WO2016068062A1 - Procédé de production d'acétonitrile - Google Patents

Procédé de production d'acétonitrile Download PDF

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WO2016068062A1
WO2016068062A1 PCT/JP2015/080064 JP2015080064W WO2016068062A1 WO 2016068062 A1 WO2016068062 A1 WO 2016068062A1 JP 2015080064 W JP2015080064 W JP 2015080064W WO 2016068062 A1 WO2016068062 A1 WO 2016068062A1
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Prior art keywords
acetonitrile
mass
water
reaction
acetic acid
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PCT/JP2015/080064
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English (en)
Japanese (ja)
Inventor
健啓 飯塚
義和 高松
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旭化成ケミカルズ株式会社
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Application filed by 旭化成ケミカルズ株式会社 filed Critical 旭化成ケミカルズ株式会社
Priority to JP2016556551A priority Critical patent/JP6391703B2/ja
Priority to CN201580051782.4A priority patent/CN107074749B/zh
Publication of WO2016068062A1 publication Critical patent/WO2016068062A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/22—Preparation of carboxylic acid nitriles by reaction of ammonia with carboxylic acids with replacement of carboxyl groups by cyano groups
    • 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
    • C07C255/02—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
    • C07C255/03—Mononitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a method for producing acetonitrile.
  • Acetonitrile is used as a solvent for chemical reaction, particularly a solvent used for synthesis and purification of pharmaceutical intermediates, a mobile phase solvent for high performance liquid chromatography, and the like. Recently, acetonitrile is also used as a solvent for DNA synthesis and a solvent for purification, a solvent for organic EL material synthesis, and a solvent for washing electronic components.
  • acetonitrile used as a solvent for high performance liquid chromatography needs to have no ultraviolet absorption at a wavelength of 200 to 400 nm so that the ultraviolet absorption does not become a background.
  • acetonitrile has been obtained by purifying crude acetonitrile.
  • acetonitrile is mainly crude acetonitrile obtained as a by-product in the production of acrylonitrile or methacrylonitrile by catalytic ammoxidation reaction of propylene or isobutene, ammonia and oxygen. , Recovered and purified.
  • Patent Document 1 in a method for producing acetonitrile by reacting acetic acid and ammonia in the gas phase in the presence of a catalyst, the reaction product gas is brought into contact with a strong acid to recover acetonitrile as an aqueous solution.
  • a method is disclosed in which ammonia forms a salt with a strong acid to prevent the formation and precipitation of ammonium carbonate. Therefore, in Patent Document 1, it is presumed that carbon dioxide and acetone by-products due to acetic acid decarboxylation reaction represented by the following formula are problematic, but there is no description of by-products produced by the reaction, and high purity. There are no problems in purifying to acetonitrile. 2CH 3 COOH ⁇ CH 3 COCH 3 + CO 2 + H 2 O
  • Patent Document 2 discloses that in a method for producing nitrile from carboxylic acid and ammonia using various zeolite catalysts, the molar ratio of ammonia / carboxylic acid is set to 1/1 to 10/1, and H-ZSM-5 is used as the catalyst. , NaY, a zeolite such as H-mordenite, SAPO-40, silica alumina, etc., a reaction temperature of 300 to 500 ° C., and a WHSV of liquid product basis of 0.4 h ⁇ 1 are disclosed. According to the example of Patent Document 2, although the yield is disclosed as 100%, the amount of catalyst is large, and it is not assumed to be industrially implemented. Moreover, there is no description about a trace by-product substance, and the problem at the time of refine
  • the present inventors produced acetonitrile by a gas phase reaction of acetic acid and ammonia by the method described in the prior art document in the presence of a solid acid catalyst having excellent reaction results and catalyst life.
  • a phenomenon that is not mentioned at all in the conventional method that is, hydrated crude acetonitrile to be produced, acetone, methyl ethyl ketone, ethylene, propylene, butene; nitrile compounds such as acrylonitrile and propionitrile; benzene, toluene, xylene, etc. It was found that aromatic compounds of the above; pyridines and the like are contained as trace by-product impurities.
