a quartz cell with an optical path length of 10 mm and a spectrophotometer 288 A manufactured by Hitachi using distilled water as a control.
  • the gas chromatographic analysis was performed using a Yokogawa Gas Chromatograph HP-5890, with a capillary column inner diameter of 0.25 mm * length of 50 m using silicon OV-1 as the packing material. Column temperature first at 40 ° C 5 After maintaining the temperature for 10 minutes, the temperature was raised to 200 ° C. at a rate of 10 ° C.Z, and finally maintained at this temperature for 10 minutes.
  • the acid analysis was performed in accordance with JISK8001 5.6 (1).
  • For the permanganate reducing substance add 0.1 m £ 0.1 N potassium permanganate to 10 g of sample, shake and mix in a cool dark place for 30 minutes, referring to the method described in JISK 8032 After standing, the permanganic acid fading rate was measured using a UV 2000 model manufactured by Shimadzu Corporation and used as an index of the permanganate reducing substance.
  • Permanganic acid fading rate (1-(A / B)) X 1 0 0
  • Purified acetonitrile was obtained by performing the same operation as in Example 1 except that 50 m ⁇ was used as the adsorbent in the second step of Example 1.
  • the absorbance of this acetonitrile for ultraviolet light at a wavelength of 200 nm was 1.500, the acid was 1.2 ppm, and the permanganic acid fading rate was 5%.
  • the raw material acetonitrile has an absorbance of 200 nm ultraviolet ray of 1.703, and the impurities are acrylonitrile 3.5 ppm, methacrylonitrile 8 ppm, and allylic alcohol 8 ppm.
  • the following operation was performed using acetonitrile containing 2 ppm of oxazole.
  • a 30 mm diameter ozone contact tower was filled with a porcelain lashing ring with an outer diameter of 5 mm, an inner diameter of 2 mm and a height of 5 mm to a height of 41 mm.
  • a non-aqueous, porous, weakly basic anion exchange resin (trade name Amberlyst A—21) was packed in a 50 mm column packed with 20 mm diameter, The acetonitrile was then supplied continuously and brought into contact at a temperature of 20.
  • a distillation apparatus with a diameter of 40 mm and a perforated plate system with a total of 65 stages was used.
  • the 10th stage is continuously supplied with the acetate tril which has passed through the second step, the operation is performed at a reflux ratio of 16 with the top pressure set to atmospheric pressure, and the base containing the low boiling point compounds is operated from the top.
  • Tonitrile was extracted in an amount of 20% of the supplied amount, and acetonitrile containing high-boiling compounds was extracted from the bottom of the column in an amount of 10% of the supplied amount, and refined from the 40th stage. Tonitrile was obtained in an amount of 70% of the supplied amount, and the recovery of acetonitrile was 70%.
  • the absorbance of ultraviolet light at a wavelength of 200 nm of this acetonitrile was 0.021, and the absorbance of ultraviolet light at 210 to 400 nm was not more than 0.013. Analysis by gas chromatography showed that acrylonitrile, methacrylonitrile, acryl alcohol and oxazole were below the detection limit.
  • FIGS. 1 and 2 show the ultraviolet ray absorption spectrum of the purified acetonitrile and the acetonitrile used as a raw material, respectively.
  • Example 5 As the basic substance in the second step of Example 4, a gel-type strongly basic anion exchange resin (trade name: IRA-400) in which the ionic form was converted to the OH form was 50 m A purified acetonitrile was obtained by performing the same operation as in Example 4 except for using. The absorbance of this acetonitrile for ultraviolet light at a wavelength of 200 nm was 0.040, and the absorbance for ultraviolet light at 210 to 400 nm was 0.025 or less.
  • IRA-400 strongly basic anion exchange resin
  • Example 4 The same procedure as in Example 4 was carried out except that 30 g of granular CaC0 was used as the basic substance in the second step of Example 4, to obtain an acetonitrile.
  • the absorbance of this acetonitrile for ultraviolet light at a wavelength of 200 nm was 0.034, and the absorbance for ultraviolet light of 210 to 400 nm was 0.021 or less.
  • the absorbance of this acetonitrile for ultraviolet light at a wavelength of 200 nm was 0.030, and the absorbance for ultraviolet light from 210 to 400 nm was 0.019 or less.
  • Example 4 The same operation as in Example 4 was performed up to the second step using 50 g of activated carbon carrying 2.0 wt% of KOH as the basic substance in the second step of Example 4.
  • the acetonitrile obtained in the second step is transferred to the 40th stage of the first column.
  • acetonitrile extracted from the bottom of the column in an amount of 80% of the feed amount was The mixture was fed to the 20th stage of the column, operated at a reflux ratio of 3, and 70% of the supplied amount of purified acetonitril was extracted from the top of the column.
  • the absorbance of this acetonitrile for ultraviolet light at a wavelength of 200 nm was 0.043, and the absorbance of ultraviolet light for 210 to 400 nm was 0.026 or less.
