WO2015099053A1 - Procédé de fabrication de cyanopyridine, procédé de fabrication de benzonitrile, procédé de fabrication d'ester de carbonate et appareil de fabrication d'ester de carbonate - Google Patents

Procédé de fabrication de cyanopyridine, procédé de fabrication de benzonitrile, procédé de fabrication d'ester de carbonate et appareil de fabrication d'ester de carbonate Download PDF

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WO2015099053A1
WO2015099053A1 PCT/JP2014/084331 JP2014084331W WO2015099053A1 WO 2015099053 A1 WO2015099053 A1 WO 2015099053A1 JP 2014084331 W JP2014084331 W JP 2014084331W WO 2015099053 A1 WO2015099053 A1 WO 2015099053A1
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catalyst
reaction
solid
cyanopyridine
carbonate ester
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PCT/JP2014/084331
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Japanese (ja)
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憲治 中尾
鈴木　公仁
藤本　健一郎
冨重　圭一
善直 中川
堂野前　等
正純 田村
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新日鐵住金株式会社
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Priority claimed from JP2013273184A external-priority patent/JP6176108B2/ja
Priority claimed from JP2014042007A external-priority patent/JP6349787B2/ja
Priority claimed from JP2014183657A external-priority patent/JP6435728B2/ja
Priority claimed from JP2014183655A external-priority patent/JP6435727B2/ja
Application filed by 新日鐵住金株式会社 filed Critical 新日鐵住金株式会社
Publication of WO2015099053A1 publication Critical patent/WO2015099053A1/fr

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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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Definitions

  • the present invention relates to a method for producing cyanopyridine, a method for producing benzonitrile, a method for producing carbonate ester, and an apparatus for producing carbonate ester.
  • Carbonate ester is a general term for compounds in which one or two of hydrogen atoms of carbon dioxide CO (OH) 2 is substituted with an alkyl group or an aryl group, and RO—C ( ⁇ O) —OR ′ ( R and R ′ each represents a saturated hydrocarbon group or an unsaturated hydrocarbon group).
  • Carbonate esters are used as additives for gasoline additives to improve octane number, diesel fuel additives for reducing particles in exhaust gas, etc., and also synthesize polycarbonate and urethane, resins and organic compounds such as pharmaceuticals and agricultural chemicals. It is a very useful compound such as an alkylating agent, a carbonylating agent, a solvent, etc., or as a raw material for a lithium ion battery electrolyte, a lubricant oil raw material, and a deoxidizer for rust prevention of boiler piping. .
  • Non-Patent Document 1 as a method for producing a carbonate ester without using phosgene, a carbonic acid ester is reacted with ethylene oxide to synthesize a cyclic carbonate, and further reacted with methanol to form dimethyl carbonate.
  • a method for obtaining the above has been put into practical use. This method is an environmentally friendly and superior method that can be expected to reduce carbon dioxide, which is expected to be reduced as a global warming gas, with little use or generation of corrosive substances such as hydrochloric acid. It is.
  • effective use of by-produced ethylene glycol is a major problem. Further, since it is difficult to safely transport ethylene, which is a raw material for ethylene oxide, and ethylene oxide, there is a restriction that a carbonate ester production process plant must be located adjacent to the ethylene and ethylene oxide production process plant.
  • Patent Document 2 a method for producing dimethyl carbonate by oxidizing methanol and carbon monoxide in a liquid phase in the presence of a cuprous chloride catalyst is also disclosed.
  • carbon monoxide harmful to the human body is handled, and, as in the production method using phosgene, a halogen purification step from the obtained carbonic acid ester is essential by including halogen in the catalyst.
  • Problems such as carbon dioxide by-product have been pointed out.
  • Non-Patent Document 2 a method for producing dimethyl carbonate from methyl nitrite and carbon monoxide in the presence of a Pd—Cu-based catalyst has been put into practical use. In this method, methyl nitrite, which is a raw material, is supplied by reacting methanol and oxygen with nitric oxide by-produced during the production of dimethyl carbonate. There are issues such as handling harmful carbon monoxide.
  • Non-patent Document 3 attempts have been made to directly synthesize carbonate esters by reacting methanol and carbon dioxide in the presence of a solid catalyst.
  • this reaction is an equilibrium reaction, since the equilibrium is largely biased toward the raw material system, the methanol conversion rate remains at most about 1%, and there is a major problem to be overcome that the reaction rate and productivity are low.
  • Non-patent Document 6 research using molecular sieves (solid dehydrating agent) (Non-patent Document 6) has been reported, but it is a process that separates and circulates the reaction part (high pressure) and the dehydration part (normal pressure). There was a problem that consumption was large and a large amount of solid dehydrating agent was required.
  • Solid catalysts used for the direct synthesis reaction of carbonate ester have so far been tin compounds such as dimethoxydibutyltin, thallium compounds such as thallium methoxide, nickel compounds such as nickel acetate, vanadium pentoxide, potassium carbonate and other alkaline carbonates.
  • tin compounds such as dimethoxydibutyltin
  • thallium compounds such as thallium methoxide
  • nickel compounds such as nickel acetate, vanadium pentoxide
  • potassium carbonate and other alkaline carbonates Various compounds such as salts and Cu / SiO 2 have been studied.
  • the present inventors pay attention to a method of directly synthesizing a carbonate ester from monohydric alcohol and carbon dioxide using a heterogeneous catalyst in the production of carbonate ester, and remove water by-produced with the carbonate ester out of the system.
  • the use of acetonitrile as a compatibilizer eliminates the need for high pressures such as 300 atmospheres and 60 atmospheres as described in Non-Patent Documents 4 and 5, and it is the first effect that the reaction is promoted under a pressure close to normal pressure. (See Patent Document 3).
  • the present inventor has further studied the types of wettable powders for further improvement in the amount of carbonate produced, and as a result, by using 2-cyanopyridine or benzonitrile, the production of carbonate ester compared to acetonitrile. It was found that the amount and the production rate were greatly improved, the reaction was likely to proceed under a relatively low pressure close to normal pressure, and the reaction rate was very fast (see Patent Documents 4 and 5). However, the treatment method and utilization method of 2-picolinamide and benzamide as a by-product have not been studied.
  • Nitriles such as 2-cyanopyridine and benzonitrile which are wettable powders in the present invention, are generally used in many applications such as solvents, synthetic resins, dyes and pharmaceutical intermediates.
  • 2-cyanopyridine is a material used as a raw material for pharmaceuticals and agricultural chemicals, and is a material used as a starting material when synthesizing a pyridine or piperidine derivative at the 2-position.
  • Benzonitrile is a material used as a raw material for pharmaceuticals and agricultural chemicals, and is a material used as a starting material when various derivatives are synthesized.
  • this regeneration reaction is highly selective (because by-products are difficult to reuse as a wettable powder), and the yield is high (if the yield is low, the residual amount of 2-picolinamide or benzamide is low). It has been found that this is a problem because the amount of separation treatment with 2-cyanopyridine or benzonitrile increases and the load increases.
  • Non-patent Document 8 In general, nucleophilic substitution reaction with inorganic cyanide is used as one of the methods for synthesizing nitriles, but there is a problem that toxic cyanide is used and halogen salts are by-produced (Non-patent Document 8). ).
  • an ammoxidation method (SOHIO method) has been industrialized in a gas phase reaction using air as an oxidant in the presence of ammonia using a Mo—Bi-based or Fe—Sn-based oxide catalyst.
  • a high reaction temperature of 400 ° C. or higher is required, and it is further limited to acrylonitrile and the like (Non-patent Document 9).
  • Patent Documents 7 and 8 disclose phosgene, phosphorus oxychloride, thionyl chloride in a solvent composed of an aliphatic nitrile or an alicyclic nitrile capable of separating an amide from water.
  • Patent Document 3 describes a catalyst for a dehydration reaction of a primary amide and a method for producing a nitrile using the same.
  • the catalyst is a solid catalyst with vanadium supported on hydrotalcite, and it is said that the primary amide is also active with aromatic amides such as benzamide, amides with heterocycles and aliphatic amides, but the reaction rate is slow. not enough. This is because the amide is generally more stable than the nitrile, and the dehydration reaction of the amide is slower, and the intramolecular hydrogen between the hydrogen atom of the amide group and the nitrogen heteroatom in the amide molecule. This is probably because amides have particularly large intramolecular hydrogen bonds, become stable substances, and are unlikely to undergo dehydration.
  • an object of the present invention is to provide a method for regenerating picolinamide or benzamide to cyanopyridine or benzonitrile without using a powerful reagent and suppressing the generation of by-products. It is to provide.
  • the inventors have shown that the pyridine ring in picolinamide is weakly basic, so if an acidic catalyst is used, the pyridine ring may be adsorbed and poisoned at the active site of the catalyst, causing a decrease in activity. Therefore, a catalyst using a basic metal as an active species was studied.
  • Non-Patent Document 12 Metal oxide particles
  • Non-Patent Document 13 a two-dimensional layered inorganic compound carrier called hydrotalcite
  • the metal-oxygen double bond is presumed that the metal-oxygen double bond in the compound acts as an active species for the dehydration reaction of the amide.
  • the inventors examined from the viewpoint that the metal oxide is supported in an optimum existence state in consideration of the surface structure, ionicity, and electronic state as the carrier.
  • the present inventor also examined application of the above knowledge to a method for producing a carbonate ester. That is, the present inventors paid attention to a method of directly synthesizing a carbonate ester from a monohydric alcohol and carbon dioxide in the production of the carbonate ester, and used acetonitrile as a hydrating agent to remove water by-produced together with the carbonate ester out of the system.
  • a high pressure such as 30 MPa (300 atm) or 6 MPa (60 atm) as described in Non-Patent Documents 4 and 5 is unnecessary, and the reaction is accelerated under a pressure close to normal pressure.
  • Patent Document 3 Patent Document 4
  • the present inventors proceeded with a study on a method for producing a carbonate ester including utilization of by-products, and the reaction was likely to proceed under a relatively low pressure close to normal pressure, and the reaction rate was very high. It was considered to use cyanopyridine or benzonitrile, which has excellent properties as a wettable powder, which is fast and has few by-products, in this production method.
  • cyanopyridine characterized in that cyanopyridine is produced by heating and dehydrating a picolinamide in the presence of a catalyst supporting an alkali metal oxide and in the presence of an organic solvent.
  • the catalyst carrying the alkali metal oxide carries one or more alkali metal oxides on a catalyst carrier composed of one or more of SiO 2 , CeO 2 and ZrO 2.
  • the method for producing cyanopyridine as described in (1) or (2) above, wherein
  • a monohydric alcohol and carbon dioxide are reacted in the presence of one or both of a solid catalyst of CeO 2 and ZrO 2 and cyanopyridine to produce a carbonate and water, and the cyanopyridine and the above
  • a first reaction step of generating picolinamide by a hydration reaction with the generated water After the picolinamide is separated from the first reaction step, the picolinamide is dehydrated by heating in the presence of a catalyst carrying an alkali metal oxide and in the presence of an organic solvent, whereby cyano Having a second reaction step to regenerate to pyridine, A method for producing a carbonic acid ester, wherein the cyanopyridine regenerated in the second reaction step is used in the first reaction step.
  • a first catalyst that produces a carbonate ester and a picolinamide by mixing and reacting one or both of a solid catalyst of CeO 2 and ZrO 2 , a monohydric alcohol, carbon dioxide, and cyanopyridine.
  • a reaction process; The carbonate ester, picolinamide, unreacted cyanopyridine, and the solid catalyst discharged from the first reaction step are subjected to solvent extraction with alkane, and then solid-liquid separation is performed to obtain a liquid phase carbonate ester and unreacted cyanopyridine.
  • a first separation step of separating the alkane and the solid catalyst and picolinamide in solid phase A second separation step of separating each of the liquid phase carbonate ester after solid-liquid separation in the first separation step, unreacted cyanopyridine, and alkane;
  • the solid phase solid catalyst and picolinamide after solid-liquid separation in the first separation step are extracted with a hydrophilic solvent and then solid-liquid separated to obtain a liquid phase picolinamide and a hydrophilic solvent, and a solid phase solid catalyst.
  • the catalyst loaded with cyanopyridine, unreacted picolinamide, and alkali metal oxide discharged from the second reaction step is filtered to separate the catalyst loaded with the solid phase alkali metal oxide. Separation process of A fifth separation step for separating cyanopyridine, picolinamide, organic solvent, and water remaining after separation in the fourth separation step, respectively.
  • Carbonate, picoline which is produced from at least one of methyl picolinate and methyl carbamate as a by-product in the first reaction step and is discharged from the first reaction step in the first separation step.
  • the amide, unreacted cyanopyridine, methyl picolinate, methyl carbamate, and the solid catalyst were subjected to solvent extraction with alkane, followed by solid-liquid separation, and the liquid phase carbonate ester, unreacted cyanopyridine, methyl picolinate, carbamine 12.
  • the method for producing a carbonate ester according to any one of (9) to (11), wherein methyl acid and alkane are separated from the solid catalyst and picolinamide in solid phase.
  • the catalyst carrying the alkali metal oxide carries one or more alkali metal oxides on a catalyst carrier composed of one or more of SiO 2 , CeO 2 and ZrO 2.
  • the method for producing a carbonate ester according to any one of (8) to (16) above, wherein
  • a production apparatus for use in the method for producing a carbonate according to any one of (8) to (23), A pressurizing part for pressurizing carbon dioxide; In the presence of either one or both of CeO 2 and ZrO 2 and a cyanopyridine, a monohydric alcohol and carbon dioxide are reacted to produce a carbonate and water, and the cyanopyridine and the produced catalyst.
  • the carbonate ester, picolinamide, unreacted cyanopyridine, and the solid catalyst discharged from the first reaction section are subjected to solvent extraction with alkane, and then solid-liquid separation is performed to obtain a liquid phase carbonate ester and unreacted cyanopyridine.
  • a first separation part for separating the alkane and the solid catalyst and picolinamide in a solid phase A second separation part for separating the carbonate, unreacted cyanopyridine, and alkane in the liquid phase after the solid-liquid separation by the first separation part;
  • the solid catalyst and picolinamide after solid-liquid separation by the first separation unit are extracted with a hydrophilic solvent and then solid-liquid separated to separate into a liquid phase picolinamide and a hydrophilic solvent and a solid phase solid catalyst.
  • a third separation unit A second reaction for producing cyanopyridine by subjecting picolinamide separated by the third separation part to a dehydration reaction by heating in the presence of a catalyst supporting an alkali metal oxide and in the presence of an organic solvent.
  • An apparatus for producing carbonate ester comprising: a transport unit that transports the cyanopyridine separated by the fifth separation unit to the first reaction unit.
  • Any one of molybdenum, tungsten, rhenium, titanium and niobium on a catalyst support composed of one or more of SiO 2 , TiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 and C Benzonitrile is produced by heating and dehydrating benzamide in the presence of a catalyst on which a metal oxide of two or more metal species is supported and in the presence of an organic solvent.
  • a method for producing benzonitrile is produced by heating and dehydrating benzamide in the presence of a catalyst on which a metal oxide of two or more metal species is supported and in the presence of an organic solvent.
  • a monohydric alcohol and carbon dioxide are reacted in the presence of either one or both of CeO 2 and ZrO 2 and benzonitrile to produce a carbonate and water, and the benzonitrile
  • a first reaction step of generating benzamide by a hydration reaction between the water and the generated water After separating the benzamide from the first reaction step, the benzamide is converted into SiO 2 , TiO 2 , a metal oxide of any one or more of molybdenum, tungsten, rhenium, titanium, and niobium.
  • a monohydric alcohol and carbon dioxide are reacted in the presence of either one or both of CeO 2 and ZrO 2 and benzonitrile to produce a carbonate and water, and the benzonitrile
  • the carbonate ester, benzamide, unreacted benzonitrile discharged from the first reaction step, and the solid catalyst are subjected to solvent extraction with alkane and then separated into solid and liquid, and the liquid phase carbonate ester, unreacted benzonitrile, And a first separation step of separating the alkane and the solid catalyst and benzamide in a solid phase;
  • a third separation step in which the solid catalyst and benzamide after the solid-liquid separation are extracted with a hydrophilic solvent, followed by solid-liquid separation, and separated into a liquid phase
  • a second reaction step The catalyst in which the solid phase metal oxide is supported on the catalyst support is filtered by filtering the catalyst in which the benzonitrile, unreacted benzamide, and metal oxide supported on the catalyst support are discharged from the second reaction step.