  • aromatic compounds such as toluene are known to be substances that greatly affect ultraviolet absorption in the wavelength region of 200 nm.
  • toluene having a boiling point with acetonitrile and estimated to cause distillation separation from azeotropic composition formation has a wavelength of 200 nm even when only 1.0 mass ppm is present with respect to acetonitrile.
  • the absorbance of UV absorption increases at 0.3 or higher. Therefore, even if it is a very small amount, the by-product of toluene and its purification become a major issue for acetonitrile product quality.
  • Patent Document 1 has proposed a method in which an acetic acid raw material is dissolved in an aromatic hydrocarbon and supplied as a solvent.
  • acetonitrile thus obtained is a solvent for chemical reaction, particularly a solvent for synthesizing and purifying pharmaceutical intermediates, or a mobile phase solvent for high-performance liquid chromatography, a solvent for DNA synthesis, and a solvent for purification. It can be suitably used as a solvent for synthesizing organic EL materials or a cleaning solvent for electronic components.
  • the present inventors have solved the above problems by using a predetermined catalyst and controlling the water content of hydrous crude acetonitrile in the gas phase reaction. The present inventors have found that this can be done and have completed the present invention.
  • the present invention is as follows.
  • a gas phase reaction step in which acetic acid and ammonia are subjected to a gas phase reaction in the presence of a solid acid catalyst to obtain hydrous crude acetonitrile; Purifying the water-containing crude acetonitrile to obtain a product acetonitrile,
  • the water content is 47% by mass or more with respect to 100% by mass of the hydrous crude acetonitrile, and the toluene content is 1 mass ppm or more with respect to 100% by mass of acetonitrile.
  • a method for producing acetonitrile is described in which acetic acid and ammonia are subjected to a gas phase reaction in the presence of a solid acid catalyst to obtain hydrous crude acetonitrile; Purifying the water-containing crude acetonitrile to obtain a product acetonitrile, In the hydrous crude acetonitrile, The water content is 47% by mass or more with respect to 100% by mass of the hydrous crude
  • the purification step comprises Separating the ammonia from the hydrated crude acetonitrile to obtain a crude acetonitrile; and
  • acetonitrile in which the amount of energy used for purification of hydrous crude acetonitrile obtained by gas phase reaction of acetic acid and ammonia using a solid acid catalyst is small, and the purification equipment and the purification process are simple.
  • acetonitrile thus obtained is a solvent for chemical reaction, particularly a solvent for synthesizing and purifying pharmaceutical intermediates, or a mobile phase solvent for high-performance liquid chromatography, a solvent for DNA synthesis, and a solvent for purification. It can be suitably used as a solvent for synthesizing organic EL materials or a cleaning solvent for electronic components.
  • the present embodiment the embodiment of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
  • the present invention is not limited to this, and various modifications are possible without departing from the scope of the present invention. It is. Note that the expression “A to B” in a numerical range indicates a numerical range of “A or more and B or less” unless otherwise specified.
  • the method for producing acetonitrile comprises a gas phase reaction step of obtaining acetic acid and ammonia in a gas phase reaction in the presence of a solid acid catalyst to obtain hydrous crude acetonitrile, and purifying the hydrous crude acetonitrile to obtain product acetonitrile. And a purification step to obtain, wherein the water content of the water-containing crude acetonitrile is 47% by mass or more with respect to 100% by mass of the water-containing crude acetonitrile, and the content of toluene is 100% by mass of acetonitrile. 1 mass ppm or more.
  • the gas phase reaction step is a step in which acetic acid and ammonia are reacted in the gas phase in the presence of a solid acid catalyst to obtain hydrous crude acetonitrile. Specifically, it can be carried out by bringing gas-phase contact between acetic acid, ammonia and a catalyst at a predetermined temperature in a reactor filled with a solid acid catalyst, but is not particularly limited.
  • Acetic acid and ammonia as raw materials for the gas phase reaction are not particularly limited, and those produced from various chemical synthesis methods can be used.