  • Example 4 acetonitrile was obtained by performing the same operation except that contact with ozone in the first step was not performed.
  • the absorbance of this acetonitrile for ultraviolet rays at a wavelength of 20 nm was 1.601.
  • Example 4 acetonitrile was obtained by performing the same operation except that the contact with the basic substance in the second step was not performed.
  • the absorbance of this acetonitrile for ultraviolet light at a wavelength of 200 nm was 0.157.
  • Example 4 the same operation was performed except that the distillation in the third step was not performed, to obtain acetonitrile.
  • the absorbance of this acetonitrile for ultraviolet light at a wavelength of 20 nm was 1.451.
  • Example 4 operations were performed in the order of the second step, the third step, and the first step to obtain acetonitrile.
  • the absorbance of this acetonitrile for ultraviolet rays at a wavelength of 200 nm was 1.655.
  • Example 4 the operations were performed in the order of the second step, the first step, and the third step. I got an acetonitrile.
  • the absorbance of this acetonitrile at a wavelength of 200 nm for ultraviolet light was 0.219.
  • Example 4 the operation was performed in the order of the third step, the first step, and the second step to obtain an acetonitrile.
  • the absorbance of this acetonitrile for ultraviolet rays at a wavelength of 200 nm was 1.552.
  • Example 4 the operation was performed in the order of the third step, the second step, and the first step to obtain acetonitrile.
  • the absorbance of this acetonitrile for ultraviolet rays at a wavelength of 200 nm was 1.550.
  • Acetonitrile which is obtained as a by-product during the production of acrylonitrile by the propylene ammoxidation reaction, is purified and recovered as a raw material acetonitrile.
  • the following operation was performed using acetonitrile having an ultraviolet absorbance of 0.503 and containing acrylonitrile as impurities at 1 ppm, oxazole at 2 ppm, and aryl alcohol at 20 ppm.
  • 150 ml of the acetonitrile was placed in a 2 £ round bottom flask with a stirrer, and 0.24 vol% (5.1 / The ozone-containing gas containing Nm 3 ) was supplied at 3 N £ Zmin for 90 minutes.
  • the pH value of an aqueous solution obtained by diluting acetonitrile to 1Z10 with water after this operation was 6.0.
  • the acetonitrile obtained in the second step was transferred to the 40th stage of the first column at 250 m / H and supply from the bottom by operating at a reflux ratio of 12 with the top pressure at atmospheric pressure
  • Acetonitrile extracted in an amount of 75% of the amount was supplied to the second column of the second column, operated at a reflux ratio of 3 and purified from the top of the column with an amount of 65% of the supplied amount. I pulled out the Settrill.
  • the absorbance of ultraviolet light at a wavelength of 200 nm of this acetate nitrile was 0.025, and the absorbance of ultraviolet light at 210 to 400 nm was 0.016 or less.
  • Example 10 In the second step of Example 10, ethanolamine was added. Purified acetonitrile was obtained in the same manner as in Example 10, except that the pH of an aqueous solution obtained by diluting this acetonitrile with water to 10 was adjusted to 9.0. . The absorbance of ultraviolet light at a wavelength of 200 nm of this acetonitrile was 0.027, and the absorbance of ultraviolet light at 210 to 400 nm was 0.013 or less.
  • Example 8 parts by weight of the raw material acetonitrile used in Example 1 was added to 2 parts by weight of the acetate nitrile obtained in Example 4, and the absorbance of ultraviolet light at a wavelength of 200 nm was 1.4.
  • Tonitrile was prepared, and the starting material was used as a raw material, and the acetonitrile was put into the same apparatus as in the first step of Example 10 at a rate of 1,500 m.
  • a gas containing ozone was supplied at 3 £ in and contacted for 240 minutes.
  • This acetonitrile was subjected to the same operation using the same apparatus as in the second and third steps of Example 4 to obtain purified acetonitrile.
  • the absorbance of ultraviolet light at a wavelength of 200 nm of this acetate tube was 0.045, and the absorbance of ultraviolet light at 210 to 400 nm was 0.028 or less.
  • acetonitrile obtained as a by-product in the production of acrylonitrile by an ammoxidation reaction of propylene is recovered and purified.
  • Ozone-containing gas containing 0.24 vo 1% of ozone was supplied at 3 N ⁇ / in, and when the ozone concentration in the exhaust gas reached 0.20 V 01%, the ozone-containing gas was supplied. Stopped. At this time, the ozone concentration in the exhaust gas was 83% of the ozone concentration in the supply gas.
  • This acetonitrile was subjected to the same operation using the same apparatus as in the second and third steps of Example 4 to obtain purified acetonitrile.
