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WO2018070165A1 - Dispositif ainsi que procédé de mesure, et dispositif de fabrication de liquide comprenant une cyanhydrine - Google Patents

Dispositif ainsi que procédé de mesure, et dispositif de fabrication de liquide comprenant une cyanhydrine Download PDF

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Publication number
WO2018070165A1
WO2018070165A1 PCT/JP2017/032843 JP2017032843W WO2018070165A1 WO 2018070165 A1 WO2018070165 A1 WO 2018070165A1 JP 2017032843 W JP2017032843 W JP 2017032843W WO 2018070165 A1 WO2018070165 A1 WO 2018070165A1
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WIPO (PCT)
Prior art keywords
raw material
concentration
cyanohydrin
carbonyl compound
cyanating agent
Prior art date
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Ceased
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PCT/JP2017/032843
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English (en)
Japanese (ja)
Inventor
隆典 青木
英雅 青木
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Resonac Holdings Corp
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Showa Denko KK
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Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Priority to JP2018544710A priority Critical patent/JP7038061B2/ja
Publication of WO2018070165A1 publication Critical patent/WO2018070165A1/fr
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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/16—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same carbon atom of an acyclic carbon skeleton
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length

Definitions

  • the present invention relates to a measuring apparatus, a manufacturing apparatus for a cyanohydrin-containing liquid, and a measuring method.
  • Cyanohydrin is industrially important as a raw material for carboxylic acids, amino acids, hydroxy esters and the like.
  • a method for producing such cyanohydrin for example, methods described in Patent Documents 1 and 2 are disclosed.
  • cyanohydrin is useful as a raw material for carboxylic acids, amino acids, hydroxyesters, and the like.
  • carboxylic acids and the like are used for food and drink materials.
  • lactonitrile which is one of cyanohydrins, is useful as a raw material for producing lactic acid and the like, and the lactic acid and the like are used for food and drink materials and the like.
  • this food / beverage material and the like have been required to have an extremely low impurity content such as a reaction raw material, and the cyanohydrin-containing liquid that is the raw material is also required to have an extremely low impurity content.
  • the conventional cyanohydrin-containing liquid production method continuously produces a cyanohydrin-containing liquid
  • the amount of the raw material carbonyl compound in the reactor and the amount of the raw material cyanating agent cannot be sufficiently controlled.
  • a cyanohydrin-containing liquid having a low impurity content could not be easily obtained because the purification conditions could not be maintained in an optimal state in the purification of the reaction liquid.
  • the present invention easily produces a cyanohydrin-containing liquid having a low impurity content such as a reaction raw material, so that it can quickly measure the concentration of a compound in the reaction liquid, a measurement method, and a cyanohydrin-containing liquid having the apparatus. It is an object to provide a liquid manufacturing apparatus.
  • the inventors of the present invention have at least one of an ultraviolet absorptiometer and a cyan meter, a refractometer, and a measurement having a specific program for calculating a cyanohydrin concentration.
  • the present inventors have found that the above problems can be solved by an apparatus, and have completed the present invention.
  • the present invention relates to the following [1] to [7], for example.
  • An apparatus used when a raw material carbonyl compound represented by formula (A) and a raw material cyanating agent represented by formula (B) are reacted to obtain a cyanohydrin-containing liquid continuously The device is An ultraviolet absorptiometer for measuring the concentration of the carbonyl compound contained in the reaction solution of the raw material carbonyl compound and the raw material cyanating agent, and a refractometer for measuring the total concentration of the carbonyl compound and the cyanohydrin are provided. And a program for calculating the concentration of the cyanohydrin from the concentration of the carbonyl compound obtained from the ultraviolet absorptiometer and the total concentration of the carbonyl compound and the cyanohydrin obtained from the refractometer.
  • a cyan meter for measuring the concentration of the cyanating agent contained in the reaction solution of the raw material carbonyl compound and the raw material cyanating agent, and a refractometer for measuring the total concentration of the cyanating agent and the cyanohydrin are provided.
  • An ultraviolet absorptiometer for measuring the concentration of the carbonyl compound contained in the reaction solution of the raw material carbonyl compound and the raw material cyanating agent, a cyan meter for measuring the concentration of the cyanating agent, and the carbonyl compound and the cyanide
  • a refractometer for measuring the total concentration of the agent and the cyanohydrin, the concentration of the carbonyl compound obtained from the ultraviolet absorptiometer, the concentration of the cyanating agent obtained from the cyan meter, and
  • a measuring apparatus comprising: a program for calculating a concentration of the cyanohydrin from a total concentration of the carbonyl compound, the cyanating agent and the cyanohydrin obtained from the refractometer.
  • R 1 and R 2 are each independently a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, or a part of these groups It is a group substituted with a substituent.
  • M is a hydrogen atom, an alkali metal, an alkaline earth metal, iron, copper, or zinc, and n is a valence of M.
  • a supply unit for supplying the raw material carbonyl compound and the raw material cyan compound to the reaction system;
  • a reactor for reacting the supplied raw material to obtain a reaction liquid containing cyanohydrin;
  • An apparatus for producing a cyanohydrin-containing liquid comprising the measurement apparatus according to [1] or [2].
  • the measuring device is provided in the reactor or on a flow path branched from the reactor, and measures the reaction liquid in the reactor. Based on the result of the measurement device, it has a control unit for controlling the supply amount to the reaction system of at least one compound selected from the raw material carbonyl compound and the raw material cyan compound, The apparatus for producing a cyanohydrin-containing liquid according to [3].
  • the apparatus further comprises a distillation apparatus for distilling the reaction solution obtained in the reactor,
  • the measuring device is provided in the distillation device or on a flow path branched from the distillation device, and measures the reaction liquid in the distillation device, Based on the result of the measurement device, having a control unit for controlling the distillation conditions,
  • the apparatus for producing a cyanohydrin-containing liquid according to [3].
  • the concentration of the compound in the reaction solution can be quickly measured, and a cyanohydrin-containing solution having a low impurity content such as a reaction raw material can be easily produced.
  • the measuring device of the present invention is an apparatus used when a raw material carbonyl compound represented by the formula (A) and a raw material cyanating agent represented by the formula (B) are reacted to continuously obtain a cyanohydrin-containing liquid. Because The device is An ultraviolet absorptiometer for measuring the concentration of the carbonyl compound contained in the reaction solution of the raw material carbonyl compound and the raw material cyanating agent, and a refractometer for measuring the total concentration of the carbonyl compound and the cyanohydrin are provided.
  • a program for calculating the concentration of the cyanohydrin from the concentration of the carbonyl compound obtained from the ultraviolet absorptiometer and the total concentration of the carbonyl compound and the cyanohydrin obtained from the refractometer A cyan meter for measuring the concentration of the cyanating agent contained in the reaction solution of the raw material carbonyl compound and the raw material cyanating agent, and a refractometer for measuring the total concentration of the cyanating agent and the cyanohydrin are provided. And a program for calculating the concentration of the cyanohydrin from the concentration of the cyanating agent obtained from the cyanometer and the total concentration of the cyanating agent and the cyanohydrin obtained from the refractometer.
  • An ultraviolet absorptiometer for measuring the concentration of the carbonyl compound contained in the reaction solution of the raw material carbonyl compound and the raw material cyanating agent, a cyan meter for measuring the concentration of the cyanating agent, and the carbonyl compound and the cyanide
  • a refractometer for measuring the total concentration of the agent and the cyanohydrin, the concentration of the carbonyl compound obtained from the ultraviolet absorptiometer, the concentration of the cyanating agent obtained from the cyan meter, and And a program for calculating the concentration of the cyanohydrin from the total concentration of the carbonyl compound, the cyanating agent and the cyanohydrin obtained from the refractometer.