  • Acetic acid and ammonia are not necessarily highly pure, and may be industrial grade.
  • acetic acid aqueous solution generally used industrially can be used as acetic acid.
  • the water content of the acetic acid aqueous solution is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 18% by mass or more. Moreover, the content of water in the acetic acid aqueous solution is preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less. When the content of water in the acetic acid aqueous solution is 10% by mass or more, the separation efficiency of impurities (such as toluene) from the hydrated crude acetonitrile tends to be further improved.
  • impurities such as toluene
  • the content of water in the acetic acid aqueous solution is 40% by mass or more, the gas phase reaction efficiency is further improved, and the energy efficiency regarding the separation of water from hydrous crude acetonitrile or crude acetonitrile tends to be further improved.
  • the melting point of acetic acid having a moisture content of 0% by mass is about 17 ° C.
  • the melting point of acetic acid having a moisture content of 40% by mass is reduced to about ⁇ 27 ° C. It is advantageous if it is carried out automatically.
  • the water content of acetic acid means the weight fraction of water contained in acetic acid based on JIS-K-1351.
  • Solid acid catalyst used in the present embodiment is not particularly limited as long as it is a solid having a Bronsted acid point, and a conventionally known catalyst is used.
  • clay minerals such as kaolin
  • Zeolites such as a medium pore diameter zeolite
  • Active aluminas Aluminum phosphates
  • Mesoporous silica alumina etc. are mentioned.
  • zeolites such as a catalyst containing an intermediate pore size zeolite and activated aluminas are preferable, and a catalyst containing an intermediate pore size zeolite is more preferable.
  • Zero zeolite is a general term for crystalline porous aluminosilicates. Zeolite has (SiO 4 ) 4- and (AlO 4 ) 5- having a tetrahedral structure as basic structural units, and these are three-dimensionally connected to form crystals. Moreover, metallosilicates in which trivalent or tetravalent elements other than aluminum ions are incorporated in the silicate skeleton are also included in the zeolite.
  • Zeolite is diverse in structure and composition, so it is classified differently from various viewpoints such as structure code, formation process, mineralogy, pore size, pore dimension, aluminum concentration, other cation concentration and structural elements. (See Zeolite Science and Engineering, Yoshio Ono and Kenaki Yashima / Edition, Kodansha Scientific). Various framework type codes are defined by the International Zeolite Society (IZA).
  • the “medium pore diameter zeolite” means a pore diameter range of a small pore diameter zeolite represented by A-type zeolite and a large pore diameter zeolite represented by mordenite, X-type or Y-type zeolite.
  • the pore diameter of the medium pore diameter zeolite is preferably 5 to 6.5 mm.
  • the structure of the intermediate pore diameter zeolite is not particularly limited.
  • FTC framework type code
  • IZA International Society of Zeolite
  • AEL EUO
  • FER FER
  • HEU FER
  • MEL MFI
  • NES TON
  • WEI TON
  • an intermediate pore size zeolite having a structure represented by MFI is preferable.
  • Specific examples of the intermediate pore size zeolite having a structure represented by MFI include ZSM-5 type zeolite.
  • a metallo in which a part of aluminum (Al) atoms constituting the zeolite skeleton is substituted with an element such as gallium (Ga), iron (Fe), boron (B), chromium (Cr), etc. It is also possible to use aluminosilicates or metallosilicates in which all the aluminum atoms constituting the zeolite skeleton are substituted with the above elements.
  • the silica / alumina ratio (molar ratio, the same shall apply hereinafter) of the medium pore diameter zeolite is preferably 20 to 1000, more preferably 20 to 500, and still more preferably 20 to 300.
  • the silica / alumina ratio is 20 or more, the stability as a catalyst tends to be further improved. Further, when the silica / alumina ratio is within the above range, the catalytic activity tends to be further improved.
  • the silica / alumina ratio of the zeolite can be determined by a known method, for example, by completely dissolving the zeolite in an alkaline aqueous solution and analyzing the resulting solution by plasma emission spectroscopy.