  • the catalyst support on which the metal oxide is supported is any one or more of SiO 2 , TiO 2 , CeO 2 , and ZrO 2 (31) to (35), The manufacturing method of carbonate ester of any one of these.
  • a monohydric alcohol and carbon dioxide are reacted to form a carbonate and water, and the benzonitrile and the above A first reaction part for producing benzamide by a hydration reaction with the produced water;
  • the carbonate ester, benzamide, unreacted benzonitrile, and the solid catalyst discharged by the first reaction unit are subjected to solvent extraction with alkane, and then solid-liquid separated to obtain a liquid phase carbonate ester, unreacted benzonitrile, And a first separation part for separating the alkane and the solid catalyst and benzamide in a solid phase;
  • a second separation unit for separating the carbonate, unreacted benzonitrile, and alkane in the liquid phase after the solid-liquid separation;
  • a carbonic acid ester producing apparatus comprising: a conveying unit configured to convey the separated benzonitrile to the first reaction unit.
  • regeneration from picolinamide or benzamide to cyanopyridine or benzonitrile can be performed without using a strong reagent and suppressing the generation of by-products.
  • the method for producing 2-cyanopyridine by the dehydration reaction of 2-picolinamide of the present invention comprises dehydrating 2-picolinamide in the presence of a catalyst supporting a basic metal oxide and an organic solvent to give 2-cyanopyridine. It produces pyridine.
  • a basic alkali metal (K, Li, Na, Rb, Cs) oxide can be used, and as the carrier, a substance that generally becomes a catalyst carrier can be used.
  • K, Li, Na, Rb, Cs a basic alkali metal
  • the carrier a substance that generally becomes a catalyst carrier can be used.
  • the pyridine ring in 2-picolinamide is weakly basic, so if an acidic catalyst is used, the pyridine ring may be adsorbed and poisoned at the active site of the catalyst, causing a decrease in activity.
  • metal oxides having basic properties are preferred.
  • Examples of the carrier production method used here are roughly divided into a dry method and a wet method as general production methods in the case of SiO 2 .
  • the dry method includes a combustion method, an arc method, etc.
  • the wet method includes a sedimentation method, a gel method, etc., and it is possible to manufacture a catalyst carrier by any of the manufacturing methods. Since it is technically and economically difficult to form, a gel method is preferred in which silica sol can be easily formed into a spherical shape by spraying in a gas medium or a liquid medium.
  • cerium acetylacetonate hydrate and cerium hydroxide cerium sulfate, cerium acetate, cerium nitrate, cerium ammonium nitrate, cerium carbonate, cerium oxalate, perchlorate cerium, cerium phosphate, cerium stearate
  • cerium oxide as a reagent it can be used as it is or by drying or baking in an air atmosphere. Furthermore, it can be used by precipitating from a solution in which cerium is dissolved, filtering, drying, and baking.
  • zirconium compounds such as zirconium ethoxide, zirconium butoxide, zirconium carbonate, zirconium hydroxide, zirconium phosphate, zirconium acetate, zirconium chloride oxide, zirconium dinitrate, zirconium sulfate and the like are fired in an air atmosphere.
  • zirconium oxide as a reagent it can be used as it is or by drying or baking in an air atmosphere. Furthermore, it can be used by precipitating from a solution in which zirconium is dissolved, filtering, drying and baking.
  • a base is added to a solution containing cerium and zirconium to form a hydroxide by coprecipitation, followed by filtration and washing, followed by drying and firing in an air atmosphere.
  • the powder particles of CeO 2 and ZrO 2 can also be prepared by firing the physical mixture, the specific surface area of the final preparation is not high, preferably easily coprecipitation reaction proceeds more.
  • a solid catalyst carrier made of a compound of cerium oxide and zirconium oxide such as CeO 2 —ZrO 2 can be obtained by these methods.
  • the firing temperature at the time of preparation of each of these catalyst carriers may be selected at a temperature at which the specific surface area of the final preparation is increased. Although it depends on the starting material, for example, 300 ° C. to 1100 ° C. is preferable.
  • the solid catalyst carrier according to the present invention may contain inevitable impurities that are mixed in the catalyst manufacturing process in addition to the above elements, but it is desirable that impurities are not mixed as much as possible.
  • An example of the method for producing the catalyst of the present invention is as follows.
  • the support is SiO 2
  • a commercially available powder or spherical SiO 2 can be used, and 100 mesh (0.15 mm) is used so that the active metal can be uniformly supported.
  • pre-baking is preferably performed in air at 700 ° C. for 1 hour.
  • SiO 2 has various properties, but a larger surface area is preferable because the active metal can be highly dispersed and the amount of 2-cyanopyridine produced is improved. Specifically, a surface area of 300 m 2 / g or more is preferable.
  • the surface area of the catalyst after preparation may be lower than the surface area of only SiO 2 due to the interaction between SiO 2 and the active metal. In that case, it is preferable that the surface area of the catalyst after manufacture is 150 m 2 / g or more.
  • the active metal oxide can be supported by an impregnation method such as an incipient wetness method or an evaporation to dryness method.
  • the metal salt used as the precursor may be water-soluble, and various compounds such as carbonates, hydrogen carbonates, chloride salts, nitrates, and silicates can be used as long as they are alkali metals.
  • the carrier can be used as a catalyst by impregnating a carrier with an aqueous precursor of a basic metal, and then dried and calcined, and the calcining temperature is preferably 400 to 600 ° C., although it depends on the precursor used.
  • the supported amount of the catalyst may be set as appropriate.
  • the supported metal amount of the alkali metal oxide is about 0.1 to 1.5 mmol / g, particularly 0.1 to 1 mmol / g based on the total catalyst weight. It is preferable to set at about g. If the loading amount is larger than this, the activity may decrease. Moreover, what is necessary is just to set suitably about the usage-amount of the catalyst at the time of reaction.
  • the catalyst in the present invention is composed of a catalyst in which one or more alkali metal oxides are supported on a carrier composed of one or more of SiO 2 , CeO 2 , and ZrO 2.
  • a carrier composed of one or more of SiO 2 , CeO 2 , and ZrO 2.
  • unavoidable impurities mixed in the catalyst production process or the like may be included. However, it is desirable to prevent impurities from entering as much as possible.
  • the catalyst in which the metal oxide serving as the active species of the present invention is supported on the support may be in the form of powder or molded body, and in the case of the molded body, it is spherical, pellet-shaped, cylinder-shaped. , Ring shape, wheel shape, granule shape and the like.
  • the method for producing 2-cyanopyridine using the catalyst of the present invention is not particularly limited as a reaction mode, and is not limited to a batch reactor, a semi-batch reactor, a continuous tank reactor or a tube reactor. Any flow reactor may be used. Moreover, any of a fixed bed, a slurry bed, etc. can be applied to the catalyst.
  • the organic solvent is preferably a substance having a boiling point of 130 ° C. or higher, and examples thereof include chlorobenzene, (o-, m-, p-) xylene, and mesitylene.
  • the reaction conditions are preferably selected from the viewpoints of the dehydration reaction rate, the boiling point of the solvent, the amount of CO 2 emitted during the reaction, and economic efficiency.
  • the usual reaction conditions in the method for producing 2-cyanopyridine of the present invention can be carried out at a reaction temperature of 160 to 200 ° C., a pressure of normal pressure, and a time of several hours to 500 hours. Is not to be done.
  • the type and shape of the molecular sieve used as the dehydrating agent are not particularly limited.
  • 3A, 4A, 5A, etc. which are generally highly water-absorbing, such as spherical or pellets are used. it can. Further, it is preferably dried in advance, and is preferably dried at 300 to 500 ° C. for about 1 hour.
  • the periphery of the reaction tube is heated to 160 to 200 ° C.
  • the melting point of each substance is 110 ° C. (2-picolinamide), 24 ° C. (2-cyanopyridine), ⁇ 45 ° C. (organic solvent such as mesitylene), and the boiling point is 143 ° C. (2-picolinamide), Since it is 212 ° C. (2-cyanopyridine), 100 ° C. (water), and 165 ° C. (organic solvent such as mesitylene), the reaction phase is all liquid except for the solid catalyst, and is partially vaporized.
  • the 2-picolinamide, by-product water, and the organic solvent are cooled by the cooler, and the by-product water is adsorbed by the dehydrating agent, and the 2-picolinamide and the organic solvent return to the reaction tube and contribute to the reaction again.
  • the boiling point of each substance present in the system after the reaction is different as described above, it can be easily separated by distillation. Further, since the catalyst is a solid, it can be separated and recovered as necessary after the reaction, and can be easily recovered by a solid-liquid separation method such as ordinary filtration.
  • 3-Cyanopyridine and 4-cyanopyridine can be synthesized by changing 2-picolinamide, which is a starting material of 2-cyanopyridine, to nicotinamide and isonicotinamide and carrying out the same treatment.
  • the method for producing benzonitrile includes the same steps as the method for producing cyanopyridine. Specifically, it is as follows.
  • the method for producing benzonitrile by dehydration reaction of benzamide according to the present invention is to produce benzonitrile by dehydration reaction of benzamide in the presence of a catalyst supporting a basic metal oxide and an organic solvent.
  • the catalyst used in the present invention may be an oxide of a basic metal (Mo, W, Re, Ti, Nb), and the support may be a substance that generally becomes a catalyst support.
  • a catalyst supporting an oxide of an active metal species is used on SiO 2 , TiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 , C, and two or more of these catalyst supports It was found to show particularly high performance.
  • any one or two of SiO 2 , TiO 2 , CeO 2 , and ZrO 2 are used. It is preferable to use more than one type of catalyst support because it shows higher performance.
  • the general production method in the case of SiO 2 are roughly classified into a dry method and a wet method.
  • the dry method includes a combustion method, an arc method, etc.
  • the wet method includes a sedimentation method, a gel method, etc., and it is possible to manufacture a catalyst carrier by any of the manufacturing methods. Since it is technically and economically difficult to form, a gel method is preferred in which silica sol can be easily formed into a spherical shape by spraying in a gas medium or a liquid medium.
  • cerium acetylacetonate hydrate and cerium hydroxide cerium sulfate, cerium acetate, cerium nitrate, cerium ammonium nitrate, cerium carbonate, cerium oxalate, perchlorate cerium, cerium phosphate, cerium stearate
  • cerium oxide as a reagent it can be used as it is or by drying or baking in an air atmosphere. Furthermore, it can be used by precipitating from a solution in which cerium is dissolved, filtering, drying, and baking.
  • zirconium compounds such as zirconium ethoxide, zirconium butoxide, zirconium carbonate, zirconium hydroxide, zirconium phosphate, zirconium acetate, zirconium chloride oxide, zirconium dinitrate, zirconium sulfate and the like are calcined in an air atmosphere.
  • zirconium oxide as a reagent it can be used as it is or by drying or baking in an air atmosphere. Furthermore, it can be used by precipitating from a solution in which zirconium is dissolved, filtering, drying and baking.
  • C is mainly composed of carbon and may be in any form as long as it does not change during the reaction period.
  • activated carbon is preferable, but it is not limited thereto.
  • a base is added to a solution containing two or more kinds of metal salts to form a hydroxide by coprecipitation, followed by filtration, washing and drying in an air atmosphere. It can be prepared by firing. Moreover, although it can prepare also by physically mixing and baking the powder of 2 or more types of oxides, since the specific surface area of a final preparation does not become high, the coprecipitation method with which reaction progresses more is preferable.
  • a base is added to a solution containing cerium and zirconium to form a hydroxide by coprecipitation, followed by filtration and washing, followed by drying and firing in an air atmosphere.
  • a base is added to a solution containing cerium and zirconium to form a hydroxide by coprecipitation, followed by filtration and washing, followed by drying and firing in an air atmosphere.
  • a solid catalyst carrier comprising a compound of cerium oxide and zirconium oxide such as CeO 2 —ZrO 2
  • the firing temperature at the time of preparation of each of these catalyst carriers may be selected at a temperature at which the specific surface area of the final preparation is increased. Although it depends on the starting material, for example, 300 ° C. to 1100 ° C. is preferable.
  • the solid catalyst carrier according to the present invention may contain inevitable impurities that are mixed in the catalyst manufacturing process in addition to the above elements, but it is desirable that impurities are not mixed as much as possible.
  • the carrier selected from one or more of SiO 2 , TiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 , and C can support active metal species in a highly dispersed manner as the surface area increases. This is preferable because the amount of nitrile produced is improved.
  • the surface area depends on the type of the carrier, but the surface area is preferably 10 m 2 / g or more as measured by the BET method. Whether it is highly dispersed can be confirmed with an image of an electron microscope (SEM, TEM, etc.).
  • a metal oxide that becomes an active species may be supported on a support by a known method.
  • a support can be supported by an impregnation method such as an incipient wetness method or an evaporation to dryness method.
  • the carrier is SiO 2
  • commercially available powder or spherical SiO 2 can be used, and the particle size is adjusted to 100 mesh (0.15 mm) or less to remove the moisture so that the active metal can be uniformly supported.
  • SiO 2 has various properties, it is preferable that the surface area is large because the active metal can be supported in a highly dispersed manner and the amount of benzonitrile produced is improved. Specifically, a surface area of 300 m 2 / g or more (BET method) is more preferable.
  • the surface area of the catalyst after preparation may be lower than the surface area of only SiO 2 due to the interaction between SiO 2 and the active metal. In that case, it is more preferable that the surface area of the catalyst after production is 150 m 2 / g or more (BET method).
  • the metal salt that is a precursor of the metal oxide that becomes the active species may be water-soluble.
  • various compounds such as carbonate, bicarbonate, chloride, nitrate, and silicate can be used.
  • the carrier can be used as a catalyst by impregnating a carrier with an aqueous precursor of a basic metal, and then dried and calcined, and the calcining temperature is preferably 400 to 600 ° C., although it depends on the precursor used.
  • the amount of metal oxide supported may be set as appropriate.
  • the amount of metal oxide supported in terms of metal based on the total catalyst weight is about 0.1 to 1.5 mmol / g, particularly 0.1 to 1 mmol. / G, preferably about 0.2 to 0.8 mmol / g.
  • the activity may be reduced due to the coarsening of the metal oxide.
  • what is necessary is just to set suitably about the usage-amount of the catalyst at the time of reaction.
  • the catalyst in the present invention is one or two kinds of metal oxides on a support composed of one or more of SiO 2 , TiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 , and C.
  • a support composed of one or more of SiO 2 , TiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 , and C.
  • the catalyst which carry
  • the impurities are preferably less than 1% by weight of the total catalyst.
  • the catalyst in which the metal oxide serving as the active species of the present invention is supported on the support may be in the form of powder or molded body, and in the case of the molded body, it is spherical, pellet-shaped, cylinder-shaped. , Ring shape, wheel shape, granule shape and the like.
  • the method for producing benzonitrile using the catalyst of the present invention is not particularly limited as a reaction mode, such as a batch reactor, a semi-batch reactor, a continuous tank reactor or a tube reactor. Any of the flow reactors may be used. Moreover, any of a fixed bed, a slurry bed, etc. can be applied to the catalyst.
  • the organic solvent is preferably a substance having a boiling point of 130 ° C. or more, and examples thereof include chlorobenzene, (o-, m-, p-) xylene, mesitylene, furfural, heptadecane and the like. , P-) xylene and mesitylene are preferred.
  • the reaction conditions are preferably selected from the viewpoints of the dehydration reaction rate, the boiling point of the solvent, the amount of CO 2 emitted during the reaction, and economic efficiency.
  • the reaction temperature is 160 to 200 ° C.
  • the pressure is normal pressure
  • the time is several hours to 24 hours. It is not a thing.
  • a dehydrating agent such as zeolite is installed in the system, and the by-product water is removed. It is desirable to carry out the reaction while removing.
  • zeolite molecular sieve
  • calcium hydride was installed in the extraction tube as a dehydrating agent, and a catalyst, benzamide, and an organic solvent were placed in the reaction tube. The amount of benzonitrile produced can be improved by reacting at normal pressure with reflux.
  • the type and shape of the molecular sieve used as the dehydrating agent are not particularly limited.
  • 3A, 4A, 5A, etc. which are generally highly water-absorbing, such as spherical or pellets are used. it can. Further, it is preferably dried in advance, and is preferably dried at 300 to 500 ° C. for about 1 hour.