  • R 1 and R 2 are each independently a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, or a part of these groups It is a group substituted with a substituent.
  • M is a hydrogen atom, an alkali metal, an alkaline earth metal, iron, copper, or zinc, and n is a valence of M.
  • the cyanohydrin-containing liquid In the production of the cyanohydrin-containing liquid, it is preferable to produce it continuously from the viewpoint of productivity and the like.
  • the present inventor tried various methods such as control of the impurity content of the reaction raw material, control of reaction, control of purification conditions, etc. in an attempt to produce a cyanohydrin-containing liquid having a low impurity content, but the cyanohydrin having a sufficiently low impurity content.
  • the containing liquid could not be produced continuously.
  • a raw material carbonyl compound and a raw material cyanating agent are reacted to obtain a cyanohydrin-containing liquid
  • a raw material carbonyl compound or a raw material cyanating agent is added to a reactor.
  • the supply amount was controlled using a flow meter or the like. Even if the supply amount is controlled using a flow meter or the like, the amount of the raw material carbonyl compound supplied to the reactor and the amount of the raw material cyanating agent cannot be sufficiently controlled, and the quality of the resulting cyanohydrin-containing liquid is poor. It was not stable.
  • the measuring device of the present invention is useful for grasping the state of the reaction liquid in the reactor or the distillation apparatus for reacting the raw material carbonyl compound and the raw material cyanide.
  • the measuring device of the present invention examples include measuring devices (I) to (III) described below.
  • the measuring device (I) is a device having an ultraviolet absorptiometer and a refractometer as a device for measuring the concentration of a raw material.
  • the measuring device (I) measures the concentration of the carbonyl compound contained in the reaction solution using an ultraviolet absorptiometer, and sums the carbonyl compound and cyanohydrin contained in the reaction solution using a refractometer. Measure the concentration of.
  • the cyanohydrin concentration is calculated from the concentration of the carbonyl compound obtained by the ultraviolet absorptiometer and the total concentration of the carbonyl compound and cyanohydrin obtained by the refractometer. calculate.
  • the measuring device (II) is a device having a cyan meter and a refractometer as a device for measuring the concentration of the raw material.
  • the measuring device (II) uses a cyan meter to measure the concentration of the cyanating agent contained in the reaction solution, and using a refractometer, the total of the cyanating agent and cyanohydrin contained in the reaction solution. Measure the concentration of.
  • the measuring apparatus (II) of the present invention normally has, from the concentration of the cyanating agent obtained with the cyan meter, and the total concentration of the cyanating agent and cyanohydrin obtained with the refractometer, Calculate the cyanohydrin concentration.
  • the measuring device (III) is a device having an ultraviolet absorptiometer, a cyan meter, and a refractometer as a device for measuring the concentration of the raw material.
  • the measuring device (III) measures the concentration of the carbonyl compound contained in the reaction solution using an ultraviolet absorptiometer, and measures the concentration of the cyanating agent contained in the reaction solution using a cyan meter, Using a refractometer, the total concentration of the carbonyl compound, the cyanating agent, and cyanohydrin contained in the reaction solution is measured.
  • the concentration of the carbonyl compound obtained with the ultraviolet absorptiometer is calculated from the total concentration of the obtained carbonyl compound, cyanating agent and cyanohydrin.
  • the measurement device of the present invention is preferably the measurement devices (I) and (II), more preferably the measurement device (I), from the viewpoint of simplicity of the device and ease of measurement.
  • the “concentration” measured and calculated by the measuring apparatus of the present invention that is, the concentration of the carbonyl compound, the concentration of the cyanating agent, the total concentration of at least one of the carbonyl compound and the cyanating agent and cyanohydrin, the cyanohydrin concentration, etc.
  • the molar concentration is preferable.
  • the concentration of the compound in the reaction solution can be quickly measured, and the supply amount of raw material and distillation conditions can be controlled based on the measurement result.
  • a cyanohydrin-containing liquid with a low content can be easily produced.
  • the measuring device of the present invention preferably has an automatic sampling function that can automatically sample the reaction solution. Sampling of the reaction solution may be performed manually, but a sample can be stably obtained by regular automatic sampling.
  • Automatic sampling is, for example, a flow path (circulation path) that sends liquid from the reactor to the instrument that performs measurement, or that sends liquid from the reactor to the instrument that performs measurement, and sends the liquid from the instrument to the reactor after measurement. Done through.
  • the term “automatic” means that the device is actively operated without human intervention during the operation of the manufacturing equipment such as the reactor. That is, setting before starting the reaction, maintenance, and the like may be performed with human intervention.
  • the concentration of the sampled reaction solution is detected by the measuring device of the present invention.
  • the detection may be performed manually or automatically, it is preferable that the detection is automatically performed.
  • Automatic detection means that the sampled reaction solution is automatically detected.
  • automatic measurement means that the reaction solution is sampled and the sampled reaction solution is automatically detected.
  • the measurement apparatus of the present invention has an automatic measurement function capable of automatic measurement, such as the concentration of the carbonyl compound, the concentration of the cyanating agent, and the total concentration of at least one of the carbonyl compound and the cyanating agent and cyanohydrin. It is preferable because it is easy to grasp such information over time. In other words, when it is not automatic measurement, it is necessary to manually perform at least one of sampling and detection of the reaction solution, which is troublesome. However, automatic measurement is preferable because such trouble is unnecessary.
  • the concentration of the carbonyl compound, the concentration of the cyanating agent, the total concentration of at least one of the carbonyl compound and the cyanating agent, and cyanohydrin, etc. are obtained.
  • the calculation of the concentration is a manual calculation. However, automatic calculation may be used, and automatic calculation is preferable from the viewpoint of calculation speed, accuracy, and labor.
  • the calculation is usually based on the relationship between the concentration of the carbonyl compound, the concentration of the cyanating agent, the total concentration of at least one of the carbonyl compound and the cyanating agent and cyanohydrin, and the physical properties to be detected. Calculated.
  • the program of the measuring device of the present invention allows the cyanohydrin. Calculate the concentration.
  • Automatic recording may be recorded as electronic data on a storage medium such as HDD (Hard Disk Drive), SSD (Solid State Drive), CD, DVD, etc., or may be recorded by printing on paper or the like, both But you can.
  • HDD Hard Disk Drive
  • SSD Solid State Drive
  • CD Compact Disc
  • DVD Digital versatile disc
  • Automatic recording may be recorded as electronic data on a storage medium such as HDD (Hard Disk Drive), SSD (Solid State Drive), CD, DVD, etc., or may be recorded by printing on paper or the like, both But you can.
  • the measurement method of the present invention is used when a raw material carbonyl compound represented by the formula (A) and a raw material cyanating agent represented by the formula (B) are reacted to obtain a cyanohydrin-containing liquid continuously.
  • Measuring method In the reaction solution of the raw material carbonyl compound and the raw material cyanating agent, when the concentration of the cyanating agent was regarded as 0, the concentration of the carbonyl compound measured with an ultraviolet absorptiometer and the refractive index were measured with a refractometer.
  • the concentration of cyanohydrin is calculated from the total concentration of carbonyl compound and cyanohydrin.