  • the silica / alumina ratio in the case where the intermediate pore diameter zeolite is a metalloaluminosilicate or a metallosilicate is obtained by converting the amount of aluminum atoms substituted by the above elements into the number of moles of Al 2 O 3 (alumina). Calculated.
  • a method for preparing the catalyst containing the intermediate pore size zeolite is not particularly limited, and a known method can be used.
  • the intermediate pore size zeolite can be changed in composition after hydrothermal synthesis by modification such as ion exchange, dealumination treatment, impregnation and loading.
  • the shape of the catalyst containing the intermediate pore diameter zeolite may be powdery or granular, and can be formed into a molded body that has been molded into a suitable shape according to a process such as a gas phase reaction step.
  • the method for forming the catalyst containing the intermediate pore size zeolite is not particularly limited, and a known method can be used. Specifically, a method of spray drying a catalyst precursor, a method of compression molding a catalyst component, and a method of extrusion molding of a catalyst component can be mentioned. In these molding methods, a binder or a diluent for molding (matrix) may be used.
  • the binder and the diluent for molding are not particularly limited, and examples thereof include porous refractory inorganic oxides such as alumina, silica, zirconia, titania, kaolin, diatomaceous earth, and clay. These may be used individually by 1 type, or may use 2 or more types together. Commercially available binders and diluents for molding may be used, or they may be synthesized by a conventional method.
  • the mass ratio of the intermediate pore size zeolite / is preferably 10/90 to 90/10, and more It is preferably 20/80 to 80/20.
  • activated aluminas Next, the activated alumina will be described below. Although it does not specifically limit as activated alumina, For example, commercially available activated alumina is mentioned.
  • the shape of the activated alumina may be powdery or granular, and can be made suitable according to a process such as a gas phase reaction step.
  • the reactor used in the gas phase reaction step is not particularly limited, and examples thereof include a fixed bed reactor, a fluidized bed reactor, and a moving bed reactor.
  • a reaction system either a batch system or a flow system can be used, but a flow system is preferable in consideration of productivity. Note that the description in the present specification does not preclude changes in reaction conditions that can be easily adjusted by those skilled in the art.
  • particulates inert to the reaction such as quartz sand and ceramic balls, may be mixed with the catalyst and packed.
  • this granular material is a particle size comparable as a catalyst from a uniform mixing property with a catalyst.
  • the gas phase reaction is an endothermic reaction
  • the reaction substrate reaction raw material
  • the reaction substrate may be divided and supplied to the reactor for the purpose of dispersing the endotherm accompanying the reaction.
  • the molar ratio of ammonia / acetic acid supplied to the reactor is preferably 1.0 or more, more preferably 1.0 to 1.5, and still more preferably 1.1 to 1. 5.
  • the reaction efficiency tends to be further improved.
  • the ammonia / acetic acid molar ratio is 1.5 or less, the energy consumption for separating and removing ammonia from hydrous crude acetonitrile described later tends to be further reduced in the purification step.
  • WHSV weight space velocity
  • WHSV weight space velocity
  • the “catalyst filling weight” means the filling weight of the solid acid catalyst into the reactor in the present embodiment.
  • the binder or molding material constituting the molded body is used. It is a reactor filling weight of the whole molded object containing a diluent.
  • the above-mentioned inert particulate matter is not included in the catalyst filling weight.
  • the “raw material weight” is the total weight of the raw material flowing to the reactor, and the “raw material” includes the diluent described later in addition to acetic acid or an acetic acid aqueous solution and ammonia as raw materials in the present embodiment. It is.
  • WHSV can be adjusted as appropriate in consideration of productivity, catalyst life, and reaction yield.
  • the WHSV in the vapor phase reaction step preferably 0.5 ⁇ 50h -1, more preferably 0.5 ⁇ 20h -1, more preferably from 0.5 ⁇ 10h -1.
  • the reactor can be made compact, and byproducts of undesirable by-products such as acetone and toluene can be reduced.
  • the raw material can be suppressed and the purification load on high-purity acetonitrile can be further reduced.