  • benzoic acid may be produced as a by-product due to the decomposition of benzamide as described above.
  • benzamide and product remained in the reaction product.
  • benzonitriles, by-product water, and organic solvents, and these by-products are hardly produced.
  • it is very small amount, can isolate
  • the reaction temperature is preferably a condition under which the benzamide dehydration reaction is performed in a liquid phase. Considering the reaction efficiency, it is preferable that the temperature is higher under liquid phase conditions.
  • the reaction is performed under normal pressure, it is preferable to heat the periphery of the reaction tube to 160 to 200 ° C.
  • the melting point of each substance in a typical reaction system is 127 ° C. (benzamide), ⁇ 13 ° C. (benzonitrile), ⁇ 45 ° C. (organic solvent such as mesitylene), and the boiling point is 288 ° C.
  • the boiling point of each substance present in the system after the reaction is different as described above, it can be easily separated by distillation. Further, since the catalyst is a solid, it can be separated and recovered as necessary after the reaction, and can be easily recovered by a solid-liquid separation method such as ordinary filtration.
  • the first reaction step in the method for producing a carbonate ester of the present invention involves directly reacting a monohydric alcohol and carbon dioxide in the presence of one or both of a solid catalyst of CeO 2 and ZrO 2 and 2-cyanopyridine. This produces a carbonate ester.
  • any alcohol selected from one or more of primary alcohol, secondary alcohol, and tertiary alcohol can be used, and methanol, ethanol, 1-propanol can be used.
  • methanol, ethanol, 1-propanol can be used.
  • Isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, allyl alcohol, 2-methyl-1-propanol, cyclohexane methanol, benzyl alcohol This is preferable because the yield of the product is high and the reaction rate is fast.
  • the produced carbonates are dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dipentyl carbonate, dihexyl carbonate, diheptyl carbonate, dioctyl carbonate, dinonane carbonate, diallyl carbonate, di-2-methyl-propyl carbonate, respectively.
  • dicyclohexane methyl carbonate and dibenzyl carbonate dibenzyl carbonate.
  • CeO 2 and ZrO 2 solid solutions and composite oxides are basically based on a mixing ratio of CeO 2 and ZrO 2 of 50:50, but the mixing ratio can be changed as appropriate.
  • the catalyst used for the direct synthesis of carbonic acid ester is required to have an acid-base complex function, and in particular, has a property of relatively low acidity and relatively high basicity. Is preferred. If the acidity is too high, it is not preferable because a large amount of ether is synthesized rather than carbonate.
  • alcohol is adsorbed in the form of HO—R... M, and RO—C ( ⁇ O) —OR is generated between both adsorbed species.
  • This solid catalyst also exhibits catalytic activity for the hydration reaction of water and 2-cyanopyridine, which are by-produced during the synthesis of carbonate ester. Therefore, although both the carbonate ester synthesis reaction and the hydration reaction proceed on the surface of the catalyst, the hydration of 2-cyanopyridine is carried out even under low pressure conditions, which is unfavorably balanced for the carbonate ester synthesis reaction.
  • the reaction proceeds under catalysis, and the water generated as a by-product from the synthesis reaction of the carbonate ester is rapidly eliminated from the catalyst surface, so that the equilibrium of the synthesis reaction of the carbonate ester shifts to the production system and the reaction pressure is low.
  • the carbonate ester synthesis reaction is allowed to have a high reaction rate without being subjected to equilibrium constraints even under mild conditions.
  • high pressure a large amount of CO 2 molecules are adsorbed on the catalyst surface, making it difficult to contact with water molecules generated during the synthesis of carbonic acid ester, so that the hydration reaction with 2-cyanopyridine does not proceed easily. Therefore, it is considered that the carbonate ester can be produced only in a state close to the equilibrium constraint, and as a result, the productivity is not increased under high pressure.
  • cerium oxide as a reagent is used, it can be used as it is or by drying or baking in an air atmosphere. Furthermore, it can be used by precipitating from a solution in which cerium is dissolved, filtering, drying, and baking.
  • zirconium oxide ZrO 2
  • various zirconium compounds such as zirconium ethoxide, zirconium butoxide, zirconium carbonate, zirconium hydroxide, zirconium phosphate, zirconium acetate, zirconium chloride oxide, zirconium oxide dinitrate, zirconium sulfate and the like are mixed with air. It can be prepared by firing in an atmosphere. When zirconium oxide as a reagent is used, it can be used as it is or by drying or baking in an air atmosphere. Furthermore, it can be used by precipitating from a solution in which zirconium is dissolved, filtering, drying and baking.
  • a base is added to a solution containing cerium and zirconium to form a hydroxide by coprecipitation, followed by filtration and washing with water. It can be prepared by drying and firing in an air atmosphere. Although the powder particles of CeO 2 and ZrO 2 can also be prepared by firing the physical mixture, the specific surface area of the final preparation is not high, preferably easily coprecipitation reaction proceeds more.
  • a solid catalyst made of a compound of cerium oxide and zirconium oxide such as CeO 2 —ZrO 2 can be obtained by these methods.
  • the solid catalyst according to the present invention may contain inevitable impurities mixed in the catalyst production process in addition to the above elements, but it is desirable that impurities are not mixed as much as possible.
  • the catalyst of the present invention may be in any form of powder or molded body, and in the case of a molded body, it may be any of spherical, pellet, cylinder, ring, wheel, granule, etc. .
  • carbon dioxide used in the present invention is not limited to those prepared as industrial gases, but can also be used that separated and recovered from exhaust gases from factories, steel mills, power plants, etc. that manufacture each product.
  • the separated liquid component contains carbonate ester, 2-cyanopyridine, and an organic solvent.
  • the melting point and boiling point of each substance are 4 ° C and 90 ° C (dimethyl carbonate). -43 ° C and 128 ° C (diethyl carbonate), -41 ° C and 167 ° C (dipropyl carbonate), 25 ° C or less and 207 ° C (dibutyl carbonate), and 24 ° C and 215 ° C (2-cyanopyridine) , ⁇ 95 ° C. and 69 ° C. (for example, hexane), the carbonate ester can be separated by distillation, and the product carbonate ester can be recovered with high purity. In addition to distillation, it is also possible to filter and recover what is solidified by cooling stepwise to below the melting point.
  • 2-picolinamide and solid catalyst separated as solid components can be separated from the solid catalyst and a filter by extracting only 2-picolinamide with a hydrophilic solvent.
  • the hydrophilic solvent used here is preferably acetone, ethanol, ether, or water in view of ease of handling and separation at a later stage.
  • the 2-picolinamide dissolved in the hydrophilic solvent can be separated by distillation, and the by-produced 2-picolinamide can be purified with high purity.
  • the separated solid catalyst is regenerated in the step of regenerating the catalyst and can be reused in the first reaction step.
  • the catalyst regeneration step is a step in which impurities on the solid catalyst are heated to burn off, and is baked at 400 to 700 ° C., preferably 500 to 600 ° C. for about 3 hours. In order to prevent structural destruction of the solid catalyst due to rapid temperature rise, it is better to consider the drying step before firing, and it is preferable to dry at 110 ° C. for about 2 hours.
  • 2-picolinamide is dehydrated in the presence of a catalyst supporting a basic metal oxide and an organic solvent to produce 2-cyanopyridine.
  • a catalyst in which an oxide of a basic alkali metal (K, Li, Na, Rb, Cs) is generally supported on a substance serving as a catalyst carrier can be used.
  • K, Li, Na, Rb, Cs a basic alkali metal
  • the pyridine ring in 2-picolinamide is weakly basic, so if an acidic catalyst is used, the pyridine ring may be adsorbed and poisoned at the active site of the catalyst, causing a decrease in activity.
  • a metal having basic properties is preferable.
  • Examples of the carrier production method used here are roughly divided into a dry method and a wet method as general production methods in the case of SiO 2 .
  • the dry method includes a combustion method, an arc method, etc.
  • the wet method includes a sedimentation method, a gel method, etc., and it is possible to manufacture a catalyst carrier by any of the manufacturing methods. Since it is technically and economically difficult to form, a gel method is preferred in which silica sol can be easily formed into a spherical shape by spraying in a gas medium or a liquid medium.
  • cerium acetylacetonate hydrate and cerium hydroxide cerium sulfate, cerium acetate, cerium nitrate, cerium ammonium nitrate, cerium carbonate, cerium oxalate, perchlorate cerium, cerium phosphate, cerium stearate
  • cerium oxide as a reagent it can be used as it is or by drying or baking in an air atmosphere. Furthermore, it can be used by precipitating from a solution in which cerium is dissolved, filtering, drying, and baking.
  • zirconium compounds such as zirconium ethoxide, zirconium butoxide, zirconium carbonate, zirconium hydroxide, zirconium phosphate, zirconium acetate, zirconium chloride oxide, zirconium dinitrate, zirconium sulfate and the like are fired in an air atmosphere.
  • zirconium oxide as a reagent it can be used as it is or by drying or baking in an air atmosphere. Furthermore, it can be used by precipitating from a solution in which zirconium is dissolved, filtering, drying and baking.
  • a base is added to a solution containing cerium and zirconium to form a hydroxide by coprecipitation, followed by filtration and washing, followed by drying and firing in an air atmosphere.
  • the powder particles of CeO 2 and ZrO 2 can also be prepared by firing the physical mixture, the specific surface area of the final preparation is not high, preferably easily coprecipitation reaction proceeds more.
  • a solid catalyst carrier made of a compound of cerium oxide and zirconium oxide such as CeO 2 —ZrO 2 can be obtained by these methods.
  • the firing temperature at the time of preparation of each of these catalyst carriers may be selected at a temperature at which the specific surface area of the final preparation is increased. Although it depends on the starting material, for example, 300 ° C. to 1100 ° C. is preferable.
  • the solid catalyst carrier according to the present invention may contain inevitable impurities that are mixed in the catalyst manufacturing process in addition to the above elements, but it is desirable that impurities are not mixed as much as possible.
  • An example of the method for producing the catalyst of the present invention is as follows.
  • the support is SiO 2
  • a commercially available powder or spherical SiO 2 can be used, and 100 mesh (0.15 mm) is used so that the active metal can be uniformly supported.
  • pre-baking is preferably performed in air at 700 ° C. for 1 hour.
  • SiO 2 has various properties, but a larger surface area is preferable because the active metal can be highly dispersed and the amount of 2-cyanopyridine produced is improved. Specifically, a surface area of 300 m 2 / g or more is preferable.
  • the surface area of the catalyst after preparation may be lower than the surface area of only SiO 2 due to the interaction between SiO 2 and the active metal. In that case, it is preferable that the surface area of the catalyst after manufacture is 150 m 2 / g or more.
  • the active metal oxide can be supported by an impregnation method such as an incipient wetness method or an evaporation to dryness method.
  • the metal salt used as the precursor may be water-soluble, and various compounds such as carbonates, hydrogen carbonates, chloride salts, nitrates, and silicates can be used as long as they are alkali metals.
  • the carrier can be used as a catalyst by impregnating a carrier with an aqueous precursor of a basic metal, and then dried and calcined, and the calcining temperature is preferably 400 to 600 ° C., although it depends on the precursor used.
  • the catalyst according to the present invention may contain inevitable impurities that are mixed in the catalyst manufacturing process in addition to the above-mentioned elements, but it is desirable that impurities are not mixed as much as possible.
  • the catalyst supported on the carrier of the present invention may be in the form of a powder or a molded body.
  • a spherical shape, a pellet shape, a cylinder shape, a ring shape, a wheel shape, a granule Any shape may be used.
  • the method for producing 2-cyanopyridine using the catalyst of the present invention is not particularly limited as a reaction mode, and is not limited to a batch reactor, a semi-batch reactor, a continuous tank reactor or a tube reactor. Any flow reactor may be used. Moreover, any of a fixed bed, a slurry bed, etc. can be applied to the catalyst.
  • the organic solvent used for the dehydration reaction is preferably a substance having a boiling point of 130 ° C. or higher, and examples thereof include chlorobenzene, (o-, m-, p-) xylene, mesitylene and the like, and mesitylene is particularly preferable.
  • reaction conditions are preferably selected from the viewpoints of the dehydration reaction rate, the boiling point of the solvent, the amount of CO 2 generated during the reaction, and economic efficiency.
  • the reaction temperature may be 160 to 200 ° C.
  • the reaction pressure may be normal pressure
  • the reaction time may be several hours to 500 hours, but is not particularly limited thereto.
  • the type and shape of the molecular sieve used as the dehydrating agent are not particularly limited.
  • 3A, 4A, 5A, etc. which are generally highly water-absorbing, such as spherical or pellets are used. it can. Further, it is preferably dried in advance, and is preferably dried at 300 to 500 ° C. for about 1 hour.
  • the periphery of the reaction tube is heated to 160 to 200 ° C.
  • the melting point of each substance is 110 ° C. (2-picolinamide), 24 ° C. (2-cyanopyridine), ⁇ 45 ° C. (organic solvent such as mesitylene), and the boiling point is 143 ° C. (2-picolinamide), Since it is 212 ° C. (2-cyanopyridine), 100 ° C. (water), and 165 ° C. (organic solvent such as mesitylene), the reaction phase is all liquid except for the solid catalyst, and is partially vaporized.
  • the 2-picolinamide, by-product water, and the organic solvent are cooled by the cooler, and the by-product water is adsorbed by the dehydrating agent, and the 2-picolinamide and the organic solvent return to the reaction tube and contribute to the reaction again.
  • the 2-cyanopyridine regenerated in the second reaction step can be reused in the first reaction step.
  • FIG. 1 is an example of a suitable facility of the present invention. Moreover, the state of each substance in each process in this equipment in FIG. 1 is shown in FIG. This equipment can be used in the case of reaction conditions in which the conversion rate of monohydric alcohol is 100% and by-products of methyl picolinate and methyl carbamate are not generated.
  • first reaction step In the first reaction step, in the first reaction column 1 (first reaction section), one or both of the solid catalyst (solid phase) of CeO 2 and ZrO 2 , the monohydric alcohol 12 (liquid phase), Carbon dioxide (gas phase) is charged through 2-cyanopyridine 13 (liquid phase) and pressure blower 10 (pressure part). As the solid catalyst, a solid catalyst 14 (solid phase) newly charged before the reaction or regenerated in the regeneration tower 6 can be used.
  • 2-cyanopyridine is a new one at the start of the reaction, it is purified by unreacted 2-cyanopyridine 20 (liquid phase) purified in the first distillation column 3 and in the third distillation column 9. 2-Cyanopyridine regenerated from picolinamide can be reused.
  • the carbon dioxide ester direct synthesis apparatus using the solid catalyst of either or both of CeO 2 and ZrO 2 of the present invention is a batch reactor, a semi-batch reactor, a continuous tank reactor, a tube type, or the like. Any flow reactor such as a reactor may be used.
  • the reaction temperature in the first reaction column 1 is preferably 50 to 300 ° C.
  • the reaction temperature is less than 50 ° C.
  • the reaction rate is low, the carbonate ester synthesis reaction and the hydration reaction with 2-cyanopyridine hardly proceed, and the carbonate ester productivity tends to be low.
  • the reaction temperature exceeds 150 ° C., the reaction rate of each reaction increases, but decomposition and modification of the carbonate ester, and 2-picolinamide easily react with the monohydric alcohol, resulting in a low carbonate ester yield.
  • this temperature is considered to vary depending on the type and amount of the solid catalyst and the amount and ratio of the raw materials (monohydric alcohol, 2-cyanopyridine), it is desirable to set optimum conditions appropriately. Since the preferable reaction temperature is 100 to 150 ° C., it is desirable to preheat the raw material (monohydric alcohol, 2-cyanopyridine) with steam or the like before the first reaction column.
  • the reaction pressure is preferably 0.1 to 5 MPa (absolute pressure).
  • a pressure reducing device is required, and not only the equipment is complicated and expensive, but also the motive energy for reducing the pressure is required, resulting in poor energy efficiency.
  • the reaction pressure exceeds 5 MPa, the hydration reaction with 2-cyanopyridine is difficult to proceed and not only the yield of the carbonate ester is deteriorated, but also the kinetic energy necessary for pressurization is required and the energy efficiency is poor.
  • the reaction pressure is more preferably 0.1 to 4 MPa (absolute pressure), and further preferably 0.2 to 2 MPa (absolute pressure).