  • concentration of the carbonyl compound is regarded as 0 in the reaction solution of the raw material carbonyl compound and the raw material cyanating agent
  • concentration of the cyanating agent measured with a cyan meter and the cyanation measured with a refractometer
  • concentration of cyanohydrin is calculated from the total concentration of the agent and cyanohydrin
  • the concentration of the carbonyl compound measured with an ultraviolet absorptiometer, cyanide The concentration of the cyanohydrin is calculated from the concentration of the cyanating agent measured with the meter and the total concentration of the carbonyl compound, the cyanating agent and cyanohydrin measured with the refractometer. That is, the measurement method of the present invention is a method
  • the reaction between the raw material carbonyl compound and the raw material cyanating agent generally proceeds rapidly and the conversion rate is almost 100%. For this reason, if the supply amount of either one of the raw material carbonyl compound and the raw material cyanating agent is excessive, the other concentration contained in the reaction solution can be regarded as zero.
  • the case where the concentration of the cyanating agent is regarded as 0 refers to a case where the amount of the raw material carbonyl compound supplied to the reactor is typically larger than the supply amount of the raw material cyanating agent.
  • the molar ratio of the raw material carbonyl compound to the cyano group of the raw material cyanating agent is 1.001 or more.
  • the measurement device (I) it is preferable to use the measurement device (I) as a measurement device.
  • the case where the concentration of the carbonyl compound is regarded as 0 refers to a case where the amount of the raw material cyanating agent supplied to the reactor is typically larger than the supply amount of the raw material carbonyl compound.
  • the molar ratio of the cyano group of the raw material cyanating agent to the raw material carbonyl compound is 1.001 or more.
  • the measurement device (II) it is preferable to use the measurement device (II) as the measurement device.
  • the case where both the concentration of the carbonyl compound and the concentration of the cyanating agent are not considered to be zero typically means that the molar ratio of the raw material carbonyl compound supplied to the reactor and the cyano group of the raw material cyanating agent is close to 1. Specifically, when the molar ratio (raw carbonyl compound / cyano group of the raw cyanating agent) supplied to the reactor cannot stably achieve 1.001 or more, or the molar ratio This is a case where (the cyano group / raw material carbonyl compound of the raw material cyanating agent) cannot stably achieve 1.001 or more.
  • the concentration of the carbonyl compound and the concentration of the cyanating agent are not regarded as 0
  • the molar ratio (raw carbonyl compound / cyano group of the raw cyanating agent) or molar ratio (raw cyanide) supplied to the reactor The case where the cyano group / raw material carbonyl compound) of the agent is 1.000 or more and less than 1.001 is also included.
  • the measurement device (III) it is preferable to use the measurement device (III) as a measurement device.
  • the measuring apparatus and measuring method of the present invention are not particularly limited as long as they are used when a raw material carbonyl compound and a raw material cyanating agent are reacted to obtain a cyanohydrin-containing liquid continuously. It is preferably used when a cyanohydrin-containing liquid is produced through 1 to 3.
  • Step 1 A step of supplying a raw material carbonyl compound and a raw material cyanating agent to the reactor, and continuously supplying at least one of the raw material carbonyl compound and the raw material cyanating agent.
  • Step 2 In the reactor, step 1 A step of obtaining a reaction liquid by reacting the raw material carbonyl compound and a raw material cyanating agent supplied in Step 3: A purification step of supplying the reaction liquid obtained in Step 2 to a distillation apparatus and distilling the reaction liquid
  • the measuring device and the measuring method of the present invention can be used, for example, for measuring the reaction liquid in the reactor obtained in the step 2 and for measuring the reaction liquid in the distillation apparatus in the step 3.
  • Step 1 is a step of supplying the raw material carbonyl compound and the raw material cyanating agent to the reactor, and is a step of continuously supplying at least one of the raw material carbonyl compound and the cyanating agent.
  • R 1 COR 2 ... Formula (A)
  • R 1 and R 2 are each independently a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, or a part of these groups It is a group substituted with a substituent.
  • the aliphatic hydrocarbon group preferably has 1 to 30 carbon atoms.
  • the alicyclic hydrocarbon group preferably has 3 to 30 carbon atoms.
  • the aromatic hydrocarbon group preferably has 6 to 30 carbon atoms.
  • the heterocyclic group preferably has 2 to 30 carbon atoms.
  • the heterocyclic group represents a group having a ring formed containing a heteroatom such as nitrogen, oxygen, or sulfur.
  • an aromatic heterocyclic group is an aromatic carbonization. It is not a hydrogen group but a heterocyclic group.
  • substituents examples include an alkyl group, allyl group, hydroxy group, carbonyl group, carboxyl group, alkoxycarbonyl group, alkoxy group, fluoro group, chloro group, bromo group, iodo group, cyano group, amino group, and alkylamino.
  • the group substituted with the substituent may have one substituent or two or more.
  • R 1 and R 2 a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or the like from the viewpoint that the effect of the present invention is more easily exhibited and the reactivity with the raw material cyanating agent is excellent.
  • An aromatic hydrocarbon group having 6 to 14 carbon atoms is preferable, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is more preferable, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is more preferable, and R 1 is a hydrogen atom.
  • R 2 is particularly preferably an alkyl group having 1 to 3 carbon atoms.
  • the raw material carbonyl compound a compound in which R 1 or R 2 is a hydrogen atom, that is, an aldehyde is preferable, and acetaldehyde is most preferable.
  • raw material carbonyl compound examples include saturated alkyl aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde; unsaturated aldehydes such as acryl aldehyde and methacrylamide; aromatic aldehydes such as benzaldehyde, phenylacetaldehyde, naphthaldehyde, and phthalaldehyde.
  • saturated alkyl aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde
  • unsaturated aldehydes such as acryl aldehyde and methacrylamide
  • aromatic aldehydes such as benzaldehyde, phenylacetaldehyde, naphthaldehyde, and phthalaldehyde.
  • a heterocyclic group-containing aldehyde such as nicotine aldehyde; acetone, 2-butanone, 2-pentanone, 3-methyl-2-butanone, 3-pentanone, 3-hexanone, 2-methyl-3-pentanone, 3-heptanone, 2 -Methyl-3-hexanone, 2,4-dimethyl-3-pentanone, acetophenone, 2-nonanone, 2-octanone, 2-heptanone, 2-hexanone, 4-methyl-2-pentanone, 4- Heptanone, cyclohexanone, ketones, such as 2,6-dimethyl-4-heptanone.
  • the raw material carbonyl compound two or more kinds may be used, but it is preferable to use one kind alone because of easy concentration measurement and purification.
  • the raw material carbonyl compound is not particularly limited and may be a compound that can be obtained for industrial use, research use, or the like, but it is preferable to use a purified carbonyl compound obtained by purifying such a raw material carbonyl compound.
  • a purified carbonyl compound obtained by purifying such a raw material carbonyl compound.
  • impurities such as dimers, trimers, tetramers and other oligomers having a higher boiling point than the carbonyl compound derived from the carbonyl compound contained in the resulting reaction solution (hereinafter also referred to as “specific impurities”).
  • the amount can be reduced.
  • the specific impurity means a component having a boiling point of 25 ° C. or higher at normal pressure.
  • the content of the specific impurity contained in the raw material acetaldehyde is preferably 300 ppm by mass or less, more preferably 250 ppm by mass or less, and further preferably 200 ppm by mass or less.
  • the content of the specific impurity can be measured by, for example, the method described in the examples, but may be below the detection limit when measured by the method.
  • the content of the specific impurity can be within the above range by purifying the raw material carbonyl compound, but it is not necessarily purified if the content of the unpurified raw material carbonyl compound is within the above range.
  • the lower limit of the range is not particularly limited. However, if a numerical value is given, for example, the lower limit value of the content of the specific impurity is preferably 0.00. 1 ppm by mass.