  • WHSV is 50 h ⁇ 1 or less, the conversion of acetic acid tends to be further improved, and the selectivity of acetonitrile tends to be further improved.
  • a diluent may be used in addition to acetic acid and ammonia.
  • the diluent is not particularly limited, and examples thereof include helium, argon, nitrogen, water, paraffinic hydrocarbon gases, and Examples thereof include gases inert to the reaction, such as a mixture thereof. Of these, nitrogen and water are preferred.
  • impurities contained in the reaction raw material may be used as they are, or a separately prepared diluent may be mixed with the reaction raw material and used.
  • the diluent may be mixed with the reaction raw material before entering the reactor, or may be supplied to the reactor separately from the reaction raw material.
  • water may be mixed with hydrous crude acetonitrile produced by a gas phase reaction of acetic acid and ammonia as a diluent for purification.
  • reaction temperature of the gas phase reaction is preferably 250 ° C. or higher, more preferably 300 ° C. or higher, and further preferably 350 ° C. or higher.
  • the reaction temperature of the gas phase reaction is preferably 600 ° C. or lower, more preferably 550 ° C. or lower, and further preferably 520 ° C. or lower.
  • reaction temperature is 250 ° C. or higher, the reaction yield tends to be further improved.
  • reaction temperature is 600 degrees C or less, it exists in the tendency which can suppress the production
  • the gas phase reaction in this embodiment is a dehydration reaction (endothermic reaction)
  • a heat source in the reactor in order to control the inside of the reactor to a desired reaction temperature.
  • a gas phase reaction is industrially carried out in a fixed bed reactor, it is conceivable to use a multi-tubular shell and tube reactor.
  • reaction pressure of the gas phase reaction is advantageously low in terms of the reaction equilibrium of the gas phase reaction of the present embodiment, but the reaction rate increases if the pressure is high. Accordingly, it is a balance between the equilibrium conversion rate and the reaction rate, preferably normal pressure to 0.3 MPaG (gauge pressure, the same shall apply hereinafter), more preferably 0.03 to 0.25 MPaG, and still more preferably 0. .05 to 0.20 MPaG.
  • Water-containing crude acetonitrile includes 10% by mass to 70% by mass of acetonitrile and 30% by mass to 90% by mass of water, in addition to 0% by mass to 60% by mass of impurities.
  • impurities include, but are not limited to, ammonia, acetic acid, acetamide, and acetone.
  • the content of water in the hydrous crude acetonitrile is preferably 47% by mass or more, more preferably 50% by mass or more, and further preferably 52% by mass or more with respect to 100% by mass of the hydrous crude acetonitrile.
  • the water content in the hydrous crude acetonitrile is preferably 90% by mass or less, more preferably 60% by mass or less, and further preferably 58% by mass or less, with respect to 100% by mass of the hydrous crude acetonitrile. is there.
  • the content of water in the hydrous crude acetonitrile is 47% by mass or more, in the purification step described later, aromatic compounds such as hydrous crude acetonitrile or toluene in the crude acetonitrile tend to be more efficiently removed simultaneously with ammonia. is there.
  • the content of water in the hydrated crude acetonitrile is 90% by mass or less, the hydrated crude acetonitrile or water in the crude acetonitrile tends to be more efficiently removed in the purification step described later.
  • the water content in the hydrous crude acetonitrile may be adjusted by mixing water as a diluent with respect to the hydrous crude acetonitrile obtained by the gas phase reaction. In this case, the content of water in the hydrous crude acetonitrile is determined by taking into account the weight of the mixed water.
  • the content of toluene in the hydrous crude acetonitrile obtained by the gas phase reaction is influenced by the reaction conditions, but is preferably 1 to 1000 ppm by mass, more preferably 1 to 100% by mass of acetonitrile. It is ⁇ 500 mass ppm, more preferably 1 to 100 mass ppm. Even if the content of toluene in the hydrous crude acetonitrile is within the above range, the production method of the present embodiment can sufficiently remove toluene. In addition, content of toluene in hydrous crude acetonitrile can be measured by the method as described in an Example.