  • the 2-cyanopyridine used for the hydration reaction is desirably introduced into the reactor in advance at a rate of 0.1 to 1 times the volume of the starting alcohol prior to the reaction. If it is introduced at less than 0.1 times, the yield of carbonate ester may be deteriorated because of the small amount of 2-cyanopyridine contributing to the hydration reaction. On the other hand, when it is introduced more than 1 time, there is no particular problem because it can be easily separated from the product after the completion of the reaction and reused. Furthermore, the amount of monohydric alcohol and 2-cyanopyridine with respect to the solid catalyst is considered to vary depending on the type and amount of the solid catalyst, the type of monohydric alcohol and the ratio with 2-cyanopyridine. It is desirable.
  • reaction product separation The reaction liquid 15 after the reaction in the first reaction tower 1 is separated into a liquid phase and a solid phase in the first extraction tower 2 (first separation section).
  • the substances contained in the reaction solution 15 are carbonate ester (liquid phase), unreacted 2-cyanopyridine (liquid phase) and 2-picolinamide (solid phase), solid catalyst (solid phase), and organic solvent (liquid phase). Phase).
  • Alkane is suitable for the organic solvent used here, and hexane, octane, nonane, decane, and undecane are preferable from the viewpoint of ease of separation by distillation in the subsequent stage.
  • the extraction process in the first extraction column 2 is preferably performed at room temperature, but the temperature is lower than the boiling point of the organic solvent (for example, in the case of hexane, the boiling point is 69 ° C.). If it is heated to about 50 ° C., the extraction time can be shortened by heating.
  • the temperature is lower than the boiling point of the organic solvent (for example, in the case of hexane, the boiling point is 69 ° C.). If it is heated to about 50 ° C., the extraction time can be shortened by heating.
  • the extract 17 extracted in the first extraction tower 2 contains carbonate ester, unreacted 2-cyanopyridine, and alkane.
  • the boiling point of each substance in the first distillation column 3 (second separation section) is 90 ° C. (for example, dimethyl carbonate), 215 ° C. (2-cyanopyridine), 69 ° C. (for example, hexane).
  • the product is distilled into carbonic acid ester 19, unreacted 2-cyanopyridine 20, and alkane 16 used for extraction.
  • the solid phase 18 separated in the first extraction tower 2 contains 2-picolinamide and a solid catalyst, and is separated in the second extraction tower 4 (third separation section).
  • a hydrophilic solvent liquid phase capable of dissolving 2-picolinamide is suitable, and acetone, ethanol, ether, and water are preferable because they are easily separated by distillation at a later stage.
  • the extraction step in the second extraction tower 4 is also preferably performed at room temperature for extraction in order to suppress energy consumption. However, the temperature is lower than the boiling point of the hydrophilic solvent (for example, in the case of acetone, the boiling point is 56.56). If it is 5 [deg.] C. and heated to about 40 [deg.] C.), the extraction time can be shortened by heating.
  • the extract solution 21 containing 2-picolinamide and a hydrophilic solvent is distilled in the second distillation column 5 so that the boiling points of the substances are 143 ° C. (2-picolinamide) and 57 ° C. (for example, in the case of acetone). To be separated.
  • the solid catalyst 22 (solid phase) separated in the second extraction tower 4 can be regenerated in the catalyst regeneration tower 6 and returned to the first reaction tower 1.
  • the catalyst regeneration is a step of heating to burn off impurities on the solid catalyst, and is fired at 400 to 700 ° C., preferably 500 to 600 ° C. for about 3 hours. In order to prevent structural destruction of the solid catalyst due to rapid temperature rise, it is better to consider the drying step before firing, and it is preferable to dry at 110 ° C. for about 2 hours.
  • the 2-picolinamide 23 (solid phase) purified in the second distillation column 5 is transferred to the second reaction column 7 (second reaction section) for regeneration to 2-cyanopyridine.
  • the solution after the reaction can be recovered as a used catalyst 26 by separating only the solid catalyst by filtering with a filter in the catalyst separation device 8. At this time, it can be easily recovered by a solid-liquid separation method such as normal filtration. Since the boiling point of each substance present in the system is different as described above after the catalyst separation, 2-cyanopyridine, organic solvent, 2-picolinamide, water are distilled by distillation in the third distillation column 9. The organic solvent 27 and 2-picolinamide 28 can be recycled for the dehydration reaction of 2-picolinamide. The purified 2-cyanopyridine 13 can be reused in a reaction for producing a carbonate ester.
  • the production apparatus of the present invention is an apparatus for producing 2-cyanopyridine by dehydrating 2-picolinamide in the presence of a catalyst supporting a basic metal oxide and an organic solvent.
  • the reaction format is not particularly limited, and any of a batch reactor, a semi-batch reactor, a flow reactor such as a continuous tank reactor and a tubular reactor may be used. Moreover, any of a fixed bed, a slurry bed, etc. can be applied to the catalyst.
  • the temperature of the second reaction column 7 can be changed according to the reaction mode, but in the case of reflux using a Soxhlet extraction tube and a cooler, it is preferable to heat the periphery of the reaction tube to 160 to 200 ° C.
  • a dehydrating agent such as reflux, distillation or zeolite is installed in the system to remove the by-product water. It is desirable to carry out the reaction.
  • the organic solvent is preferably a substance having a boiling point of 130 ° C. or higher, and examples thereof include chlorobenzene, (o-, m-, p-) xylene, mesitylene and the like.
  • the periphery of the reaction tube is heated to 160 to 200 ° C.
  • the melting point of each substance is 110 ° C. (2-picolinamide), 24 ° C. (2-cyanopyridine), ⁇ 45 ° C. (organic solvent such as mesitylene), and the boiling point is 143 ° C. (2-picolinamide), Since it is 212 ° C. (2-cyanopyridine), 100 ° C. (water), and 165 ° C. (organic solvent such as mesitylene), the reaction phase is all liquid except for the solid catalyst, and is partially vaporized.
  • the 2-picolinamide, by-product water, and the organic solvent are cooled by the cooler, and the by-product water is adsorbed by the dehydrating agent, and the 2-picolinamide and the organic solvent return to the reaction tube and contribute to the reaction again.
  • the solution after the reaction is recovered as a used catalyst 26 by separating only the catalyst in the catalyst separation column 8 (fourth separation section) while being heated to 103 ° C. or higher, which is the melting point of 2-picolinamide, with low-pressure steam or the like. To do. At this time, it can be easily recovered by a solid-liquid separation method such as normal filtration. After the catalyst separation, the boiling points of the substances present in the system are different from each other as described above. Therefore, by distilling in the third distillation column 9 (fifth separation part), 2-cyanopyridine 13, The organic solvent 27, 2-picolinamide 28 and water 29 can be easily separated, and the organic solvent 27 and 2-picolinamide 28 can be returned to the previous stage of the third reaction column 7 and recycled. . The purified 2-cyanopyridine 13 is transported to the first reaction column 1 where the carbonate ester is produced by the transport unit, and is reused in the first reaction column 1.
  • FIG. 3 shows another example of the preferred equipment of the present invention
  • FIG. 4 shows the state of each substance in each process in the equipment of FIG.
  • This equipment can also be used in the case of reaction conditions where unreacted monohydric alcohol remains and byproducts of methyl picolinate and methyl carbamate are generated.
  • the basic configuration is the same as in the case of FIG. 1 described above, but the extract 17 extracted in the first extraction tower 2 includes carbonate ester, unreacted 2-cyanopyridine, alkane, and monohydric alcohol. Contains methyl carbamate and methyl picolinate.
  • the boiling point of each substance in the first distillation column 3 is 90 ° C. (for example, dimethyl carbonate), 215 ° C.
  • the first reaction step in the method for producing a carbonate ester of the present invention involves directly reacting a monohydric alcohol and carbon dioxide in the presence of one or both of a solid catalyst of CeO 2 and ZrO 2 and benzonitrile to produce carbonic acid. An ester is produced.
  • any alcohol selected from one or more of primary alcohol, secondary alcohol, and tertiary alcohol can be used, and methanol, ethanol, 1-propanol can be used.
  • methanol, ethanol, 1-propanol can be used.
  • Isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, allyl alcohol, 2-methyl-1-propanol, cyclohexane methanol, benzyl alcohol This is preferable because the yield of the product is high and the reaction rate is fast.
  • the produced carbonates are dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dipentyl carbonate, dihexyl carbonate, diheptyl carbonate, dioctyl carbonate, dinonane carbonate, diallyl carbonate, di-2-methyl-propyl carbonate, respectively.
  • dicyclohexane methyl carbonate and dibenzyl carbonate dibenzyl carbonate.
  • the solid catalyst of CeO 2 and ZrO 2, only CeO 2, only ZrO 2, a CeO 2 and mixtures of ZrO 2, or CeO 2 solid solution or a composite oxide of ZrO 2, in particular Only CeO 2 is preferred.
  • the CeO 2 and ZrO 2 solid solution or a composite oxide the mixing ratio of CeO 2 and ZrO 2 (molar ratio) is not particularly limited, for example, 1:99 to 99: it can be a 1, For example, the molar ratio may be 50:50.
  • the catalyst used for the direct synthesis of carbonic acid ester is required to have an acid-base complex function, and in particular, has a property of relatively low acidity and relatively high basicity. Is preferred. If the acidity is too high, it is not preferable because a large amount of ether is synthesized rather than carbonate.
  • alcohol is adsorbed in the form of HO—R... M, and RO—C ( ⁇ O) —OR is generated between both adsorbed species.
  • This solid catalyst also exhibits catalytic activity for the hydration reaction of water and benzonitrile by-produced during the synthesis of the carbonate ester. Therefore, although both carbonate synthesis reaction and hydration reaction proceed on the surface of this catalyst, the hydration reaction of benzonitrile does not occur even under low pressure conditions, which is unfavorably balanced for the synthesis reaction of carbonate ester.
  • the reaction proceeds under catalysis, and water generated as a by-product in the synthesis reaction of the carbonate ester is quickly eliminated from the catalyst surface, so that the equilibrium of the synthesis reaction of the carbonate ester shifts to the production system, and the mild reaction pressure is low.
  • benzonitrile is catalyzed by the solid catalyst in the present invention in the liquid phase, and the hydration reaction is promoted on the surface thereof. Therefore, when the pressure is increased, the surface of the solid catalyst is covered with CO 2 , and the hydration reaction rate is reduced because it becomes difficult to be catalyzed by the hydration reaction with water molecules generated in the main reaction. Inferred.
  • acetal and 2,2-dimethoxypropane described in Non-Patent Document 4 and Non-Patent Document 5 do not undergo any catalytic action in the liquid phase and cause a hydration reaction with water molecules generated in the main reaction. Therefore, since the main reaction proceeds predominantly at high pressure, it is presumed that the hydration reaction begins to occur under high pressure.
  • cerium oxide CeO 2
  • cerium acetylacetonate hydrate cerium hydroxide
  • cerium sulfate cerium acetate
  • cerium nitrate It can be prepared by firing various cerium compounds such as ammonium cerium nitrate, cerium carbonate, cerium oxalate, cerium perchlorate, cerium phosphate and cerium stearate in an air atmosphere.
  • cerium oxide as a reagent it can be used as it is or by drying or baking in an air atmosphere.
  • zirconium oxide ZrO 2
  • various zirconium compounds such as zirconium ethoxide, zirconium butoxide, zirconium carbonate, zirconium hydroxide, zirconium phosphate, zirconium acetate, zirconium chloride oxide, zirconium oxide nitrate, zirconium sulfate, etc. It can be prepared by firing in an atmosphere.
  • zirconium oxide as a reagent it can be used as it is or by drying or baking in an air atmosphere.
  • it can be used by precipitating from a solution in which zirconium is dissolved, filtering, drying and baking.
  • a base is added to a solution containing cerium and zirconium to form a hydroxide by coprecipitation, followed by filtration and washing with water. It can be prepared by drying and firing in an air atmosphere. Although the powder particles of CeO 2 and ZrO 2 can also be prepared by firing the physical mixture, the specific surface area of the final preparation is not high, preferably easily coprecipitation reaction proceeds more.
  • a solid catalyst made of a compound of cerium oxide and zirconium oxide such as CeO 2 —ZrO 2 can be obtained by these methods.
  • the solid catalyst according to the present invention may contain inevitable impurities mixed in the catalyst production process in addition to the above elements, but it is desirable that impurities are not mixed as much as possible.
  • the impurities are preferably less than 1% by mass with respect to the catalyst.
  • the catalyst of the present invention may be in any form of powder or molded body, and in the case of a molded body, it may be any of spherical, pellet, cylinder, ring, wheel, granule, etc. .
  • carbon dioxide used in the present invention is not limited to those prepared as industrial gases, but can also be used that separated and recovered from exhaust gases from factories, steel mills, power plants, etc. that manufacture each product.
  • Solid-liquid separation Under the conditions where the conversion rate of monohydric alcohol is 100% and no by-products such as methyl benzoate and methyl carbamate are produced, the main product carbonate ester, by-product benzamide, unreacted It becomes a solid catalyst such as benzonitrile and CeO 2 .
  • a liquid component carbonate ester, benzonitrile
  • the organic solvent used here is preferably an alkane that can dissolve the carbonate, and more preferably hexane, octane, nonane, decane, and undecane.
  • the separated liquid component contains carbonate ester, benzonitrile, and organic solvent.
  • the melting point and boiling point of each substance are 4 ° C and 90 ° C (dimethyl carbonate), -43 °C and 128 °C (diethyl carbonate), -41 °C and 167 °C (dipropyl carbonate), 25 °C or less and 207 °C (dibutyl carbonate), -13 °C and 188 °C (benzonitrile), -95 °C And 69 ° C. (for example, hexane), the carbonate ester can be separated by distillation, and the product carbonate ester can be recovered with high purity. In addition to distillation, it is also possible to filter and recover what is solidified by cooling stepwise to below the melting point.
  • the benzamide and the solid catalyst separated as solid components can be separated from the solid catalyst and the filter by extracting only benzamide with a hydrophilic solvent.
  • the hydrophilic solvent used here is preferably acetone, ethanol, ether, or water in view of ease of handling and separation at a later stage.
  • the benzamide dissolved in the hydrophilic solvent can be separated by distillation, and the by-product benzamide can be purified with high purity.
  • the separated solid catalyst is regenerated in the step of regenerating the catalyst and can be reused in the first reaction step.
  • the catalyst regeneration step is a step of heating to burn off impurities etc. on the solid catalyst, and is preferably calcined at 400 to 700 ° C., more preferably at 500 to 600 ° C. for about 3 hours. In order to prevent structural destruction of the solid catalyst due to rapid temperature rise, it is better to consider the drying step before firing, and it is preferable to dry at 110 ° C. for about 2 hours.
  • the benzamide produced as a by-product in the first reaction step is separated from the system after the carbonic acid ester formation reaction, and then benzonitrile is produced by a dehydration reaction.
  • the second reaction step corresponds to the above-described method for producing benzonitrile.
  • benzamide is produced by dehydrating benzamide in the presence of a catalyst supporting a basic metal oxide and an organic solvent.
  • the catalyst used in the present invention is generally an oxide (metal oxide) of a metal species (molybdenum, tungsten, rhenium, titanium, niobium) having a double bond between the metal and oxygen as a catalyst carrier.
  • a catalyst supported on a substance can be used, as a result of examining various supports, a catalyst composed of one or more of SiO 2 , TiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 , and C is used. It has been found that high performance is exhibited when a catalyst supported on a carrier is used.
  • any one or two or more catalyst carriers of SiO 2 , TiO 2 , CeO 2 , and ZrO 2 because higher performance is exhibited. This is because, in the reaction with benzamide, it is considered that the double bond portion between the metal and oxygen may be active, and thus a metal element having a double bond is preferable among the metal oxides.
  • Examples of the carrier production method used here are roughly divided into a dry method and a wet method as general production methods in the case of SiO 2 .
  • the dry method includes a combustion method, an arc method, etc.
  • the wet method includes a sedimentation method, a gel method, etc., and it is possible to manufacture a catalyst carrier by any of the manufacturing methods. Since it is technically and economically difficult to form, a gel method is preferred in which silica sol can be easily formed into a spherical shape by spraying in a gas medium or a liquid medium.