  • the method for obtaining the purified carbonyl compound is not particularly limited, and a conventionally known method can be adopted. However, from the viewpoint that a purified carbonyl compound can be easily obtained by a simple method, the starting carbonyl compound is used. A distillation method is preferred.
  • the raw material cyanide is represented by the following formula (B).
  • M is a hydrogen atom, an alkali metal, an alkaline earth metal, iron, copper, or zinc, and n is a valence of M.
  • n is usually an integer of 1 to 3, preferably 1 or 2.
  • alkali metal examples include lithium, sodium, potassium, rubidium, and cesium.
  • alkaline earth metal examples include magnesium, calcium, strontium, and barium.
  • the raw material cyanating agent examples include HCN, LiCN, NaCN, KCN, RbCN, CsCN, Mg (CN) 2 , Ca (CN) 2 , Sr (CN) 2 , Ba (CN) 2 , Fe (CN) 2 , Fe (CN) 3 , CuCN, Cu (CN) 2 , Zn (CN) 2, etc., among these, making pH control of the reaction liquid easier and by-product of salt.
  • Hydrogen cyanide (HCN) is preferable because it can be suppressed.
  • Two or more kinds of the raw material cyanating agent may be used, but it is preferable to use one kind alone for ease of concentration measurement and purification.
  • the raw material cyanating agent is not particularly limited, and may be a compound that can be obtained for industrial use, research use, and the like. Specifically, in the case of hydrogen cyanide, hydrogen cyanide by-produced by an ammoxidation reaction or the like can be used, and methane or the like can be produced from a raw material. It is also possible to produce sodium cyanide by reacting with a strong acid such as sulfuric acid. Industrially, it is preferable to use hydrogen cyanide by-produced in the production of (meth) acrylonitrile.
  • the raw material cyanating agent may be a purified cyanating agent purified in advance by distillation, adsorption or the like.
  • a purified cyanating agent may be used for the purpose of obtaining a higher purity cyanohydrin-containing liquid.
  • impure components in the cyanating agent are And can be removed in the purification step of Step 2 below.
  • Step 1 is a step of supplying the raw material carbonyl compound and the raw material cyanating agent to the reactor, and continuously supplying at least one of the raw material carbonyl compound and the cyanating agent.
  • the reactor is not particularly limited as long as the raw material can be continuously supplied and the raw material carbonyl compound and the raw material cyanating agent can be reacted.
  • a continuous tank reactor, a tube A type reactor, a screw feeder type mixer, a static mixer and the like can be used.
  • a reactor capable of continuously taking out the cyanohydrin-containing liquid is preferable. Further, as the reactor, a batch reactor cannot be used because the raw material cannot be continuously supplied.
  • the reactor is preferably made of a material other than iron since the generation of impurities is promoted when the raw material carbonyl compound comes into contact with the iron member.
  • Specific examples of the material of the reactor include copper, titanium, nickel, stainless steel, Monel (trademark), Hastelloy (trademark), Inconel (trademark), Incoloy (trademark), fluororesin, glass, porcelain and the like. It is done.
  • step 1 it is preferable to supply a solvent.
  • the solvent one kind or two or more kinds of solvents can be used.
  • the solvent either water or an organic solvent can be used.
  • the organic solvent include alcohol, carboxylic acid, ester and the like.
  • the solvent it is preferable to use water that can easily adjust the concentration of the cyanohydrin-containing liquid after the reaction and is excellent in terms of cost.
  • the amount of the solvent supplied to the reactor is not particularly limited, but the amount of the solvent in the reaction solution in Step 2 is preferably 5 to 95% by mass. Supplied in quantity. The above range is preferable because the reaction proceeds efficiently in Step 2 and a cyanohydrin-containing liquid having a desired concentration can be easily obtained.
  • the solvent may be supplied to the reactor only with the solvent, or may be supplied to the reactor together with the raw material carbonyl compound, the raw material cyanating agent, the catalyst described later, and the like.
  • the raw material carbonyl compound and the raw material cyanating agent are solid at the temperature at which they are supplied to the reactor and the temperature in the reactor, it is preferable to dissolve or suspend them in a solvent.
  • an introduction unit for supplying the raw material carbonyl compound and the raw material cyanating agent to the reactor is connected to the reactor used in the measuring device of the present invention.
  • the introduction unit can be supplied while adjusting the amount of the raw material carbonyl compound supplied to the reactor, and can be supplied while adjusting the amount of the raw material carbonyl compound introduction portion and the raw material cyanating agent supplied to the reactor.
  • a raw material cyanating agent introduction part is connected to the reactor used in the measuring device of the present invention.
  • the introduction unit usually has a supply amount measurement unit such as a flow meter for measuring the amount of the supplied raw material carbonyl compound or raw material cyanating agent.
  • a supply amount measurement unit such as a flow meter for measuring the amount of the supplied raw material carbonyl compound or raw material cyanating agent.
  • the amount of the raw material carbonyl compound and the raw material cyanating agent supplied to the reactor is the molar ratio of the raw material carbonyl compound and the raw material cyanating agent (raw material carbonyl compound / the raw material cyanating agent has a cyano group). However, it is preferably 0.80 to 1.25, more preferably 0.90 to 1.11.
  • the molar ratio of the raw material carbonyl compound and the cyano group of the raw material cyanating agent is preferably closer to 1, more specifically 0.95 to 1.05.
  • the raw material carbonyl compound is excessive, it is necessary to recover the raw material carbonyl compound, and when the raw material cyanating agent is excessive, it is necessary to recover the raw material cyanating agent.
  • the molar ratio of the cyano group to which N is close to 1, which is excessive is not stable, an equipment capable of recovering both is required. For this reason, it is preferable to supply one raw material slightly in advance in advance.
  • the molar ratio of the raw material carbonyl compound to the cyano group of the raw material cyanating agent is particularly preferably from 1.001 to 1.100.
  • the molar ratio of the cyano group possessed by the cyanating agent to the raw material carbonyl compound is particularly preferably from 1.001 to 1.100.
  • the reaction liquid in the reactor is measured using the measuring device (I), and the molar concentrations of the raw material carbonyl compound and cyanohydrin are the requirements (described later). By controlling the amount of raw material supplied so as to satisfy 1), the yield of cyanohydrin can be maintained high.
  • the reaction solution in the distillation apparatus is measured using the measuring apparatus (I), and the distillation conditions are controlled based on the result of the measurement. By doing so, the content of the raw material carbonyl compound contained in the cyanohydrin-containing liquid can be reduced and the concentration of the cyanohydrin-containing liquid can be adjusted.
  • the reaction liquid in the reactor is measured using the measuring device (II), and the molar concentrations of the raw material cyanating agent and cyanohydrin are described later.
  • the yield of cyanohydrin can be maintained high.
  • the reaction solution in the distillation apparatus is measured using the measuring apparatus (II), and the distillation conditions are determined based on the result of the measurement. By controlling, the content of the raw material cyanating agent contained in the cyanohydrin-containing liquid can be reduced and the concentration of the cyanohydrin-containing liquid can be adjusted.
  • the measuring device (III) When the molar ratio of the raw material carbonyl compound to the cyano group of the raw material cyanating agent is close to 1, measurement of the reaction solution in the reactor or distillation apparatus in step 2 and step 3 described later is performed by the measuring device (III). It is preferable to carry out using However, it is preferable to use one of the raw materials in excess because it is sufficient to provide a facility for recovering the excessive component, and the manufacturing apparatus can be simplified.
  • controlling the molar concentration of the raw material carbonyl compound and the raw material cyanating agent is preferable because the raw material carbonyl compound or the raw material cyanating agent is not supplied to the reactor in a large excess.