  • the purification step is a step of purifying hydrous crude acetonitrile to obtain product acetonitrile.
  • the step included in the purification step is not particularly limited as long as it is configured to remove water, ammonia and other impurities from the hydrous crude acetonitrile, and examples thereof include a concentration step and a dehydration step.
  • the concentration step is a step in which ammonia is separated from hydrous crude acetonitrile to obtain crude acetonitrile.
  • a separation method of ammonia For example, the method of using a distillation column is mentioned.
  • “crude acetonitrile” is acetonitrile obtained by removing most of the ammonia from water-containing crude acetonitrile and concentrating, and mainly contains 50% by mass or more and less than 75% by mass of acetonitrile, and 25% by mass or more and 50% by mass. % Or less water and other impurities.
  • toluene in the water-containing crude acetonitrile can be efficiently removed simultaneously with ammonia.
  • this effect tends to be improved.
  • the dehydration step is a step in which water is separated from crude acetonitrile to obtain dehydrated acetonitrile.
  • the method for separating water is not particularly limited, and examples thereof include a method of adding alkali to crude acetonitrile and performing extraction dehydration. Although it does not specifically limit as an alkali which can be used, For example, caustic soda is mentioned.
  • the amount of alkali used can be appropriately adjusted depending on the water content in the crude acetonitrile, and is preferably 10 to 90% by mass, more preferably 30 to 60% by mass, based on the water content of the crude acetonitrile. %.
  • the extraction temperature is preferably 5 to 60 ° C, more preferably 10 to 35 ° C.
  • the extraction dehydration method is not particularly limited, but for example, a method using a continuous countercurrent contact tower is preferable.
  • the packing for the continuous countercurrent contact tower is not particularly limited, but for example, Raschig ring, Lessing ring, Pole ring, Berle saddle, Interlock saddle, Terralet packing, Dixon ring, McMahon packing are preferable, and regular packing is Although not particularly limited, for example, a mesh-structured packing is preferable.
  • Dehydrated acetonitrile is a mixture that may contain 75% by mass or more and 99% by mass or less of acetonitrile, 0% by mass or more and less than 25% by mass of water, and other impurities.
  • purification process may have other processes, such as a low boiling point removal process and a high boiling point removal process.
  • the low boiling point removal step and the high boiling point removal step are steps for removing a low boiling component below the boiling point of acetonitrile and a high boiling component above the boiling point of acetonitrile from dehydrated acetonitrile to obtain a product acetonitrile described later.
  • a low boiling point removal method and a high boiling point removal method For example, the method of using a distillation column is mentioned.
  • water-containing crude acetonitrile is a known method for distillation purification of crude acetonitrile obtained as a by-product when producing acrylonitrile or methacrylonitrile by the catalytic ammoxidation reaction of propylene or isobutene with ammonia and molecular oxygen. It is also possible to purify in the same manner as above or according to the distillation purification method.
  • the conventional techniques to be referred to are not particularly limited, and examples thereof include Japanese Patent Application Laid-Open No. 55-153757, Japanese Patent No. 3104312 and WO 2013/146609.
  • the product acetonitrile can be obtained through the above purification step.
  • Process acetonitrile refers to acetonitrile having an acetonitrile content of more than 99% by mass and an impurity content other than acetonitrile of less than 1% by mass.
  • the content of acetonitrile contained in the product acetonitrile is preferably 99.5% by mass or more and 100% by mass or less, more preferably 99.9% by mass or more and 100% by mass or less, and further preferably 99.99% by mass. It is 100 mass% or less.
  • the content of toluene in the product acetonitrile is preferably less than 1.0 ppm by mass, more preferably 0.5 ppm by mass or less, and even more preferably 0.1 ppm by mass or less with respect to 100% by mass of acetonitrile. More preferably, it is less than 0.1 mass ppm.
  • the lower limit of the content of toluene contained in the product acetonitrile is not particularly limited, but is preferably not more than the detection limit, and more preferably 0% by mass with respect to 100% by mass of acetonitrile. When the content of toluene in the product acetonitrile is within the above range, higher quality acetonitrile is obtained.