  • cerium acetylacetonate hydrate and cerium hydroxide cerium sulfate, cerium acetate, cerium nitrate, cerium ammonium nitrate, cerium carbonate, cerium oxalate, perchlorate cerium, cerium phosphate, cerium stearate
  • cerium oxide as a reagent it can be used as it is or by drying or baking in an air atmosphere. Furthermore, it can be used by precipitating from a solution in which cerium is dissolved, filtering, drying, and baking.
  • zirconium compounds such as zirconium ethoxide, zirconium butoxide, zirconium carbonate, zirconium hydroxide, zirconium phosphate, zirconium acetate, zirconium chloride oxide, zirconium dinitrate, zirconium sulfate and the like are calcined in an air atmosphere.
  • zirconium oxide as a reagent it can be used as it is or by drying or baking in an air atmosphere. Furthermore, it can be used by precipitating from a solution in which zirconium is dissolved, filtering, drying and baking.
  • C is mainly composed of carbon and may be in any form as long as it does not change during the reaction period.
  • activated carbon is preferable, but it is not limited thereto.
  • a base is added to a solution containing two or more metal salts to form a hydroxide by coprecipitation, followed by filtration and washing in an air atmosphere.
  • it can prepare also by physically mixing and baking the powder of 2 or more types of oxides, since the homogeneity of the component of a final preparation does not become high, the coprecipitation method with which reaction progresses more is preferable.
  • a base is added to a solution containing cerium and zirconium to form a hydroxide by coprecipitation, followed by filtration and washing, followed by drying and firing in an air atmosphere.
  • a base is added to a solution containing cerium and zirconium to form a hydroxide by coprecipitation, followed by filtration and washing, followed by drying and firing in an air atmosphere.
  • a solid catalyst carrier comprising a compound of cerium oxide and zirconium oxide such as CeO 2 —ZrO 2
  • the firing temperature at the time of preparation of each of these catalyst carriers may be selected at a temperature at which the specific surface area of the final preparation is increased. Although it depends on the starting material, for example, 300 ° C. to 1100 ° C. is preferable.
  • the solid catalyst carrier according to the present invention may contain inevitable impurities that are mixed in the catalyst manufacturing process in addition to the above elements, but it is desirable that impurities are not mixed as much as possible.
  • the carrier selected from one or more of SiO 2 , TiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 , and C can support active metal species in a highly dispersed manner as the surface area increases. This is preferable because the amount of nitrile produced is improved.
  • the surface area depends on the type of the carrier, but the surface area is preferably 10 m 2 / g or more as measured by the BET method.
  • a metal oxide that becomes an active species may be supported on a support by a known method.
  • a precipitation loading method using a general solution, for example, it can be loaded by an impregnation method such as an incipient wetness method or an evaporation to dryness method.
  • the carrier is SiO 2
  • a commercially available powder or spherical SiO 2 can be used, and pre-baking is performed to adjust the particle size to 100 mesh (0.15 mm) or less and to remove moisture so that the active metal can be uniformly supported. It is preferable to carry out at 700 degreeC in air for 1 hour.
  • SiO 2 has various properties, it is preferable that the surface area is large because the active metal can be highly dispersed and the amount of benzonitrile produced is improved. Specifically, a surface area of 300 m 2 / g or more is more preferable.
  • the surface area of the catalyst after preparation may be lower than the surface area of only SiO 2 due to the interaction between SiO 2 and the active metal. In that case, it is more preferable that the surface area of the catalyst after manufacture is 150 m 2 / g or more.
  • the metal salt that is the precursor of the metal oxide that becomes the active species only needs to have high solubility in various solvents.
  • Various compounds such as can be used.
  • the precursor solution of the metal compound After impregnating the precursor solution of the metal compound into the support, it can be used as a catalyst by drying and firing, and the firing temperature is preferably 400 to 600 ° C., although it depends on the precursor used.
  • the amount of metal oxide supported may be set as appropriate.
  • the amount of metal oxide supported in terms of metal based on the total catalyst weight is about 0.1 to 1.5 mmol / g, particularly 0.1 to 1 mmol. / G, preferably about 0.2 to 0.8 mmol / g.
  • the activity may be reduced due to the coarsening of the metal oxide.
  • what is necessary is just to set suitably about the usage-amount of the catalyst at the time of reaction.
  • the catalyst according to the present invention may contain inevitable impurities that are mixed in the catalyst manufacturing process in addition to the above-mentioned elements, but it is desirable that impurities are not mixed as much as possible.
  • the catalyst supported on the carrier of the present invention may be in the form of a powder or a molded body.
  • a spherical shape, a pellet shape, a cylinder shape, a ring shape, a wheel shape, a granule Any shape may be used.
  • Organic solvent As the organic solvent used in the dehydration reaction, various substances having a boiling point of 130 ° C. or higher are preferably used. Among them, chlorobenzene, (o-, m-, p-) xylene, mesitylene, and the like are more preferably used, and in particular, mesitylene. Is preferred.
  • reaction conditions are preferably selected from the viewpoints of the dehydration reaction rate, the boiling point of the solvent, the amount of CO 2 emitted during the reaction, and the economy.
  • the reaction temperature may be 160 to 200 ° C.
  • the reaction pressure may be normal pressure
  • the reaction time may be several hours to 24 hours, but is not particularly limited thereto.
  • reaction format the method for producing benzonitrile using the catalyst of the present invention is not particularly limited as a reaction format, and is distributed as a batch reactor, a semi-batch reactor, a continuous tank reactor or a tubular reactor. Any of the type reactors may be used. Moreover, any of a fixed bed, a slurry bed, etc. can be applied to the catalyst.
  • the second reaction step of producing (regenerating) benzonitrile from the by-produced benzamide in the production method of the present invention it is carried out while removing the by-product water produced by the dehydration reaction, as in the step of producing carbonate ester.
  • a dehydrating agent such as zeolite
  • zeolite molecular sieve
  • calcium hydride was installed in the extraction tube as a dehydrating agent, and a catalyst, benzamide, and an organic solvent were placed in the reaction tube.
  • the amount of benzonitrile produced can be improved by reacting at normal pressure with reflux.
  • the type and shape of the molecular sieve used as the dehydrating agent are not particularly limited.
  • 3A, 4A, 5A, etc. which are generally highly water-absorbing, such as spherical or pellets are used. it can. Further, it is preferably dried in advance, and is preferably dried at 300 to 500 ° C. for about 1 hour.
  • reaction product In the dehydration reaction of benzamide, benzoic acid may be produced as a by-product due to the decomposition of benzamide as described above. However, after the dehydration reaction using the catalyst of the present invention, a small amount of benzamide and product remained in the reaction product. There are only some benzonitriles, by-product water, and organic solvents, and these by-products are hardly produced.
  • the reaction temperature is preferably a condition under which the benzamide dehydration reaction is performed in a liquid phase. Considering the reaction efficiency, it is preferable that the temperature is higher under liquid phase conditions.
  • the reaction is performed under normal pressure, it is preferable to heat the periphery of the reaction tube to 160 to 200 ° C.
  • the melting point of each substance in a typical reaction system is 127 ° C. (benzamide), ⁇ 13 ° C. (benzonitrile), ⁇ 45 ° C. (organic solvent such as mesitylene), and the boiling point is 288 ° C.
  • the benzonitrile regenerated in the second reaction step can be reused in the first reaction step.
  • the apparatus for producing carbonate ester using benzonitrile has substantially the same configuration as the apparatus for producing 2-cyanopyridine.
  • an apparatus for producing a carbonate ester using benzonitrile is such that 2-cyanopyridine and 2-picolinamide in FIG. 1 and the like are replaced with benzonitrile and benzamide. Therefore, in the following, an apparatus for producing a carbonate using benzonitrile will be described with reference to FIGS.
  • FIG. 1 is an example of a suitable facility of the present invention. Moreover, the state of each substance in each process in this equipment in FIG. 1 is shown in FIG. This equipment can be used in the case of reaction conditions in which the conversion rate of monohydric alcohol is 100% and byproducts of methyl benzoate and methyl carbamate are not generated.
  • first reaction step In the first reaction step, in the first reaction column 1 (first reaction section), one or both of the solid catalyst (solid phase) of CeO 2 and ZrO 2 , the monohydric alcohol 12 (liquid phase), Carbon dioxide (gas phase) is filled through the benzonitrile 13 (liquid phase) and the pressure booster 10 (pressure part).
  • a solid catalyst 14 solid phase newly charged before the reaction or regenerated in the regeneration tower 6 can be used.
  • a new benzonitrile is used at the start of the reaction, but the unreacted benzonitrile 20 (liquid phase) purified in the first distillation column 3 and the benzamide regenerated from the benzamide purified in the third distillation column 9 are used. Nitriles can be reused.
  • the carbon dioxide ester direct synthesis apparatus using the solid catalyst of either or both of CeO 2 and ZrO 2 of the present invention is a batch reactor, a semi-batch reactor, a continuous tank reactor, a tube type, or the like. Any flow reactor such as a reactor may be used.
  • the reaction temperature in the first reaction column 1 is preferably 50 to 300 ° C.
  • the reaction temperature is less than 50 ° C., the reaction rate is low, the carbonate ester synthesis reaction and the hydration reaction with benzonitrile hardly proceed, and the carbonate ester productivity tends to be low.
  • the reaction temperature exceeds 150 ° C., the reaction rate of each reaction increases, but decomposition and modification of the carbonate ester, and benzamide easily react with the monohydric alcohol, so that the yield of the carbonate ester tends to decrease. is there. More preferably, it is 100 to 150 ° C.
  • this temperature is considered to vary depending on the type and amount of the solid catalyst and the amount and ratio of the raw materials (monohydric alcohol and benzonitrile), it is desirable to appropriately set the optimum conditions. Since the preferred reaction temperature is 100 to 150 ° C., it is desirable to preheat the raw material (monohydric alcohol, benzonitrile) with steam or the like before the first reaction column.
  • the reaction pressure is preferably 0.1 to 5 MPa (absolute pressure).
  • a pressure reducing device is required, and not only the equipment is complicated and expensive, but also the motive energy for reducing the pressure is required, resulting in poor energy efficiency.
  • the reaction pressure exceeds 5 MPa, the hydration reaction by benzonitrile is difficult to proceed and not only the yield of the carbonate ester is deteriorated, but also the kinetic energy necessary for pressurization is required and the energy efficiency is deteriorated.
  • the reaction pressure is more preferably 0.1 to 4 MPa (absolute pressure), and further preferably 0.2 to 2 MPa (absolute pressure).
  • the benzonitrile used for the hydration reaction is preferably introduced into the reactor in advance at a rate of 0.1 to 1 times the volume of the starting alcohol prior to the reaction. If it is introduced at less than 0.1 times, the yield of the carbonate ester may be deteriorated because there is little benzonitrile contributing to the hydration reaction. On the other hand, when it is introduced more than 1 time, there is no particular problem because it can be easily separated from the product after the completion of the reaction and reused.
  • the amount of monohydric alcohol and benzonitrile with respect to the solid catalyst is considered to vary depending on the type and amount of the solid catalyst, the type of monohydric alcohol and the ratio with benzonitrile, and therefore it is desirable to appropriately set optimum conditions.
  • reaction product separation The reaction liquid 15 after the reaction in the first reaction tower 1 is separated into a liquid phase and a solid phase in the first extraction tower 2 (first separation section).
  • the substances contained in the reaction solution 15 are carbonate ester (liquid phase), unreacted benzonitrile (liquid phase), benzamide (solid phase), and solid catalyst (solid phase), and are extracted with an organic solvent (liquid phase).
  • Alkane is suitable for the organic solvent used here, and hexane, octane, nonane, decane, and undecane are preferable from the viewpoint of ease of separation by distillation in the subsequent stage.
  • the extraction process in the first extraction column 2 is preferably performed at room temperature, but the temperature is lower than the boiling point of the organic solvent (for example, in the case of hexane, the boiling point is 69 ° C.). If it is heated to about 50 ° C., the extraction time can be shortened by heating.
  • the temperature is lower than the boiling point of the organic solvent (for example, in the case of hexane, the boiling point is 69 ° C.). If it is heated to about 50 ° C., the extraction time can be shortened by heating.
  • the extract 17 extracted in the first extraction tower 2 contains carbonate ester, unreacted benzonitrile, and alkane. Utilizing that the boiling point of each substance is 90 ° C. (for example, dimethyl carbonate), 188 ° C. (benzonitrile), 69 ° C. (for example, hexane) in the first distillation column 3 (second separation section). The product is then distilled and separated into the product carbonate 19, unreacted benzonitrile 20, and alkane 16 used for extraction.
  • the boiling point of each substance is 90 ° C. (for example, dimethyl carbonate), 188 ° C. (benzonitrile), 69 ° C. (for example, hexane) in the first distillation column 3 (second separation section).
  • the product is then distilled and separated into the product carbonate 19, unreacted benzonitrile 20, and alkane 16 used for extraction.
  • the solid phase 18 separated in the first extraction tower 2 contains benzamide and a solid catalyst, and is separated in the second extraction tower 4 (third separation section).
  • a hydrophilic solvent liquid phase capable of dissolving benzamide is suitable, and acetone, ethanol, ether, and water are preferable because they are easily separated by distillation at a later stage.
  • the extraction step in the second extraction tower 4 is also preferably performed at room temperature for extraction in order to suppress energy consumption. However, the temperature is lower than the boiling point of the hydrophilic solvent (for example, in the case of acetone, the boiling point is 56.56). If it is 5 [deg.] C. and heated to about 40 [deg.] C.), the extraction time can be shortened by heating.
  • the extract 21 containing benzamide and a hydrophilic solvent is distilled in the second distillation column 5, and the boiling point of each substance is separated into 127 ° C. (benzamide) and 57 ° C. (for example, in the case of acetone).
  • the solid catalyst 22 (solid phase) separated by the second extraction tower 4 can be regenerated by the catalyst regeneration tower 6 and returned to the first reaction tower 1.
  • the catalyst regeneration is a step of heating to burn off impurities on the solid catalyst, and is fired at 400 to 700 ° C., preferably 500 to 600 ° C. for about 3 hours. In order to prevent structural destruction of the solid catalyst due to rapid temperature rise, it is better to consider the drying step before firing, and it is preferable to dry at 110 ° C. for about 2 hours.
  • the benzamide 23 (solid phase) purified in the second distillation column 5 is transferred to the second reaction column 7 (second reaction part) for regeneration to benzonitrile, but in order to avoid blockage in the piping.
  • the piping is preferably heated to 127 ° C. or higher, which is the melting point, with low pressure steam or the like.
  • the solution after the reaction can be recovered as a used catalyst 26 by separating only the solid catalyst by filtering with a filter in the catalyst separation device 8. At this time, it can be easily recovered by a solid-liquid separation method such as normal filtration. Since the boiling point of each substance present in the system is different as described above after the catalyst separation, it can be easily separated into benzonitrile, organic solvent, benzamide, and water by distillation. The organic solvent 27 and the benzamide 28 can be recycled for the dehydration reaction of benzamide. The purified benzonitrile 13 can be reused in a reaction for producing a carbonate ester.
  • the production apparatus of the present invention is an apparatus for producing benzonitrile by dehydrating benzamide in the presence of a catalyst supporting a metal oxide having a double bond and an organic solvent.
  • the reaction format is not particularly limited, and any of a batch reactor, a semi-batch reactor, a flow reactor such as a continuous tank reactor and a tubular reactor may be used. Moreover, any of a fixed bed, a slurry bed, etc. can be applied to the catalyst.
  • the temperature of the second reaction column can be changed according to the reaction mode, but in the case of reflux using a Soxhlet extraction tube and a cooler, the periphery of the reaction tube is preferably heated to 160 to 200 ° C.
  • a dehydrating agent such as reflux, distillation or zeolite is installed in the system to remove the by-product water. It is desirable to carry out the reaction.
  • zeolite molecular sieve
  • calcium hydride a catalyst, benzamide, and an organic solvent were placed in the reaction tube.
  • the amount of benzonitrile produced can be improved by reacting at normal pressure with reflux.
  • the organic solvent is preferably a substance having a boiling point of 130 ° C. or higher, and examples thereof include chlorobenzene, (o-, m-, p-) xylene, mesitylene and the like.
  • the periphery of the reaction tube is heated to 160 to 200 ° C.
  • the melting point of each substance is 127 ° C. (benzamide), ⁇ 13 ° C. (benzonitrile), ⁇ 45 ° C. (organic solvent such as mesitylene), and the boiling point is 288 ° C. (benzamide), 188 ° C. (benzonitrile), Since the reaction phase is 100 ° C. (water) and 165 ° C.