  • step 1 at least one of the raw material carbonyl compound and the cyanating agent is continuously supplied.
  • both the raw material carbonyl compound and the raw material cyanating agent are preferably supplied continuously. It is preferable to continuously supply the raw material carbonyl compound and the raw material cyanating agent because the raw material in the reactor and the concentration of cyanohydrin tend to be constant.
  • the continuous supply includes not only continuous supply to the reactor but also a slight interval such as dropping. Note that the continuous supply means that the supply is supplied in a few seconds to a few minutes.
  • Step 2 is a step of obtaining a reaction solution by reacting the raw material carbonyl compound supplied in Step 1 with the raw material cyanating agent in a reactor.
  • reaction of the raw material carbonyl compound and the raw material cyanating agent can be exemplified by the following reaction formula.
  • HX is an acid or water
  • M, n, R 1 and R 2 are as described above.
  • reaction liquid containing cyanohydrin By reacting the raw material carbonyl compound and the raw material cyanating agent, a reaction liquid containing cyanohydrin is obtained.
  • cyanohydrin ⁇ -cyanohydrin is preferable, and lactonitrile is particularly preferable.
  • the reaction is usually performed continuously but may be performed semi-batch.
  • cyanohydrin is obtained by the reaction of the raw material carbonyl compound and the cyanating agent.
  • cyanohydrin ⁇ -cyanohydrin is preferable, and lactonitrile is particularly preferable. That is, as the raw material carbonyl compound, acetaldehyde is particularly preferable.
  • Step 2 is preferably performed in the presence of a catalyst.
  • a catalyst a basic compound is preferably used.
  • the basic compound is preferable because it also acts as a pH adjuster.
  • Examples of the basic compound include organic basic compounds and inorganic basic compounds.
  • Examples of the organic basic compound include basic compounds such as amine compounds, quaternary ammonium salts, alkali metal compounds, alkaline earth metal compounds, and metal alkoxides.
  • the pH of the reaction solution in the reactor is preferably 3 to 7, more preferably 4 to 6, and particularly preferably 5 to 6.
  • the catalyst is preferably used in such an amount that the pH of the reaction solution falls within the above range.
  • Step 2 is preferably performed in the presence of a solvent.
  • the solvent used in Step 1 is preferable.
  • the reaction may be performed in the presence of an acid.
  • an acid for the purpose of adjusting the pH to the above range.
  • acids such as sulfuric acid, hydrochloric acid, phosphoric acid and acetic acid can be used.
  • reaction temperature is not particularly limited as long as the raw material carbonyl compound and the cyanating agent can be suitably reacted.
  • the temperature is 0 to 40 ° C., preferably 0 to 30 ° C., more preferably 5 -25 ° C, particularly preferably 10-20 ° C.
  • the average residence time in step 2 is not particularly limited as long as the raw material carbonyl compound and the cyanating agent can sufficiently react.
  • the average residence time is 0.1 to 24 hours, preferably 0.5 to 12 hours. Preferably it is 1 to 6 hours.
  • the measuring apparatus and measuring method of the present invention can be used for measuring the concentration of at least one of the carbonyl compound and the cyanating agent contained in the reaction solution obtained in step 2 and the concentration of cyanohydrin.
  • the measuring device of the present invention may be installed anywhere as long as the status of the reaction solution obtained in step 2 can be grasped, but it is preferably installed in the reactor or on the flow path branched from the reactor. It is more preferable to install on the flow path branched from the reactor from the viewpoint of easy handling and the simplification of the apparatus.
  • the reaction liquid extracted for measuring the concentration from the reactor may be discarded after measuring the concentration, but it is preferable from the viewpoint of productivity to return the measured reaction liquid to the reactor. . After measuring the concentration, it is preferable from the viewpoint of simplicity to discard the measured reaction solution without returning it to the reactor.
  • the raw material carbonyl compound and raw material supplied to the reactor in Step 1 based on the concentration of at least one of the carbonyl compound and the cyanating agent obtained using the measuring apparatus and measuring method of the present invention, and the concentration of cyanohydrin It is preferable to control the concentration of at least one of the cyanating agent. Thereby, according to the density
  • the control is performed by satisfying at least one of the following requirements (1) and (2): It is preferable to control the supply amount of the raw material so as to satisfy.
  • M1 / M3 is preferably 0.001 to 0.050.
  • M2 / M3 is preferably 0.001 to 0.050.
  • the molar ratio of the raw material carbonyl compound supplied to the reactor and the cyano group of the raw material cyanating agent is 1.001 to 1.100.
  • the measuring device (I) or the measuring device (III) can be used, but it is preferable to perform measurement using the measuring device (I), and at this time, it is preferable to satisfy the requirement (1).
  • the concentration of the cyanohydrin can be determined by measuring the concentration of the starting carbonyl compound with an ultraviolet absorptiometer and measuring the total concentration of the carbonyl compound and cyanohydrin with a refractometer.
  • the concentration of the cyanohydrin can be obtained by measuring the concentration of the cyanating agent with a cyan meter and measuring the total concentration of the cyanating agent and cyanohydrin with a refractometer.
  • the supply amount of the raw material carbonyl compound is reduced. Control such as increasing the supply amount of the cyanating agent can be performed. On the other hand, when it is found that the raw material cyanating agent is excessive with respect to the set value as a result obtained using the measuring device of the present invention, the supply amount of the raw material carbonyl compound is reduced. Control such as increasing the amount can be performed. In addition, as a result obtained using the measuring device of the present invention, when it is found that the molar concentration of cyanohydrin is too low, it means that the reaction has not progressed sufficiently. The supply amount of the agent can be reduced.
  • the reaction liquid After reacting the raw material carbonyl compound and raw material cyanating agent supplied in step 1, the reaction liquid may be recovered, the pH of the recovered reaction liquid may be adjusted, and the like. May measure the reaction solution obtained through the step of collecting the reaction solution, the step of adjusting the pH of the collected reaction solution, and the like.
  • the step of recovering the reaction solution is usually a step of recovering the reaction solution from the flow path provided in the reactor, and the recovery speed is usually all components supplied to the reactor such as raw materials and water. Is almost the same as the supply amount. It is preferable that the supply amount of all components is equal to the recovery amount of the reaction liquid because the amount of the reaction liquid present in the reactor becomes constant.
  • the flow path provided for collecting the reaction liquid is usually a flow path different from the flow path provided for performing step 3.
  • the step of adjusting the pH of the collected reaction solution is a step that can be performed to stabilize the reaction solution. Specifically, a step of adding a pH adjusting agent to the recovered reaction solution can be mentioned.
  • the pH adjuster include acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and acetic acid.
  • the solution after adding the pH adjusting agent to the reaction solution is preferably pH 0.0 to 5.0, more preferably pH 0.5 to 3.0.
  • Step 3 is a purification step in which the reaction solution obtained in Step 2 is supplied to a distillation apparatus and the reaction solution is distilled.
  • the “reaction solution obtained in step 2” means the reaction after the step of recovering the reaction solution as described above or the step of adjusting the pH of the reaction solution. It means the reaction solution after the process of adjusting pH.
  • the supply method to the distillation apparatus is not particularly limited and may be supplied intermittently, but it is preferable to supply continuously from the viewpoint of productivity and the like.
  • the distillation method is not particularly limited as long as it can be industrially implemented. Specific methods include simple distillation, precision distillation, thin-film distillation, and the like. In precision distillation, a method using a plate tower or a packed tower, or the like can be given. Examples of the method using a packed tower include a method using regular packing or irregular packing.