  • the absorbance of ultraviolet absorption at a wavelength of 200 nm of the product acetonitrile is preferably 0.3 or less, more preferably 0.25 or less, and further preferably 0.2 or less.
  • the lower limit of the absorbance of ultraviolet absorption at a wavelength of 200 nm of the product acetonitrile is not particularly limited, and it is preferably as low as possible, more preferably 0.
  • the absorbance of ultraviolet absorption at a wavelength of 200 nm is an indicator of the content of the aromatic compound in the product acetonitrile. From this point of view, when the absorbance of ultraviolet absorption at a wavelength of 200 nm of the product acetonitrile is within the above range, higher quality acetonitrile is obtained.
  • Acetonitrile of this embodiment is obtained by the above production method.
  • Acetonitrile thus obtained is a solvent for chemical reaction, particularly a pharmaceutical intermediate synthesis solvent, a purification solvent, a mobile phase solvent for high performance liquid chromatography, a DNA synthesis solvent and a purification solvent, and an organic EL material. It can be suitably used as a solvent for synthesis or as a cleaning solvent for electronic parts.
  • acetonitrile of this embodiment is synonymous with product acetonitrile.
  • H-ZSM-5 zeolite manufactured by JGC Catalysts & Chemicals Co., Ltd. Went A flow-type fixed bed reactor was used for the reaction.
  • the reaction temperature was the average temperature of the catalyst layer.
  • the reaction product gas flowing out from the reaction tube was cooled and condensed by a cooler connected to the lower part of the reaction tube to obtain a solution of hydrous crude acetonitrile.
  • the reaction was continued for 200 hours, and water-containing crude acetonitrile was appropriately sampled, and composition analysis was performed by gas chromatography (“GC2010” manufactured by Shimadzu Corporation). The composition analysis was performed under the following conditions (the same applies hereinafter).
  • Acetonitrile concentration tower assumption experiment-2 The water-containing crude acetonitrile solution obtained by removing ammonia in the acetonitrile concentration tower assumption experiment-1 was redistilled in the same distillation tower, and the gas recovered from the top of the tower was cooled and recovered.
  • the composition of the obtained crude acetonitrile was as follows. (Crude acetonitrile composition) Ammonia (mass%) 0.03 Water (mass%) 34.62 Acetonitrile (mass%) 64.57 Acetic acid (mass%) 0.66 Acetone (mass%) 0.12
  • Procedure 3 Dehydration tower assumption experiment In order to make the water content in crude acetonitrile below an azeotropic composition, it extracted and dehydrated by adding an alkali. That is, dehydrated acetonitrile having a water content of 5% by mass or less was obtained by countercurrent contact with a 48% sodium hydroxide aqueous solution by a Dixon packing packed tower.
  • Procedure 4 Low-boiling, high-boiling separation column Using a glass Oldershaw distillation column having 50 stages, by carrying out continuous atmospheric distillation of dehydrated acetonitrile twice under the condition of a reflux ratio of 15, Removal of high-boiling substances and purification were performed to obtain a product acetonitrile.
  • Example 2 A gas phase reaction was performed in the same manner as in Example 1 except that acetic acid having a water content of 8% by mass was used instead of the acetic acid aqueous solution having a water content of 20% by mass. Hydrous crude acetonitrile was collected after 120 hours had passed since the start of the gas phase reaction, and the composition was analyzed by gas chromatography. The results were as follows. The water content of the reaction product liquid was about 47% by mass. The reaction was continued for 120 hours to obtain hydrous crude acetonitrile.
  • the content of toluene was separately separately analyzed in detail by gas chromatography, whereby it was 19 ppm by mass with respect to 100% by mass of acetonitrile.
  • Example 1 A gas phase reaction was performed in the same manner as in Example 1 except that acetic acid having a moisture content of 0% by mass was used instead of the acetic acid aqueous solution having a moisture content of 20% by mass. Water-containing crude acetonitrile was recovered after 11.0 hours had passed since the start of the gas phase reaction, and composition analysis was performed by gas chromatography. The results were as follows. The water content of the reaction product liquid was about 43% by mass. The reaction was continued for 120 hours to obtain hydrous crude acetonitrile.