  • the reaction phase is all liquid except for the solid catalyst, and partially evaporated benzamide, by-product water, Cooled by a cooler, by-product water is adsorbed by a dehydrating agent, and benzamide and the organic solvent return to the reaction tube and contribute to the reaction again.
  • organic solvent such as mesitylene
  • the solution after the reaction is recovered as a used catalyst 26 by separating only the catalyst in the catalyst separation tower 8 (fourth separation section) while being heated to 288 ° C. or higher, which is the melting point of benzamide, with low-pressure steam or the like. At this time, it can be easily recovered by a solid-liquid separation method such as normal filtration. After the catalyst separation, the boiling point of each substance present in the system is different as described above. Therefore, by distilling in the third distillation column 9 (fifth separation section), the benzonitrile 13 and the organic solvent are separated. 27, benzamide 28, and water 29 can be easily separated, and the organic solvent 27 and benzamide 28 can be returned to the previous stage of the third reaction column 7 and recycled. Further, the purified benzonitrile 13 is transported to the first reaction column 1 where the carbonate is produced by the transport unit, and is reused in the first reaction column 1.
  • FIG. 3 shows another example of the preferred equipment of the present invention
  • FIG. 4 shows the state of each substance in each process in the equipment of FIG.
  • This equipment can also be used in the case of reaction conditions in which unreacted monohydric alcohol remains and by-products of methyl benzoate and methyl carbamate are generated.
  • the basic configuration is the same as in the case of FIG. 1 described above, but the extract 17 extracted in the first extraction tower 2 includes carbonate, unreacted benzonitrile, alkane, methyl carbamate and benzoic acid. Contains methyl acid.
  • the boiling point of each substance in the first distillation column 3 is 90 ° C. (for example, dimethyl carbonate), 215 ° C.
  • methyl benzoate having a melting point of 103 ° C., so that it can be separated into solid and liquid with the filter 30 or the like, and unreacted benzonitrile 20, It can be separated into methyl benzoate 31.
  • the mixture 33 of alkane and monohydric alcohol is mostly alkane, it can be reused as a solvent for extraction.
  • Example and comparative example of the manufacturing method of cyanopyridine are demonstrated.
  • Example 1 SiO 2 as a carrier (manufactured by Fuji Silysia, CARiACT, G-6, surface area: 535 m 2 / g) was sized to 100 mesh or less and pre-baked at 700 ° C. for about 1 hour. Thereafter, in order to carry the Na as the alkali metal, finally Na 2 CO 3 as Na amount of metal supported is 0.5 mmol / g (manufactured by Kanto Kagaku, special grade) was used to adjust the aqueous solution, SiO 2 Impregnated. Thereafter, about 6 hours drying at 110 ° C., and calcined at 500 ° C. for about 3 hours to obtain a Na 2 O / SiO 2 catalyst.
  • a magnetic stir bar, the above catalyst (0.1 g), 2-picolinamide (2-PA, 1 mmol), and mesitylene (20 ml) were introduced into a test tube, and molecular sieve 4A (preliminarily dried at 300 ° C. for 1 hour).
  • a filled Soxhlet extractor and Liebig condenser were connected, the temperature of the condenser was set to 10 ° C., and the magnetic stirrer was set to about 200 ° C. and 600 rpm.
  • the reaction start time was defined as the time when the solution started to evaporate, and the reaction was performed for 24 hours.
  • test tube solution
  • 20 ml of ethanol and anthracene 0.1 g as an internal standard substance are added to the reaction solution, a sample is taken, and GC-MS (gas chromatograph-mass spectrometer) And quantitative analysis by FID-GC.
  • GC-MS gas chromatograph-mass spectrometer
  • Example 2 Is similar to Example 1, the catalyst preparation, eventually Li metal support amount 0.5 mmol / g and composed as Li 2 CO 3 (manufactured by Kanto Kagaku, special grade) to adjust the aqueous solution with, SiO 2 was impregnated. Thereafter, about 6 hours drying at 110 ° C., and calcined at 500 ° C. for about 3 hours to obtain a Li 2 O / SiO 2 catalyst.
  • 2-CP was produced from 2-PA in the same manner as in Example 1 except that a Li 2 O / SiO 2 catalyst was used. As a result, as shown in Table 1, 0.43 mmol of 2-CP was produced. By-product was only water, yield was 43%, and selectivity was 100%.
  • Example 3 As in Example 1, but in the catalyst preparation, an aqueous solution was prepared using K 2 CO 3 (manufactured by Kanto Chemical Co., Ltd., special grade) so that the amount of supported K metal was 0.5 mmol / g, and SiO 2 It was impregnated to 2. Thereafter, about 6 hours drying at 110 ° C., and calcined at 500 ° C. for about 3 hours to obtain K 2 O / SiO 2 catalyst. 2-CP was produced from 2-PA in the same manner as in Example 1 except that a K 2 O / SiO 2 catalyst was used. As a result, as shown in Table 1, 0.42 mmol of 2-CP was produced. The byproduct was only water, yield was 42%, and selectivity was 100%.
  • K 2 CO 3 manufactured by Kanto Chemical Co., Ltd., special grade
  • Example 4 Is similar to Example 1, the catalyst preparation, finally Rb amount of metal supported is adjusted aqueous solution using a Rb 2 CO 3 (manufactured by Kanto Chemical) as a 0.5 mmol / g, the SiO 2 Impregnated. Thereafter, about 6 hours drying at 110 ° C., and calcined at 500 ° C. for about 3 hours to obtain Rb 2 O / SiO 2 catalyst.
  • 2-CP was produced from 2-PA in the same manner as in Example 1 except that the Rb 2 O / SiO 2 catalyst was used. As a result, as shown in Table 1, 0.43 mmol of 2-CP was produced. By-product was only water, yield was 43%, and selectivity was 100%.
  • Example 5 Although it is the same as that of Example 1, in the catalyst preparation, the aqueous solution was adjusted using Cs 2 CO 3 (manufactured by Kanto Chemical Co., 4N) so that the Cs metal loading was finally 0.5 mmol / g, and SiO 2 2 was impregnated. Thereafter, about 6 hours drying at 110 ° C., and calcined at 500 ° C. for about 3 hours to obtain Cs 2 O / SiO 2 catalyst. Cs but using 2 O / SiO 2 catalyst was prepared 2-CP from 2-PA as in Example 1. As a result, as shown in Table 1, 0.45 mmol of 2-CP was produced. The byproduct was only water, yield was 45%, and selectivity was 100%.
  • Cs 2 CO 3 manufactured by Kanto Chemical Co., 4N
  • Example 6 As in Example 1, but in the catalyst preparation, Na 2 CO 3 (manufactured by Kanto Chemical Co., Ltd., special grade) and K are used so that the total amount of Na metal loading and K metal loading is finally 0.5 mmol / g.
  • 2 CO 3 manufactured by Kanto Chemical Co., Ltd., special grade
  • the molar ratio was changed to prepare an aqueous solution, and SiO 2 was impregnated. Thereafter, it was dried at 110 ° C. for about 6 hours and calcined at 500 ° C. for about 3 hours to obtain a Na 2 O—K 2 O / SiO 2 catalyst.
  • 2-CP was produced from 2-PA in the same manner as in Example 1 except that a Na 2 O—K 2 O / SiO 2 catalyst was used.
  • 2-CP was produced at any molar ratio, the byproduct was only water, the yield was 41 to 43%, and the selectivity was 100%. From the above results, it was found that the amount of alkali metal used can be changed according to the market price.
  • Example 1 (Comparative Example 1) Example 1 except that only SiO 2 (Fuji Silysia, CARiACT, G-6, surface area: 535 m 2 / g) preliminarily calcined at 700 ° C. for about 1 hour was used as the catalyst. And so on. As a result, as shown in Table 3, 2-CP produced only 0.03 mmol and was very low in activity.
  • Example 2 The same procedure as in Example 1 was performed except that 1 mmol of Na 2 CO 3 (manufactured by Kanto Chemical Co., Ltd., special grade) was used as the catalyst. As a result, as shown in Table 3, 2-CP was not generated at all.
  • Example 3 The same procedure as in Example 1 was performed except that 1 mmol of Li 2 CO 3 (manufactured by Kanto Chemical Co., Ltd., special grade) was used as the catalyst. As a result, as shown in Table 3, 2-0.01 produced 2-CP only.
  • Example 4 The same procedure as in Example 1 was conducted except that 1 mmol of K 2 CO 3 (manufactured by Kanto Chemical Co., Ltd., special grade) was used as the catalyst. As a result, as shown in Table 3, 2-CP was not generated at all.
  • Example 5 The same procedure as in Example 1 was carried out except that 1 mmol of Rb 2 CO 3 (manufactured by Kanto Chemical) was used as the catalyst. As a result, as shown in Table 3, 2-CP was hardly generated.
  • Example 6 The same procedure as in Example 1 was performed except that 1 mmol of Cs 2 CO 3 (manufactured by Kanto Chemical Co., 4N) alone was used as the catalyst. As a result, as shown in Table 3, 2-CP produced only 0.01 mmol, and its activity was very low. From the above results, it was found that a catalyst having an alkali metal oxide supported on a SiO 2 carrier is effective.
  • Example 7 In the catalyst preparation, the final amount of Na metal supported was as shown in Table 4, and 5 mmol of 2-picolinamide (PA) was introduced, and the reaction time was 4 hours. The results are shown in Table 4.
  • the amount of Na supported was high at 0.1 to 1 mmol / g, and about 0.5 mmol / g was particularly suitable.
  • Example 8 In the catalyst preparation, Examples were used except that CeO 2 (manufactured by 1st rare element, HS, surface area: 74 m 2 / g) was sized to 100 mesh or less and pre-fired at 500 ° C. for about 3 hours. Same as 5. As a result, as shown in Table 5, 0.11 mmol of 2-CP was produced. The byproduct was only water, yield was 11%, and selectivity was 100%.
  • Example 9 In the preparation of the catalyst, the same procedure as in Example 5 was performed except that ZrO 2 (manufactured by the first rare element, surface area: 88 m 2 / g) was sized to 100 mesh or less and used without preliminary firing. As a result, as shown in Table 5, 0.10 mmol of 2-CP was produced. The byproduct was only water, yield was 10%, and selectivity was 100%.
  • Example 10 In the catalyst preparation, for using the CeO 2 -ZrO 2 solid solution as a carrier, Ce (NO 3) 3 (manufactured by Kanto Chemical Co., Inc.) and Zr (NO 3) 4 dissolved (manufactured by Kanto Chemical) and so Ce is 20 atomic weight% An aqueous NaOH solution was introduced into the resulting solution to form a precipitate, which was filtered, washed with water, fired at 1000 ° C. in an air atmosphere for 3 hours, and then powdered solid solution (surface area: 65 m 2 / g ) This solid solution was sized to 100 mesh or less, and the same procedure as in Example 5 was used except that a pre-baked product was used at 500 ° C. for about 3 hours. As a result, as shown in Table 5, 0.11 mmol of 2-CP was produced. The byproduct was only water, yield was 11%, and selectivity was 100%.
  • Example 11 Example 1 was repeated except that 5 mmol of 2-picolinamide (2-PA) as a reaction product was introduced and the reaction time was as shown in Table 6. The results are shown in Table 6.
  • Example 12 Except for using o-xylene, m-xylene and p-xylene as solvents, the reaction was carried out under the same conditions as in Example 1 to produce 2-CP from 2-PA. As a result, as shown in Table 4, a certain amount of 2-CP was produced with any carrier.
  • Example 13 The reaction was carried out under the same conditions as in Example 1 except that nicotinamide and isonicotinamide were used as reactants instead of 2-PA, and 3-cyanopyridine (3-CP), 4-cyanopyridine (4-CP) ) was manufactured.
  • nicotinamide and isonicotinamide were used as reactants instead of 2-PA
  • 3-cyanopyridine 3-cyanopyridine
  • 4-cyanopyridine 4-cyanopyridine
  • Example 14 examples and comparative examples of benzonitrile will be described.
  • SiO 2 as a carrier manufactured by Fuji Silysia, CARiACT, G-6, surface area: 535 m 2 / g
  • SiO 2 as a carrier manufactured by Fuji Silysia, CARiACT, G-6, surface area: 535 m 2 / g
  • an aqueous solution was prepared using (NH 4 ) 6 Mo 7 O 24 (manufactured by Kanto Kagaku, special grade) so that the Mo support amount was finally 0.5 mmol / g. And impregnated with SiO 2 .
  • a magnetic stir bar the above catalyst (0.1 g), benzamide (hereinafter referred to as BA. 20 mmol), and mesitylene (20 ml) were introduced into a test tube, and molecular sieve 4A (pre-dried at 300 ° C. for 1 hour) was filled.
  • the Soxhlet extractor and Liebig condenser were connected, the temperature of the condenser was set to 10 ° C., and the magnetic stirrer was set to about 200 ° C. and 600 rpm.
  • the reaction start time was defined as the time when the solution started to evaporate, and the reaction was performed for 24 hours.
  • test tube solution
  • 20 ml of ethanol and anthracene 0.1 g as an internal standard substance are added to the reaction solution, a sample is taken, and GC-MS (gas chromatograph-mass spectrometer) And quantitative analysis by FID-GC.
  • BN benzonitrile
  • Example 15 Similar to Example 14, but in the catalyst preparation, an aqueous solution was used using (NH 4 ) 6 W 12 O 41 (manufactured by Kanto Chemical Co., Ltd., deer grade 1) so that the final W loading was 0.5 mmol / g. Was prepared and impregnated with SiO 2 . Thereafter, about 6 hours drying at 110 ° C., and calcined at 500 ° C. for about 3 hours to obtain WO 3 / SiO 2 catalyst.
  • BN was produced from BA in the same manner as in Example 14 except that a WO 3 / SiO 2 catalyst was used. As a result, as shown in Table 9, 3 mmol of BN was generated. By-product was only water, yield was 15%, and selectivity was 100%.
  • Example 16 As in Example 14, but in the catalyst preparation, the aqueous solution was adjusted using NH 4 ReO 4 (manufactured by Mitsuwa Chemicals) so that the final amount of Re supported was 0.5 mmol / g, and SiO 2 Impregnated. Thereafter, about 6 hours drying at 110 ° C., and calcined at 500 ° C. for about 3 hours to obtain a Re 2 O 7 / SiO 2 catalyst.
  • Benzonitrile (BN) was produced from benzamide (BA) in the same manner as in Example 14 except that the Re 2 O 7 / SiO 2 catalyst was used. As a result, as shown in Table 9, 1 mmol of BN was generated. The byproduct was only water, yield was 5%, and selectivity was 100%.
  • Example 17 As in Example 14, except that in the catalyst preparation, an aqueous solution was prepared using TiCl 3 (manufactured by Kanto Chemical Co., Ltd., deer grade 1) so that the Ti loading amount was finally 0.5 mmol / g, and the SiO 2 Impregnated. Thereafter, about 6 hours drying at 110 ° C., and calcined at 500 ° C. for about 3 hours to obtain a TiO 2 / SiO 2 catalyst.
  • BN was produced from BA in the same manner as in Example 14 except that a TiO 2 / SiO 2 catalyst was used. As a result, as shown in Table 9, 1 mmol of BN was generated. The byproduct was only water, yield was 5%, and selectivity was 100%.
  • Example 18 As in Example 14, but in the catalyst preparation, (NH 4 ) 3 (NbO (C 2 O 4 ) 3 ) (manufactured by Sigma-Aldrich, so that the Nb supported amount is finally 0.5 mmol / g, The aqueous solution was prepared using 4N) and impregnated with SiO 2 . Thereafter, about 6 hours drying at 110 ° C., and calcined at 500 ° C. for about 3 hours to obtain a Nb 2 O 5 / SiO 2 catalyst. BN was produced from BA in the same manner as in Example 14 except that the Nb 2 O 5 / SiO 2 catalyst was used. As a result, as shown in Table 9, 1 mmol of BN was generated. The byproduct was only water, yield was 5%, and selectivity was 100%.
  • SiO 2 manufactured by Fuji Silysia, CARiACT, G-3, surface area: 700 m 2 / g
  • SiO 2 was impregnated using (NH 4 ) 6 Mo 7 O 24 (manufactured by Kanto Chemical Co., Ltd., special grade) so that the Mo loading amount finally became as shown in Table 10.