  • the distillation can be carried out by any of batch, semi-batch and continuous methods, but a semi-batch or continuous method is preferred.
  • the conditions for the distillation are not particularly limited. However, when acetaldehyde is used as the starting carbonyl compound and hydrogen cyanide is used as the starting cyanating agent to obtain lactonitrile, the distillation temperature is preferably 20 It is ⁇ 60 ° C., more preferably 30 ° -50 ° C., and the distillation time (residence time) is preferably 1 to 300 minutes, more preferably 5 to 150 minutes. Although the distillation pressure is determined by the relationship with the distillation temperature, the distillation temperature is preferably 0.1 to 400 KPaA, more preferably 1 to 200 KPaA.
  • the reflux ratio when refluxing is preferably 0.1 to 20, more preferably 1 to 10.
  • the separation rate of each component such as a carbonyl compound, a cyanating agent, cyanohydrin, and a solvent can be improved without significantly reducing production efficiency.
  • the distillation is usually performed in a distillation apparatus. At this time, since the raw material carbonyl compound and the raw material cyanating agent tend to have a lower boiling point than the cyanohydrin-containing liquid, the target cyanohydrin-containing liquid tends to accumulate at the bottom of the apparatus.
  • the distillation preferably includes a step of extracting the cyanohydrin-containing liquid from the bottom of the distillation apparatus from the viewpoint that the distillation conditions can be controlled more easily.
  • the measuring device and measuring method of the present invention can be used to measure the concentration of at least one of a carbonyl compound and a cyanating agent and the concentration of cyanohydrin contained in a reaction solution in a distillation apparatus.
  • the said reaction liquid measured with the measuring apparatus of this invention usually means the cyanohydrin containing liquid which exists in the bottom part of a distillation apparatus.
  • the concentration of components in the actual reaction liquid in the distillation apparatus can be ascertained using the measuring apparatus and measuring method of the present invention.
  • step 1 when the raw material carbonyl compound is excessive, it is preferable to measure the reaction liquid in the distillation apparatus using the measuring device (I).
  • the measuring device When the raw material cyanating agent is excessive, the measuring device ( It is preferable to measure the reaction liquid in the distillation apparatus using II).
  • the molar ratio of the raw material carbonyl compound and the cyano group of the raw material cyanating agent is close to 1, it is preferable to measure the reaction liquid in the distillation apparatus using the measuring apparatus (III).
  • the concentration of cyanohydrin by measuring the concentration of cyanohydrin with the measurement device or measurement method of the present invention, the actual situation of the reaction liquid in the distillation device, specifically, from the comparison between the measured cyanohydrin concentration and the expected value, It is possible to evaluate how the temperature of the reaction liquid in the apparatus is in relation to the temperature of external control.
  • the measuring device of the present invention may be installed anywhere as long as the state of reaction in the distillation device can be grasped, but it is preferably installed in the distillation device or on a flow path branched from the distillation device. It is more preferable to install on the flow path branched from the distillation apparatus from the viewpoint of ease of use and the simplification of the apparatus.
  • the reaction liquid after the measurement may be allowed to flow into the distillation device again or taken out from the distillation device.
  • the measurement is preferably performed near the outlet (extraction port) of the cyanohydrin-containing liquid in the distillation apparatus. That is, when measuring in the distillation apparatus, it is preferable that a measuring instrument is installed near the outlet of the cyanohydrin-containing liquid of the distillation apparatus, and when measuring on the flow path branched from the distillation apparatus, The flow path is preferably branched from the vicinity of the outlet of the cyanohydrin-containing liquid of the distillation apparatus.
  • the concentration of the reaction liquid after sufficiently purifying can be measured, which is preferable because the suitability of the distillation conditions can be determined more accurately.
  • a cyanohydrin-containing liquid with a small impurity content can be easily obtained with high productivity, and the concentration of the cyanohydrin-containing liquid can be adjusted.
  • Control factors include controlling at least one factor selected from distillation temperature, distillation pressure and reflux ratio, and controlling at least one factor selected from distillation temperature and distillation pressure for ease of control. It is preferable to do.
  • carbonyl compounds and cyanating agents have a boiling point lower than that of cyanohydrin. Therefore, the carbonyl compounds in the reaction in the distillation apparatus measured by the measuring apparatus or measuring method of the present invention are not used.
  • the concentration is higher than the upper limit described later, it is preferable to perform at least one control selected from a control for increasing the distillation temperature and a control for decreasing the distillation pressure. Thereby, the density
  • Control is performed so that the content of the carbonyl compound and the cyanating agent in the reaction liquid in the distillation apparatus measured by the measurement apparatus or measurement method of the present invention is preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, respectively. It is preferable to do.
  • the content of the carbonyl compound and the cyanating agent is preferably as small as possible, and it is preferable that they are not present. Therefore, the lower limit of the range is not particularly limited. , Each of which is 0.1 mass ppm.
  • the concentration of cyanohydrin in the reaction solution in the distillation apparatus measured by the measuring apparatus or measuring method of the present invention is preferably 5 to 100% by mass, more preferably 10 to 100% by mass, and still more preferably 50 to 100% by mass. It is preferable to control so that.
  • the control is preferably automatic control that is automatically performed without intervention of an artificial operation from the viewpoint that a cyanohydrin-containing liquid can be obtained with high productivity.
  • automatic control adjusts distillation conditions based on the detected data, post-computation data, post-recording data, etc., and the desired carbonyl compound and cyanating agent content and cyanohydrin concentration. This is done by a program set to do this.
  • An apparatus for producing a cyanohydrin-containing liquid according to the present invention includes a supply unit that supplies a raw material carbonyl compound and a raw material cyan compound to a reaction system, a reactor that reacts the supplied raw material to obtain a reaction liquid containing cyanohydrin, and the above-described measurement device And have.
  • the measuring device can be provided in the reactor or on a flow path branched from the reactor, and can measure the reaction liquid in the reactor.
  • the apparatus for producing a cyanohydrin-containing liquid of the present invention uses the measurement It is preferable to have a control unit (hereinafter also referred to as “control unit 1”) that controls the supply amount of at least one compound selected from the raw material carbonyl compound and the raw material cyan compound to the reaction system based on the results of the apparatus. .
  • the apparatus for producing a cyanohydrin-containing liquid of the present invention preferably further has a distillation apparatus for distilling the reaction liquid obtained in the reactor.
  • the measuring device of the apparatus for producing a cyanohydrin-containing liquid of the present invention can be provided in the distillation apparatus or on a flow path branched from the distillation apparatus, and can measure the reaction liquid in the distillation apparatus.
  • the apparatus for producing a cyanohydrin-containing liquid of the present invention It is preferable to have a control unit (hereinafter also referred to as “control unit 2”) that controls the distillation conditions based on the result of the measurement device.
  • the measuring device of the apparatus for producing a cyanohydrin-containing liquid of the present invention may be provided in the reactor or on a flow path branched from the reactor, and the flow branched in the distillation apparatus or from the distillation apparatus. It may be provided on the road.
  • the production apparatus for a cyanohydrin-containing liquid of the present invention preferably has at least two measuring devices from the viewpoint of producing a cyanohydrin-containing liquid having a low impurity content such as reaction raw materials. Furthermore, in the apparatus for producing a cyanohydrin-containing liquid of the present invention, at least one of the measuring devices is provided in the reactor or on a flow path branched from the reactor, and measures the reaction liquid in the reactor. Based on the result of the measurement device, the control unit 1 for controlling the supply amount of at least one compound selected from the raw material carbonyl compound and the raw material cyan compound to the reaction system, and at least one of the measurement devices is the distillation device. Or a control unit 2 that is provided on a flow path branched from the distillation apparatus, measures a reaction liquid in the distillation apparatus, and controls distillation conditions based on a result of the measurement apparatus. More preferred.