  • the absorbance of this acetonitrile at ultraviolet wavelength of 200 nm was 0.040, and the absorbance of ultraviolet light at 210 to 400 nm was 0.026 or less.
  • Example 4 As the first step of Example 4, the acetonitrile 1 was placed in the round bottom flask equipped with a stirrer 2 and Wako Pure Chemical's special grade potassium permanganate 1 was used as a compound to generate nascent oxygen. .09 g was added, and the mixture was stirred at 60 ° C for 2 hours. Thereafter, simple distillation was performed to obtain acetonitrile containing no potassium permanganate. Next, the second and third steps were performed in the same manner as in Example 4 to obtain purified acetonitrile. The absorbance of this acetonitrile for ultraviolet light at a wavelength of 200 nm was 0.045, and the absorbance for ultraviolet light of 210 to 400 nm was 0.027 or less.
  • the absorbance of ultraviolet light at a wavelength of 200 nm of this acetate is 0.011, and the absorbance of ultraviolet light at a wavelength of 210 nm to 400 nm.
  • the luminous intensity was less than 0.05.
  • Lipid analysis was performed using this acetonitril.
  • Acetonitrile used for high-performance liquid chromatography-mobile phase Requires high purity.
  • commercially available acetonitrile for liquid chromatography and acetonitrile of Comparative Example 2 purified according to East German Patent No. DD 217 212 A1 have high impurity levels and lipid analysis. was unsuitable for However, this acetonitrile having an absorbance of 0.011 for ultraviolet rays having a wavelength of 200 nm was remarkably low in impurity level and was suitable for lipid analysis.
  • Purified acetonitrile was obtained by performing the same operation as in Example 13 except that 50 ml of activated carbon was used as the adsorbent in the second step of Example 13.
  • the absorbance of this acetonitrile for ultraviolet light at a wavelength of 200 nm was 0.013, and the absorbance for ultraviolet light of 210 to 400 nm was not more than 0.006.
  • Example 4 the first step, the third step, and the second step were performed in this order to obtain purified acetonitrile.
  • the absorbance of this acetonitrile for ultraviolet light at a wavelength of 200 nm was 0.048, and the absorbance for ultraviolet light of 210 to 400 nm was 0.028 or less.
  • the crude acetonitrile is brought into contact with nascent oxygen and then passed through a packed column filled with a basic substance and at least one substance selected from the group consisting of a basic substance and an adsorbent to reduce acid and permanganate.
  • Acetonitrile containing less active substances can be produced.
  • This method does not require a cooler, heat source, and advanced temperature control technology compared to the distillation method disclosed in East Germany DD 217 12 12 A1, and is a very simple method for purifying acetonitrile. is there.
  • crude acetonitrile can be used as a solvent for high-performance liquid chromatography in the production of acetonitrile having an ultraviolet absorbance of 200 to 400 nm having an ultraviolet absorbance of 0.05 or less.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Acétonitrile de grande pureté, présentant un niveau d'absorption inférieur dans la région ultraviolette des longueurs d'ondes de 200 à 400 nm, et pouvant être utilisé comme solvant à phase mobile en chromatographie liquide, plus particulièrement en chromatographie liquide à haute performance. Un procédé simplifié de purification d'acétonitrile brut consiste soit à mettre l'acétonitrile brut en contact avec de l'oxygène naissant, puis avec au moins un composé choisi entre des adsorbants et des substances de base; après quoi on sépare et on enlève éventuellement les composés à bas point d'ébullition et à point d'ébullition élevé; soit à mettre l'acétonitrile brut en contact avec de l'oxygène naissant, à séparer et enlever des composés à bas point d'ébullition et à point d'ébullition élevé, et à mettre l'acétonitrile ainsi traité en contact avec au moins un composé choisi parmi des adsorbants et des substances de base.
PCT/JP1993/000638 1993-05-14 1993-05-14 Acetonitrile de grande purete et purification d'acetonitrile brut Ceased WO1994026698A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
KR1019950700150A KR0171245B1 (ko) 1993-05-14 1993-05-14 고 순도 아세토니트릴 및 미정제 아세토니트릴의 정제 방법
DE4397378A DE4397378B3 (de) 1993-05-14 1993-05-14 Hochgereinigtes Acetonitril und Verfahren zur Reinigung von rohem Acetonitril
PCT/JP1993/000638 WO1994026698A1 (fr) 1993-05-14 1993-05-14 Acetonitrile de grande purete et purification d'acetonitrile brut
GB9500707A GB2285443B (en) 1993-05-14 1993-05-14 Highly purified acetonitrile and process for purifying crude acetonitrile
DE4397378T DE4397378T1 (de) 1993-05-14 1993-05-14 Hochgereinigtes Acetonitril und Verfahren zur Reinigung von rohem Acetonitril
FR9306051A FR2705342B1 (fr) 1993-05-14 1993-05-19 Acétonitrile très purifié et procédé de purification d'acétonitrile brut.
US08/371,180 US5629443A (en) 1993-05-14 1995-01-11 Highly purified acetonitrile and process for purifying crude acetonitrile