  • BN was produced from BA in the same manner as in Example 14 except that the supported amount of the MoO 3 / SiO 2 catalyst was changed. As a result, as shown in Table 10, at any molar ratio, BN is generated, the byproduct is only water, and the amount of generation increases as the amount of Mo loaded increases, but there is a tendency to saturate above a certain level. It was.
  • Example 20 Carrier TiO 2 (manufactured by Nippon Aerosil Co., P25, surface area: 50m 2 / g), ZrO 2 ( Daiichi Kigenso made, surface area: 88m 2 / g), CeO 2 ( Daiichi Kigenso made, surface area: 74m 2 / g), Al 2 O 3 (manufactured by Sumitomo Chemical Co., Ltd., KHO, surface area: 10 m 2 / g), carbon black (manufactured by Cabot, Vulcan, XC-72, surface area: 254 m 2 / g), and the amount of supported Mo is 0.
  • Each support was impregnated with (NH 4 ) 6 Mo 7 O 24 (manufactured by Kanto Chemical Co., Ltd., special grade) so as to be 19 mmol / g.
  • BN was produced from BA in the same manner as in Example 14 using the catalyst thus prepared. As a result, as shown in Table 11, a fixed amount of BN was produced with any carrier.
  • Example 21 Except for using o-xylene, m-xylene, p-xylene and chlorobenzene as the solvent, the reaction was carried out under the same conditions as in Example 14 to produce BN from BA. As a result, as shown in Table 12, a fixed amount of BN was produced with any carrier.
  • Example 22 Evaluation was performed in the same manner as in Example 14 except that no dehydrating agent was used. As a result, after the reaction for 24 hours, the yield was 10% and the selectivity was almost 100%.
  • Example 14 The same procedure as in Example 14 was performed, except that only MgO (sized by Ube Industries, 500A, surface area: 28 m 2 / g) which had been sized to 100 mesh or less and pre-fired at 700 ° C. for about 1 hour was used as the catalyst. As a result, BN was not generated at all.
  • MgO sized by Ube Industries, 500A, surface area: 28 m 2 / g
  • Example 23 Next, the Example of the manufacturing method of carbonate ester using cyanopyridine is demonstrated.
  • Carbonate was produced using the production apparatus shown in FIG. CeO 2 (manufactured by the first rare element: impurity concentration of 0.02% or less) was calcined at 873 K in an air atmosphere for 3 hours to obtain a powdered solid catalyst. Therefore, a magnetic stirrer, the above solid catalyst (1 mmol), methanol (100 mmol) and 2-cyanopyridine (2-CP, 50 mmol) were introduced into a 190 ml autoclave (reactor), and about 5 g of CO 2 in the autoclave. After purging air three times, a predetermined amount of CO 2 was introduced and pressurized.
  • the autoclave was heated to 120 ° C. with a band heater and a hot stirrer, and the time when the target temperature was reached was defined as the reaction start time. After reacting at 120 ° C. for 12 hours, the autoclave was cooled with water, and after cooling to room temperature, the pressure was reduced and 0.2 mL of 1-hexanol as an internal standard substance was added, and the product was collected and analyzed by GC (gas chromatography). . In this way, test Nos. Shown in Table 13 were performed by changing the amount of CO 2 introduced and the reaction pressure. 37-40 experiments were performed.
  • DMC dimethyl carbonate
  • the liquid includes DMC, 2-CP, methanol, and hexane
  • the solid includes 2-PA and CeO 2 .
  • the liquid component after solvent extraction with hexane can be separated into DMC, 2-CP, hexane and methanol by distillation that gradually increases the temperature to about 120 ° C., and DMC with a purity of 96% or more can be recovered. It was.
  • 2-PA and CeO 2 in the solid component are dissolved in 200 ml of acetone and filtered through a filter to separate CeO 2 , 2-PA and acetone, and 2-PA and acetone are separated by distillation. As a result, 2-PA having a purity of 97% or more was recovered.
  • SiO 2 as a carrier manufactured by Fuji Silysia, CARiACT, G-6, surface area: 535 m 2 / g
  • SiO 2 Impregnated was used to adjust the aqueous solution, SiO 2 Impregnated. Thereafter, about 6 hours drying at 110 ° C., and calcined at 500 ° C.
  • a magnetic stir bar for about 3 hours to obtain a Na 2 O / SiO 2 catalyst. Therefore, a magnetic stir bar, the above catalyst (0.1 g), 2-PA produced as a byproduct of DMC generation, and mesitylene (20 ml) were introduced into a test tube, and molecular sieve 4A (pre-dried at 300 ° C. for 1 hour) was filled. A Soxhlet extractor and a Liebig condenser were connected, the temperature of the condenser was set to 10 ° C., and the magnetic stirrer was set to about 200 ° C. and 600 rpm.
  • the reaction start time was defined as the time when the solution started to evaporate, and the reaction was performed for 500 hours.
  • the test tube (solution) is cooled to room temperature, 20 ml of ethanol and anthracene (0.1 g) as an internal standard substance are added to the reaction solution, a sample is taken, and GC-MS (gas chromatograph-mass spectrometer) And quantitative analysis by FID-GC.
  • GC-MS gas chromatograph-mass spectrometer
  • Liquids include 2-CP, water, unreacted 2-PA, and mesitylene. This liquid component is separated into 2-CP, water, unreacted 2-PA, and mesitylene by distillation that gradually increases the temperature to about 180 ° C., and 2-CP having a purity of 98% or more is recovered. I was able to. The separated unreacted 2-PA and mesitylene can be recycled again for 2-PA dehydration reaction.
  • a second DMC production reaction was performed using 2-CP regenerated in this way.
  • the reaction conditions were the same, and a small amount of new 2-CP was added to 2-CP that was regenerated and 2-CP that had not been reacted in the first reaction, so that the amount of 2-CP was 50 mmol. did.
  • the amount of 2-CP was 50 mmol. did.
  • DMC was obtained in a high yield, and the amount of 2-PA produced as a by-product was almost the same as DMC, and other by-products were not detected at all. There wasn't.
  • Example 24 Example 23 was repeated except that ethanol (100 mmol) was used as a monohydric alcohol.
  • Liquids, DEC, 2-CP, ethanol, hexane, the solid include 2-PA and CeO 2.
  • the liquid component after solvent extraction with hexane can be separated into DEC, 2-CP, hexane and ethanol by distillation that gradually increases the temperature to about 130 ° C, and DEC with a purity of 96% or more can be recovered. It was.
  • 2-PA and CeO 2 in the fixed component are dissolved in 200 ml of acetone and filtered through a filter to separate CeO 2 , 2-PA and acetone, and 2-PA and acetone are separated by distillation. As a result, 2-PA having a purity of 97% or more was recovered.
  • each liquid and solid was separated in the same manner as in Example 1, and 2-CP having a purity of 98% or more could be recovered.
  • Example 25 The same procedure as in Example 23 was performed except that 1-propanol (100 mmol) was used as the monohydric alcohol and the reaction was performed for 24 hours.
  • Example 23 200 ml of hexane was added to the solid-liquid coexisting substance after each test, followed by stirring, solvent extraction, and filtration through a filter to separate the liquid and the solid.
  • the liquid contains DPrC, 2-CP, 1-propanol and hexane, and the solid contains 2-PA and CeO 2 .
  • the liquid component after solvent extraction with hexane is separated into DPrC, 2-CP, hexane, and 1-propanol by distillation that gradually increases the temperature to about 170 ° C., and DPrC having a purity of 96% or more is recovered. I was able to.
  • 2-PA and CeO 2 in the fixed component are dissolved in 200 ml of acetone and filtered through a filter to separate CeO 2 , 2-PA and acetone, and 2-PA and acetone are separated by distillation.
  • 2-PA having a purity of 97% or more was recovered.
  • regeneration from the recovered 2-PA to 2-CP was performed in the same manner as in Example 1.
  • test no. When 45 to 48 were carried out, 2-CP was produced at 9.5, 12.2, 15.4 and 21.4 mmol, respectively. In all experiments, the byproduct was only water, yield was 90% or more, and selectivity was 100%.
  • each liquid and solid was separated in the same manner as in Example 1, and 2-CP having a purity of 98% or more could be recovered.
  • Example 26 Example 23 was repeated except that 2-propanol (100 mmol) was used as a monohydric alcohol and the reaction was performed for 24 hours.
  • Example 23 200 ml of hexane was added to the solid-liquid coexisting substance after each test, followed by stirring, solvent extraction, and filtration through a filter to separate the liquid and the solid.
  • the liquid includes DiPrC, 2-CP, 2-propanol, and hexane
  • the solid includes 2-PA and CeO 2 .
  • the liquid component after solvent extraction with hexane is separated into DiPrC, 2-CP, hexane, and 2-propanol by distillation that gradually increases the temperature to about 170 ° C., and DiPrC having a purity of 96% or more is recovered. I was able to.
  • 2-PA and CeO 2 in the fixed component are dissolved in 200 ml of acetone and filtered through a filter to separate CeO 2 , 2-PA and acetone, and 2-PA and acetone are separated by distillation. As a result, 2-PA having a purity of 97% or more was recovered.
  • each liquid and solid was separated in the same manner as in Example 23, and 2-CP having a purity of 98% or more could be recovered.
  • Example 27 Example 23 was repeated except that 1-butanol (100 mmol) was used as a monohydric alcohol and the reaction was performed for 24 hours.
  • Example 23 200 ml of hexane was added to the solid-liquid coexisting substance after each test, followed by stirring, solvent extraction, and filtration through a filter to separate the liquid and the solid.
  • the liquid contains DBtC, 2-CP, 1-butanol and hexane, and the solid contains 2-PA and CeO 2 .
  • the liquid component after solvent extraction with hexane first separates hexane and 1-butanol by distillation that gradually increases the temperature to about 120 ° C., and then cools to about 0 ° C. As a result, DBC having a purity of 96% or more was recovered.
  • 2-PA and CeO 2 in the fixed component are dissolved in 200 ml of acetone and then filtered through a filter to separate CeO 2 , 2-PA and acetone, and 2-PA and acetone are separated by distillation.
  • the 2-PA having a purity of 97% or more was recovered.
  • each liquid and solid was separated in the same manner as in Example 23, and 2-CP having a purity of 98% or more could be recovered.
  • Example 28 The same procedure as in Example 23 was performed except that allyl alcohol (100 mmol) was used as a monohydric alcohol and the reaction was performed for 24 hours.
  • Example 23 200 ml of hexane was added to the solid-liquid coexisting substance after each test, followed by stirring, solvent extraction, and filtration through a filter to separate the liquid and the solid.
  • the liquid contains DAC, 2-CP, allyl alcohol, and hexane, and the solid contains 2-PA and CeO 2 .
  • the liquid component after solvent extraction with hexane first separates hexane and allyl alcohol by distillation that gradually increases the temperature to about 120 ° C, and then cools to about 0 ° C to precipitate 2-CP. As a result, DAC having a purity of 96% or more was recovered.
  • 2-PA and CeO 2 in the fixed component are dissolved in 200 ml of acetone and then filtered through a filter to separate CeO 2 , 2-PA and acetone, and 2-PA and acetone are separated by distillation.
  • the 2-PA having a purity of 97% or more was recovered.
  • each liquid and solid was separated in the same manner as in Example 23, and 2-CP having a purity of 98% or more could be recovered.
  • Example 29 The same procedure as in Example 23 was performed except that benzyl alcohol (100 mmol) was used as a monohydric alcohol and the reaction was performed for 24 hours.
  • the yield of DBnC based on benzyl alcohol is 13.0% at 0.08 MPa, 16.6% at 0.2 MPa, 16.6% at 1 MPa, and 1 MPa at the time of dibenzyl carbonate (DBnC). It was confirmed that it was obtained at 31.8% at 21.8% and 5 MPa. The amount of 2-PA produced as a by-product was almost the same as that of DBnC, and no other by-products were detected.
  • Liquids, DBnC, 2-CP, benzyl alcohol, hexane, the solid, include 2-PA and CeO 2.
  • the liquid component after solvent extraction with hexane first separates hexane and benzyl alcohol by distillation that gradually increases the temperature to about 120 ° C, and then cools to about 0 ° C to precipitate 2-CP.
  • DBnC having a purity of 96% or higher was recovered.
  • 2-PA and CeO 2 in the fixed component are dissolved in 200 ml of acetone and then filtered through a filter to separate CeO 2 , 2-PA and acetone, and 2-PA and acetone are separated by distillation.
  • the 2-PA having a purity of 97% or more was recovered.
  • each liquid and solid was separated in the same manner as in Example 23, and 2-CP having a purity of 98% or more could be recovered.
  • Example 30 In the catalyst preparation in reproduction from the recovered 2-PA to 2-CP, the other catalyst was a Li 2 O / SiO 2, K 2 O / SiO 2, Rb 2 O / SiO 2, Cs 2 O / SiO 2 Is the same test No. as in Example 23. 65-72 was performed.
  • the catalyst carrier described above was used, and the catalyst was supported on the catalyst carrier according to the method described above.
  • Example 31 In the catalyst preparation in the regeneration from the recovered 2-PA to 2-CP, Na 2 CO 3 (manufactured by Kanto Chemical Co., Ltd.) so that the total amount of the Na metal loading and the K metal loading is finally 0.5 mmol / g. , Special grade) and K 2 CO 3 (manufactured by Kanto Chemical Co., Ltd., special grade) were used to adjust the aqueous solution by changing the molar ratio and impregnated with SiO 2 . Thereafter, about 6 hours drying at 110 ° C., and calcined at 500 ° C. for about 3 hours to obtain a Na 2 O-K 2 O / SiO 2 catalyst.
  • Na 2 CO 3 manufactured by Kanto Chemical Co., Ltd.
  • Example 23 As in Example 23, except that a Na 2 O—K 2 O / SiO 2 catalyst was used, NO. 73-80 tests were conducted. As a result, as shown in Table 21, 2-CP was produced at any molar ratio, the by-product was only water, the yield was around 90%, and the selectivity was 100%. From the above results, it was found that the amount of alkali metal used can be changed according to the market price.
  • Example 32 In the catalyst preparation in the regeneration from recovered 2-PA to 2-CP, NO is the same as in Example 23 except that the final amount of supported Na metal is as shown in Table 22 and the reaction pressure is only 1 MPa. . 81-88 tests were conducted. As a result, as shown in Table 22, it was found that Na supported amount showed high activity at 0.1 to 1 mmol, and about 0.5 mmol was a suitable supported amount. On the other hand, it is confirmed that when the loading amount is too large, the activity is lowered. This is because the structure of the SiO 2 carrier is changed due to the loading of a large amount of Na oxide, and the surface area is greatly reduced. It was assumed that the oxide was also a large aggregate.
  • Na 2 O / SiO 2 catalyst was used in the regeneration reaction from 2-PA to 2-CP, but any of Li, Na, K, Rb, and Cs was used as the alkali metal.
  • One or two of these are prepared by adjusting the aqueous solution so that the final concentration is 0.5 mmol / g, then impregnating with SiO 2 , drying at 110 ° C. for about 6 hours, and baking at 500 ° C. for about 3 hours. Even when a catalyst was used, the same effect was obtained.
  • CeO 2 , ZrO 2 , or CeO 2 —ZrO 2 was used in addition to SiO 2 .
  • Example 23 200 ml of hexane was added to the solid-liquid coexisting substance after each test, followed by stirring, solvent extraction, and filtration through a filter to separate the liquid and the solid.
  • the liquid contains DMC, unreacted AN, methanol, and hexane, and the solid contains AA and CeO 2 . Since the liquid component after solvent extraction with hexane has a melting point and boiling point of AN of -45 ° C and 82 ° C, respectively, DMC and AN cannot be separated by distillation, so it is once cooled to -30 to 0 ° C It is possible to separate the precipitated DMC.
  • a mixture of methanol and hexane and unreacted AN can be separated.
  • the unreacted AN can be reused for the DMC formation reaction. Since the concentration of methanol contained in the mixture is high, it is difficult to reuse it as a solvent for extraction, and it is necessary to dispose of it.
  • AA and CeO 2 in the fixed component are dissolved in 100 ml of acetone and filtered through a filter to separate CeO 2 , AA and acetone, and AA and acetone are separated by distillation heated to about 70 ° C. As a result, AA having a purity of 95% or more was recovered.