  • the supply unit is a supply unit of a raw material carbonyl compound, and when the raw material carbonyl compound is a purified carbonyl compound, it is preferably not made of iron.
  • the reactor is not particularly limited, and examples thereof include a continuous tank reactor, a tube reactor, a screw feeder mixer, and a static mixer.
  • a reactor capable of continuously taking out the cyanohydrin-containing liquid is preferable.
  • the reactor is preferably made of a material other than iron since the generation of impurities is promoted when the raw material carbonyl compound comes into contact with the iron member.
  • the distillation apparatus preferably has an outlet (extraction port) for the cyanohydrin-containing liquid at the bottom of the apparatus, and preferably has the measuring instrument near the outlet.
  • the apparatus for producing a cyanohydrin-containing liquid of the present invention includes a member for controlling the supply amount of raw materials, distillation conditions, etc. based on the results measured by the measurement device, such as a measuring instrument and a pump (controlling the supply amount of raw materials) Device that controls the supply amount of raw materials, distillation conditions, etc. based on the signal from the command unit. Etc. are preferable.
  • the apparatus for producing a cyanohydrin-containing liquid according to the present invention includes, in addition to the above-described members, a storage tank for storing raw materials and products, a supply unit for supplying a reaction liquid to a distillation apparatus, a catalyst and the like for a reactor, and the like. You may have the member which has been used for this manufacturing apparatus.
  • refractometer calibration curve> Prior to obtaining the refractive index of the reaction solution, the following calibration curve was prepared. 1) A plurality of lactonitrile aqueous solutions in which the composition ratio of water / lactonitrile is changed between 100% water and 100% lactonitrile are prepared, and the refractive index of each is measured. A calibration curve was prepared (calibration curve A-0). 2) Acetaldehyde was added to the specific aqueous solution of lactonitrile to prepare a composition solution of acetaldehyde / lactonitrile / water having different acetaldehyde concentrations, and the respective refractive indexes were measured.
  • a calibration curve corresponding to the molar concentration of acetaldehyde obtained from the ultraviolet absorption spectrophotometer of the liquid is selected from (A-0 to AX) or created by interpolating from the calibration curve group.
  • the molar concentration of lactonitrile were determined from the refractive index n of the liquid.
  • the lactonitrile molar concentration was quantified using a program (calculation software) incorporated in the measuring device.
  • refractometer calibration curve> Prior to obtaining the refractive index of the reaction solution, the following calibration curve was prepared. 1) A plurality of lactonitrile aqueous solutions in which the composition ratio of water / lactonitrile is changed between 100% water and 100% lactonitrile are prepared, and the refractive index of each is measured. A calibration curve was created (calibration curve B-0). 2) Hydrogen cyanide was added to the specific aqueous lactonitrile solution to prepare hydrogen cyanide / lactonitrile / water composition liquids having different hydrogen cyanide concentrations, and the respective refractive indexes were measured.
  • a calibration curve corresponding to the molar concentration of hydrogen cyanide obtained from the cyan meter of the reaction solution is selected from (B-0 to BX) or created by interpolating from the calibration curve group. From the refractive index n of the reaction solution, the molar concentration of lactonitrile was quantified. The lactonitrile molar concentration was quantified using a program (calculation software) incorporated in the measuring device.
  • Example 1 A flask equipped with a distillation tube and a condenser tube was charged with raw material acetaldehyde having a content of a component (specific impurity) having a boiling point of 25 ° C. or higher at normal pressure of 600 mass ppm, and the temperature was adjusted to 40 ° C. under a pressure of 50 KPaG. When heated and distilled, a purified acetaldehyde having a specific impurity content of 160 ppm by mass was obtained.
  • a component specific impurity
  • Purified acetaldehyde obtained is continuously supplied as it is with stirring to a CSTR type reactor (continuous tank reactor) equipped with a stirrer and a cooler. Each flow rate was measured with a Coriolis flowmeter so as to be 0.01, and continuously supplied while controlling the flow rate with a pump. The reaction was carried out while extracting the reaction solution so that the residence time was 3 hours while adjusting the pH to 5 to 6 with a 5 mass% aqueous sodium hydroxide solution at a reaction temperature of 15 to 20 ° C. .
  • the reaction liquid was extracted on a flow path branched from the bottom of the reactor.
  • the measuring device Using the measuring device, the molar concentration of acetaldehyde and lactonitrile in the extracted reaction solution was automatically measured.
  • a controller that can automatically adjust the supply amount of acetaldehyde and hydrogen cyanide corresponding to the molar concentration of acetaldehyde and lactonitrile output by the ultraviolet absorptiometer and refractometer is connected to the measuring device online. .
  • the conversion rate of acetaldehyde at 10 hours after the start of the reaction was 99.0%
  • the conversion rate of hydrogen cyanide was 100.0%
  • the yield of lactonitrile was 98.9% with respect to the amount of supplied acetaldehyde. It was 100.0% with respect to the amount of hydrogen cyanide.
  • the conversion rate of acetaldehyde at 20 hours was 99.0%
  • the conversion rate of hydrogen cyanide was 100.0%
  • the yield of lactonitrile was 98.9% with respect to the amount of supplied acetaldehyde, with respect to the amount of supplied hydrogen cyanide. It was 100.0%.
  • the conversion rate of acetaldehyde at 30 hours was 99.0%, the conversion rate of hydrogen cyanide was 100.0%, and the yield of lactonitrile was 98.9% with respect to the amount of supplied acetaldehyde and with respect to the amount of supplied hydrogen cyanide. And 100.0%.
  • the results are summarized in Table 1. Therefore, the conversion rate of acetaldehyde and the yield of lactonitrile were always stable, and the yield of lactonitrile was always high.
  • a controller that can automatically adjust the distillation temperature in accordance with the molar concentration of acetaldehyde and lactonitrile output by an ultraviolet absorptiometer and a refractometer was connected to the measuring device online.
  • the control device sets the distillation temperature to 40 ° C. ⁇ 2 so that the lactonitrile concentration of the lactonitrile-containing liquid at the bottom of the distillation column is 80 mass% and the acetaldehyde concentration is 300 mass ppm or less. Fine adjustment in the range of 5 ° C.
  • the acetaldehyde content in the lactonitrile-containing liquid obtained by distillation was in the range of 200 mass ppm ⁇ 10 mass ppm, and the concentration of lactonitrile was in the range of 80 mass% ⁇ 0.25 mass%. Since the conversion rate of hydrogen cyanide in the reaction solution was 100.0%, the solution after distillation did not contain hydrogen cyanide.
  • the conversion rate of acetaldehyde at 10 hours after the start of the reaction was 99.0%
  • the conversion rate of hydrogen cyanide was 100.0%
  • the yield of lactonitrile was 98.9% with respect to the amount of supplied acetaldehyde. It was 100.0% with respect to the amount of hydrogen cyanide.
  • the conversion rate of acetaldehyde at 20 hours was 98.1%
  • the conversion rate of hydrogen cyanide was 100%
  • the yield of lactonitrile was 97.2% with respect to the amount of supplied acetaldehyde
  • 99.9% with respect to the amount of supplied hydrogen cyanide It was 6%.
  • the conversion rate of acetaldehyde at 30 hours was 97.0%, the conversion rate of hydrogen cyanide was 100.0%, the yield of lactonitrile was 95.2% with respect to the amount of supplied acetaldehyde, and with respect to the amount of supplied hydrogen cyanide. 99.1%.