  • the content of toluene was separately analyzed in detail by gas chromatography and found to be 21 ppm by mass with respect to 100% by mass of acetonitrile.
  • Example 3 Product acetonitrile was produced in the same manner as in Example 1 using water-containing crude acetonitrile having the following composition in which water was added to the water-containing crude acetonitrile obtained at the reactor outlet of Comparative Example 1 and the water content was increased to 52% by mass. .
  • (Hydrous crude acetonitrile composition) Ammonia (mass%) 5.4 Water (mass%) 52.0 Acetonitrile (mass%) 41.5 Acetic acid (mass%) 0.6 Acetone (mass%) 0.2 Acetamide (mass%) 0.3
  • a flow-type fixed bed reactor was used for the reaction.
  • a quartz glass reaction tube having an inner diameter of 20 mm was filled with 10 g of the catalyst.
  • the catalyst layer height was 48 mm.
  • Acetic acid and ammonia having a water content of 20% by mass were supplied to the reaction tube.
  • the reaction temperature was the average temperature of the catalyst layer.
  • the reaction product gas flowing out of the reaction tube was cooled and condensed by a cooler connected to the lower part of the reaction tube to obtain hydrous crude acetonitrile.
  • Example 4 Example 5
  • Example 6 Catalyst H- ⁇ KHD MFI Conversion rate of acetic acid (mol%) 86.4 98.8 96.4 Acetonitrile yield (mol%) 83.1 85.4 96.0 (Hydrous crude acetonitrile composition) Ammonia (mass%) 5.9 5.2 5.8 Water (mass%) 52.9 51.4 51.3 Acetonitrile (mass%) 31.9 38.3 40.6 Acetic acid (mass%) 7.7 0.8 1.8 Acetone (mass%) 0.1 4.1 0.1 Acetamide (mass%) 1.6 0.3 0.5
  • the energy consumption used for the purification of the hydrous crude acetonitrile produced by the gas phase reaction is small, and the purification equipment and the process are simple. Process can be realized. Therefore, while minimizing the increase in cost, ultraviolet light at a wavelength of 200 nm is low in toluene content for applications such as solvents used in the synthesis and purification of pharmaceutical intermediates and solvents for high performance liquid chromatography.
  • the present invention has industrial applicability as a method for providing a method for producing high-purity acetonitrile with low absorbance of absorption.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de production d'acétonitrile par l'exécution d'une étape de réaction en phase gazeuse pour obtenir de l'acétonitrile brut contenant de l'eau en soumettant de l'acide acétique et de l'ammoniac à une réaction en phase gazeuse en présence d'un catalyseur contenant un catalyseur acide solide, et d'une étape de raffinage pour obtenir un produit d'acétonitrile par raffinage de l'acétonitrile brut contenant de l'eau, la teneur en eau dans l'acétonitrile brut contenant de l'eau étant de 47 % en masse ou plus par rapport à 100 % en masse de l'acétonitrile brut contenant de l'eau, et la teneur en toluène à l'intérieur de celui-ci étant de 1 ppm en masse ou plus par rapport à 100 % en masse de l'acétonitrile.
PCT/JP2015/080064 2014-10-31 2015-10-26 Procédé de production d'acétonitrile WO2016068062A1 (fr)

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CN115772095A (zh) * 2022-11-25 2023-03-10 大连华毅众信新材料有限公司 一种醋酸氨化法一步合成乙腈的方法

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JP2019194283A (ja) * 2018-05-01 2019-11-07 旭化成株式会社 高分子電解質溶液及び高分子電解質膜
CN113620836A (zh) * 2021-08-13 2021-11-09 山东达民化工股份有限公司 一种乙腈的制备方法
CN115772095A (zh) * 2022-11-25 2023-03-10 大连华毅众信新材料有限公司 一种醋酸氨化法一步合成乙腈的方法
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