Applications Claiming Priority (2)

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PCT/JP1993/000638 WO1994026698A1 (fr) 1993-05-14 1993-05-14 Acetonitrile de grande purete et purification d'acetonitrile brut
FR9306051A FR2705342B1 (fr) 1993-05-14 1993-05-19 Acétonitrile très purifié et procédé de purification d'acétonitrile brut.

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CN113461570A (zh) * 2021-06-24 2021-10-01 索闻特环保科技(上海)有限公司 含有异丙醇、乙腈、三乙胺和水的混合液的处理方法
CN113956179A (zh) * 2021-12-20 2022-01-21 潍坊中汇化工有限公司 一种乙腈精制方法及其应用
CN117417269A (zh) * 2023-12-19 2024-01-19 潍坊中汇化工有限公司 一种无水乙腈的制备方法

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FR2766388B1 (fr) * 1997-07-24 2000-01-14 Rhodia Chimie Sa Procede d'elimination de composes organophosphores contenus dans un gaz ou liquide
US6395142B1 (en) * 1999-10-14 2002-05-28 Chemcycles, Inc. Method and apparatus for purifying low grade acetonitrile and other constituents from hazardous waste
US10336690B2 (en) * 2014-02-24 2019-07-02 Honeywell International Inc. Methods and systems for processing an acetonitrile waste stream

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JPS5132518A (ja) * 1974-09-06 1976-03-19 Mitsubishi Chem Ind Asetonitorirunoseiseiho
JPS5732259A (en) * 1980-06-26 1982-02-20 Du Pont Purification of acetanilide by caustic alkali extraction

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DD217212A1 (de) * 1983-05-10 1985-01-09 Petrolchemisches Kombinat Verfahren zur reinigung von acetonitril
DD282818A7 (de) * 1988-04-20 1990-09-26 Petrolchemisches Kombinat Verfahren destillativ und oxidativ vorbehandelten technischen acetonitrils
JP3104312B2 (ja) * 1991-07-16 2000-10-30 旭化成工業株式会社 アセトニトリルの精製方法
JPH05140070A (ja) * 1991-11-14 1993-06-08 Asahi Chem Ind Co Ltd アセトニトリルの精製方法
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JPS5132518A (ja) * 1974-09-06 1976-03-19 Mitsubishi Chem Ind Asetonitorirunoseiseiho
JPS5732259A (en) * 1980-06-26 1982-02-20 Du Pont Purification of acetanilide by caustic alkali extraction

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113461570A (zh) * 2021-06-24 2021-10-01 索闻特环保科技(上海)有限公司 含有异丙醇、乙腈、三乙胺和水的混合液的处理方法
CN113461570B (zh) * 2021-06-24 2023-02-17 索闻特环保科技(上海)有限公司 含有异丙醇、乙腈、三乙胺和水的混合液的处理方法
CN113956179A (zh) * 2021-12-20 2022-01-21 潍坊中汇化工有限公司 一种乙腈精制方法及其应用
CN117417269A (zh) * 2023-12-19 2024-01-19 潍坊中汇化工有限公司 一种无水乙腈的制备方法
CN117417269B (zh) * 2023-12-19 2024-03-12 潍坊中汇化工有限公司 一种无水乙腈的制备方法

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GB9500707D0 (en) 1995-03-08
FR2705342A1 (fr) 1994-11-25

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