  • the results are summarized in Table 1. Therefore, the conversion rate of acetaldehyde and the yield of lactonitrile were not stable, and the yield of lactonitrile decreased with the passage of time.
  • Example 2 In the CSTR type reactor (continuous tank reactor) equipped with a stirrer and a cooler, the purification described in Example 1 was carried out so that the molar ratio of hydrogen cyanide / acetaldehyde was 1.01 while stirring acetaldehyde and hydrogen cyanide. Acetaldehyde and hydrogen cyanide were supplied with their respective flow rates measured with a Coriolis flow meter and controlled with a pump. The reaction was carried out while extracting the reaction solution so that the residence time was 3 hours while adjusting the pH to 5 to 6 with a 5 mass% aqueous sodium hydroxide solution at a reaction temperature of 15 to 20 ° C. .
  • the reaction liquid was extracted on a flow path branched from the bottom of the reactor.
  • the measuring device Using the measuring device, the molar concentration of hydrogen cyanide and lactonitrile of the extracted reaction solution was automatically measured.
  • a controller that can automatically adjust the supply amounts of acetaldehyde and hydrogen cyanide corresponding to the molar concentrations of hydrogen cyanide and lactonitrile output by the cyan meter and the refractometer was connected to the measuring device online.
  • the conversion rate of hydrogen cyanide after 10 hours from the start of the reaction was 99.0%
  • the conversion rate of acetaldehyde was 100.0%
  • the yield of lactonitrile was 98.9% with respect to the supplied hydrogen cyanide amount. It was 100.0% with respect to acetaldehyde.
  • the conversion rate of hydrogen cyanide at the 20th hour was 99.0%
  • the conversion rate of acetaldehyde was 100.0%
  • the yield of lactonitrile was 98.9% with respect to the supplied hydrogen cyanide amount, with respect to the supplied acetaldehyde amount. It was 100.0%.
  • the conversion rate of hydrogen cyanide at 30 hours was 99.0%, the conversion rate of acetaldehyde was 100.0%, and the yield of lactonitrile was 98.9% with respect to the supplied hydrogen cyanide amount, with respect to the supplied acetaldehyde amount. And 100.0%.
  • the results are summarized in Table 2. Therefore, the conversion rate of hydrogen cyanide, the conversion rate of acetaldehyde and the yield of lactonitrile were always stable, and the yield of lactonitrile was high.
  • the conversion rate of hydrogen cyanide after 10 hours from the start of the reaction was 98.9%
  • the conversion rate of acetaldehyde was 100.0%
  • the yield of lactonitrile was 98.6% with respect to the supplied hydrogen cyanide amount. It was 100.0% with respect to acetaldehyde.
  • the conversion rate of hydrogen cyanide at 20 hours was 98.0%
  • the conversion rate of acetaldehyde was 100.0%
  • the yield of lactonitrile was 97.0% with respect to the amount of supplied hydrogen cyanide, with respect to the amount of supplied acetaldehyde. It was 99.6%.
  • the conversion rate of hydrogen cyanide at 30 hours was 96.9%, the conversion rate of acetaldehyde was 100%, and the yield of lactonitrile was 95.0% with respect to the supplied hydrogen cyanide amount and 98% with respect to the supplied acetaldehyde amount. 9%.
  • the results are summarized in Table 2. Therefore, the conversion of hydrogen cyanide and the yield of lactonitrile were not stable, and the yield of lactonitrile decreased with time.
  • Example 3 lactonitrile was used in the same manner as in Example 1 except that the distillation was controlled only by controlling the distillation temperature, distillation pressure and residence time without measuring the molar concentrations of acetaldehyde and lactonitrile in the distillation column. A containing liquid was produced.
  • the acetaldehyde content in the obtained lactonitrile-containing liquid was 840 mass ppm ⁇ 200 mass ppm, and the concentration of lactonitrile was 75 mass% ⁇ 5 mass%.

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Abstract

L'invention a pour objet de fabriquer facilement un liquide comprenant une cyanhydrine à faible teneur en impuretés telles que des matières premières réactives, et de fournir un dispositif de mesure qui permet de mesurer rapidement la concentration en composés dans un liquide de réaction. Le dispositif de mesure de l'invention est mis en œuvre dans le cas où un liquide comprenant une cyanhydrine est obtenu en continu par réaction d'un composé carbonyle de matière première spécifique, et d'un agent de cyanuration spécifique. Ledit dispositif possède un absorptiomètre d'ultraviolets destiné à mesurer la concentration du composé carbonyle contenu dans le liquide de réaction, et/ou un cyanomètre destiné à mesurer la concentration de l'agent de cyanuration contenu dans ledit liquide de réaction. En outre, ledit dispositif possède un réfractomètre destiné à mesurer la concentration totale en composé carbonyle et/ou agent de cyanuration et en cyanhydrine contenus dans ledit liquide de réaction, et possède un programme calculant la concentration en cyanhydrine à partir de ladite concentration.
PCT/JP2017/032843 2016-10-11 2017-09-12 Dispositif ainsi que procédé de mesure, et dispositif de fabrication de liquide comprenant une cyanhydrine Ceased WO2018070165A1 (fr)

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Citations (4)

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JP2007040845A (ja) * 2005-08-03 2007-02-15 Olympus Corp 反応容器とこの反応容器を用いた分析装置
WO2008123099A1 (fr) * 2007-03-22 2008-10-16 Tsukishima Kankyo Engineering Ltd. Procédé de séparation d'une substance cible selon une séparation sur membrane et appareil pour la mise en œuvre de ce procédé
WO2009054356A1 (fr) * 2007-10-23 2009-04-30 Nippoh Chemicals Co., Ltd. PROCÉDÉ DE FABRICATION D'UN COMPOSÉ DE CYANHYDRINE ET PROCÉDÉ DE FABRICATION D'UN COMPOSÉ α-HYDROXYESTER
WO2009054355A1 (fr) * 2007-10-23 2009-04-30 Nippoh Chemicals Co., Ltd. PROCÉDÉ ET APPAREIL POUR LA FABRICATION D'UN COMPOSÉ DE CYANHYDRINE ET PROCÉDÉ DE FABRICATION D'UN COMPOSÉ α-HYDROXYESTER

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JP2000317468A (ja) * 1999-04-30 2000-11-21 Kawasaki Steel Corp シアノ錯体含有排水の処理方法及びその処理装置
JP2006141263A (ja) * 2004-11-18 2006-06-08 Kyoto Univ （ｒ）−ヒドロキシニトリルリアーゼの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007040845A (ja) * 2005-08-03 2007-02-15 Olympus Corp 反応容器とこの反応容器を用いた分析装置
WO2008123099A1 (fr) * 2007-03-22 2008-10-16 Tsukishima Kankyo Engineering Ltd. Procédé de séparation d'une substance cible selon une séparation sur membrane et appareil pour la mise en œuvre de ce procédé
WO2009054356A1 (fr) * 2007-10-23 2009-04-30 Nippoh Chemicals Co., Ltd. PROCÉDÉ DE FABRICATION D'UN COMPOSÉ DE CYANHYDRINE ET PROCÉDÉ DE FABRICATION D'UN COMPOSÉ α-HYDROXYESTER
WO2009054355A1 (fr) * 2007-10-23 2009-04-30 Nippoh Chemicals Co., Ltd. PROCÉDÉ ET APPAREIL POUR LA FABRICATION D'UN COMPOSÉ DE CYANHYDRINE ET PROCÉDÉ DE FABRICATION D'UN COMPOSÉ α-HYDROXYESTER

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