  • the second DMC formation reaction was performed by adding new AN to the unreacted AN so that the amount of AN was 300 mmol.
  • the reaction was conducted in the same manner as in Example 23 except that the reaction was performed at 150 ° C. for 24 hours.
  • the amount of DMC produced was reduced to about 1/10 compared to the case of 2-CP, and the DMC yield based on methanol was the highest at 8.0% at 0.5 MPa. It became.
  • Test NO. 2 was conducted under the same conditions as in Example 23 except that the regeneration step from 2-PA to 2-CP and the separation step after the regeneration step were not performed. 92 and 93 were performed. As a result, DMC with a purity of 96% or more and 2-PA with a purity of 97% or more could be recovered, but 2-PA had almost no use and was treated as industrial waste. In addition, the second DMC production reaction newly required at least 29.2 or 42.0 mmol of 2-CP, leading to an increase in raw material costs.
  • Example 33 In catalyst preparation by regeneration from recovered 2-PA to 2-CP, CeO 2 (manufactured by 1st rare element, HS, surface area: 74 m 2 / g) is sized to 100 mesh or less at a carrier, and about 500 ° C. The same material as Example 30 (NO. 71) was used after pre-baking for 3 hours. As a result, 3.3 mmol of 2-CP was produced as shown in Table 27 (NO. 102). The byproduct was only water, yield was 11.2%, and selectivity was 100%.
  • Example 34 In catalyst preparation by regeneration from recovered 2-PA to 2-CP, ZrO 2 (manufactured by Daiichi Rare Element, HS, surface area: 88 m 2 / g) is sized to 100 mesh or less on the support, and about 500 ° C.
  • the same material as Example 30 (NO. 71) was used after pre-baking for 3 hours.
  • Table 27 (NO. 103) 3.0 mmol of 2-CP was produced.
  • the byproduct was only water, yield was 10.2%, and selectivity was 100%.
  • Example 35 Ce (NO 3 ) 3 (manufactured by Kanto Chemical Co., Ltd.) and Zr (NO 3 ) 4 (Kanto) are used in the catalyst preparation in the regeneration from the recovered 2-PA to 2-CP, because CeO 2 —ZrO 2 solid solution is used as a support.
  • (Chemical) was dissolved in a solution of Ce at 20 atomic% to introduce an aqueous NaOH solution to form a precipitate. The precipitate was filtered and washed with water at 1000 ° C. in an air atmosphere for 3 hours. After firing, a powdered solid solution (surface area: 65 m 2 / g) was obtained. This solid solution was sized to 100 mesh or less, pre-baked at 500 ° C. for about 3 hours, and the same as in Example 30 (NO. 71). As a result, 3.2 mmol of 2-CP was produced as shown in Table 27 (NO. 104). The byproduct was only water, yield was 10.8%, and selectivity was 100%.
  • Example 36 In the recovery step from recovered 2-PA to 2-CP, the same procedure as in Example 1 was performed except that o-xylene (20 ml) was used instead of mesitylene as the organic solvent and the reaction pressure was only 1 MPa. As a result, as shown in Table 28 (NO. 105), 9.5 mmol of 2-CP was produced. By-product was only water, yield was 32.2%, and selectivity was 100%.
  • Carbonate ester was produced using the production apparatus shown in FIG. CeO 2 (manufactured by the first rare element: impurity concentration of 0.02% or less) was calcined at 873 K in an air atmosphere for 3 hours to obtain a powdered solid catalyst. Therefore, a magnetic stirrer, the solid catalyst (1 mmol), methanol (100 mmol) and benzonitrile (BN, 50 mmol) were introduced into a 190 ml autoclave (reactor), and the air in the autoclave was blown 3 times with about 5 g of CO 2.
  • DMC dimethyl carbonate
  • BA by-product benzamide
  • BA and CeO 2 in the fixed component are dissolved in 200 ml of acetone and then filtered through a filter to separate CeO 2 , BA and acetone, and further, BA and acetone are separated by distillation, respectively, and purity is 97% or more. Of BA could be recovered.
  • SiO 2 as a carrier manufactured by Fuji Silysia, CARiACT, G-6, surface area: 535 m 2 / g
  • SiO 2 as a carrier was sized to 100 mesh or less and pre-baked at 700 ° C. for about 1 hour.
  • an aqueous solution is prepared using (NH 4 ) 6 Mo 7 O 24 (manufactured by Kanto Kagaku, special grade) so that the amount of Mo metal supported is finally 0.5 mmol / g. and it was impregnated in SiO 2. Thereafter, about 6 hours drying at 110 ° C., and calcined at 500 ° C.
  • test tube solution
  • 20 ml of ethanol and anthracene 0.1 g as an internal standard substance are added to the reaction solution, a sample is taken, and GC-MS (gas chromatograph-mass spectrometer) And quantitative analysis by FID-GC.
  • Table 29 the test No.
  • BN was produced in a proportion of 1.5 mmol, 2.6 mmol, 3.3 mmol, 5.1 mmol, 6.3 mmol, 6.0 mmol, and 3.5 mmol, respectively.
  • water was the only byproduct, yield was about 90%, and selectivity was almost 100%.
  • the solid-liquid coexisting substance after the above test was filtered with a filter under heating at 120 ° C. to separate the liquid and the solid (catalyst).
  • the liquid includes BN, water, unreacted BA, and mesitylene.
  • This liquid component was separated into BN, water, unreacted BA, and mesitylene by distillation that gradually increased the temperature to about 180 ° C., and BN having a purity of 98% or more could be recovered.
  • the separated unreacted BA and mesitylene can be recycled again for the dehydration reaction of BA.
  • Example 38 Example 37 was repeated except that ethanol (100 mmol) was used as a monohydric alcohol.
  • Example 37 200 ml of hexane was added to the solid-liquid coexisting substance after each test, and the mixture was stirred, extracted with a solvent, and filtered through a filter to separate a liquid and a solid.
  • the liquid includes DEC, BN, ethanol, and hexane
  • the solid includes BA and CeO 2 .
  • the liquid component after solvent extraction with hexane was separated into DEC, BN, hexane and ethanol by distillation that gradually increased the temperature to about 130 ° C., and DEC having a purity of 96% or more could be recovered.
  • BA and CeO 2 in the fixed component are dissolved in 200 ml of acetone and then filtered through a filter to separate CeO 2 , BA and acetone, and further, BA and acetone are separated by distillation, respectively, and purity is 97% or more. Of BA could be recovered.
  • each liquid and solid was separated in the same manner as in Example 37, and BN having a purity of 98% or more could be recovered.
  • Example 39 The same procedure as in Example 37 was performed, except that 1-propanol (100 mmol) was used as a monohydric alcohol and the reaction was performed for 24 hours.
  • Example 37 200 ml of hexane was added to the solid-liquid coexisting substance after each test, and the mixture was stirred, extracted with a solvent, and filtered through a filter to separate a liquid and a solid.
  • the liquid includes DPC, BN, 1-propanol, and hexane
  • the solid includes BA and CeO 2 .
  • the liquid component after solvent extraction with hexane can be separated into DPC, BN, hexane, and 1-propanol by distillation that gradually increases the temperature to about 170 ° C., and DPC with a purity of 96% or more can be recovered. It was.
  • BA and CeO 2 in the fixed component are dissolved in 200 ml of acetone and then filtered through a filter to separate CeO 2 , BA and acetone, and further, BA and acetone are separated by distillation, respectively, and purity is 97% or more. Of BA could be recovered.
  • each liquid and solid was separated in the same manner as in Example 37, and BN having a purity of 98% or more could be recovered.
  • the monohydric alcohol is 1-propanol and the product is DPC
  • the temperature is raised to about 180 ° C., so this heat is used by supplying it through a heated pipe when reusing it for DPC production. be able to.
  • Example 40 The same procedure as in Example 37 was performed, except that 1-butanol (100 mmol) was used as a monohydric alcohol and the reaction was performed for 24 hours.
  • Example 37 200 ml of hexane was added to the solid-liquid coexisting substance after each test, and the mixture was stirred, extracted with a solvent, and filtered through a filter to separate a liquid and a solid.
  • the liquid contains DBC, BN, 1-butanol and hexane, and the solid contains BA and CeO 2 .
  • the liquid component after solvent extraction with hexane first separates hexane and 1-butanol by distillation that gradually increases the temperature to about 120 ° C., and then cools to about 0 ° C. to precipitate BN. It was possible to recover DBC having a purity of 96% or more.
  • BA and CeO 2 in the fixed component are dissolved in 200 ml of acetone and then filtered through a filter to separate CeO 2 , BA and acetone, and further, BA and acetone are separated by distillation, respectively, and purity is 97% or more. Of BA could be recovered.
  • each liquid and solid was separated in the same manner as in Example 37, and BN having a purity of 98% or more could be recovered.
  • the monohydric alcohol is 1-butanol and the product is DBC
  • the temperature is increased to about 180 ° C., so this heat is used by supplying it through a heated pipe when reusing it for DBC production. be able to.
  • Example 41 The same procedure as in Example 37 was performed except that 100 mmol each of benzyl alcohol, allyl alcohol, and 2-propanol was used as a monohydric alcohol and the reaction was performed for 24 hours.
  • Example 37 200 ml of hexane was added to the solid-liquid coexisting substance after each test, and the mixture was stirred, extracted with a solvent, and filtered through a filter to separate a liquid and a solid.
  • the liquid contains EC, BN and each alcohol component, and hexane, and the solid contains BA and CeO 2 .
  • the liquid component after solvent extraction with hexane first separates hexane and each alcohol by distillation that gradually increases the temperature to about 120 ° C., and then cools to about 0 ° C. to precipitate BN, EC with a purity of 96% or more could be recovered.
  • BA and CeO 2 in the fixed component are dissolved in 200 ml of acetone and then filtered through a filter to separate CeO 2 , BA and acetone, and further, BA and acetone are separated by distillation, respectively, and purity is 97% or more. Of BA could be recovered.
  • each liquid and solid was separated in the same manner as in Example 37, and BN having a purity of 98% or more could be recovered.
  • Example 42 In the catalyst preparation in the regeneration from the recovered BA to BN, the catalyst was MoO 3 / TiO 2 , Re 2 O 7 / CeO 2 , WO 3 / SiO 2 , Nb 2 O 5 / ZrO 2 Test NO. 122-129 were performed.
  • the catalyst carrier described above was used, and the catalyst was supported on the catalyst carrier according to the method described above.
  • Example 43 In the catalyst preparation in the regeneration from the recovered BA to BN, NO. Is the same as in Example 37 except that the final Mo loading is as shown in Table 35 and the reaction pressure is only 1 MPa. 130-135 tests were performed. As a result, as shown in Table 35, it was found that Mo loading was high at 0.1 to 1 mmol, and about 0.6 mmol was a suitable loading amount. On the other hand, when the loading amount was excessively increased, the activity was relatively lowered. This is because the Mo oxide on the SiO 2 carrier becomes a large aggregate because the Mo oxide is loaded in a large amount. Inferred.
  • the MoO 3 / SiO 2 catalyst was used in the regeneration reaction from BA to BN, but one or two of W, Re, and Nb were used as metal elements in the final reaction.
  • the same effect can be obtained by using a catalyst obtained by adjusting an aqueous solution to 0.5 mmol / g, then impregnating with SiO 2 , drying at 110 ° C. for about 6 hours, and calcining at 500 ° C. for about 3 hours. was gotten.
  • the same effect was obtained when CeO 2 , ZrO 2 , or CeO 2 —ZrO 2 was used in addition to SiO 2 .
  • Example 44 In the recovered BA to BN regeneration step, the procedure was the same as Example 37, except that o-xylene (20 ml) was used instead of mesitylene as the organic solvent, and the reaction pressure was only 1 MPa. As a result, as shown in Table 36 (NO. 136), 3.2 mmol of BN was generated. By-product was only water, yield was 42.7%, and selectivity was almost 100%.
  • Example 37 200 ml of hexane was added to the solid-liquid coexisting substance after each test, and the mixture was stirred, extracted with a solvent, and filtered through a filter to separate a liquid and a solid.
  • the liquid contains DMC, unreacted AN, methanol, and hexane, and the solid contains AA and CeO 2 . Since the liquid component after solvent extraction with hexane has a melting point and boiling point of AN of -45 ° C and 82 ° C, respectively, DMC and AN cannot be separated by distillation, so it is once cooled to -30 to 0 ° C It is possible to separate the precipitated DMC.
  • a mixture of methanol and hexane can separate the unreacted AN, and the unreacted AN can be reused for the DMC formation reaction. Since the concentration of methanol contained in the mixture is high, it is difficult to reuse as a solvent for extraction and it is necessary to dispose of it.
  • AA and CeO 2 in the fixed component are dissolved in 100 ml of acetone and filtered through a filter to separate CeO 2 , AA and acetone, and AA and acetone are separated by distillation heated to about 70 ° C. As a result, AA having a purity of 95% or more was recovered.
  • the second DMC formation reaction was performed by adding new AN to the unreacted AN so that the amount of AN was 300 mmol.
  • the reaction was conducted in the same manner as in Example 37 except that the reaction was performed at 150 ° C. for 24 hours.
  • the amount of DMC produced was reduced to about 1/10 compared to the case of BN, and the DMC yield based on methanol reached 1.7% at 0.5 MPa. It was.

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Abstract

La présente invention concerne un procédé permettant d'effectuer une régénération à partir de picolinamide ou de benzamide en cyanopyridine ou benzonitrile sans utiliser de réactifs forts tout en limitant également la production de sous-produits. Un mode de réalisation de la présente invention concerne un procédé de fabrication de cyanopyridine caractérisé en ce que le cyanopyridine est fabriqué par chauffage du picolinamide en présence d'un catalyseur chargé d'un oxyde de métal alcalin et en présence d'un solvant organique pour provoquer une réaction de déshydratation. Un autre mode de réalisation de la présente invention concerne un procédé de fabrication de benzonitrile caractérisé en ce que le benzonitrile est fabriqué par chauffage du benzamide en présence d'un catalyseur dans lequel un oxyde métallique d'une espèce métallique telle que le molybdène est chargé sur un support catalytique obtenue à partir de SiO2, etc. et en présence d'un solvant organique pour provoquer une réaction de déshydratation.
PCT/JP2014/084331 2013-12-27 2014-12-25 Procédé de fabrication de cyanopyridine, procédé de fabrication de benzonitrile, procédé de fabrication d'ester de carbonate et appareil de fabrication d'ester de carbonate WO2015099053A1 (fr)

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JP2013273184A JP6176108B2 (ja) 2013-12-27 2013-12-27 ２−シアノピリジンの製造方法
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JP2014042007A JP6349787B2 (ja) 2014-03-04 2014-03-04 炭酸エステルの製造方法
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RU2785279C1 (ru) * 2019-01-29 2022-12-05 Эвоник Оперейшенс ГмбХ Катализатор для синтеза алкилмеркаптана и способ его получения
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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI654178B (zh) 2017-12-28 2019-03-21 財團法人工業技術研究院 二烷基碳酸酯之製備方法
CN113817153B (zh) * 2021-09-30 2022-10-11 大连理工大学 一类氰基功能化碳酸酯单体、氰基功能化聚碳酸酯及制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003252845A (ja) * 2002-03-01 2003-09-10 Japan Science & Technology Corp ニトリルの製造方法及びニトリル製造用触媒
JP2010077113A (ja) * 2008-08-27 2010-04-08 Nippon Steel Corp 炭酸エステルの製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003252845A (ja) * 2002-03-01 2003-09-10 Japan Science & Technology Corp ニトリルの製造方法及びニトリル製造用触媒
JP2010077113A (ja) * 2008-08-27 2010-04-08 Nippon Steel Corp 炭酸エステルの製造方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CAMPBELL, JACQUELINE A. ET AL.: "Laboratory- Scale Synthesis of Nitriles by Catalysed Dehydration of Amides and Oximes under Flash Vacuum Pyrolysis (FVP) Conditions", SYNTHESIS, vol. 20, 2007, pages 3179 - 3184 *
HONDA, MASAYOSHI ET AL.: "Ceria-Catalyzed Conversion of Carbon Dioxide into Dimethyl Carbonate with 2-Cyanopyridine", CHEMSUSCHEM, vol. 6, no. 8, 2013, pages 1341 - 1344 *
JOSHI, GOPAL W. ET AL.: "Dehydration of carboxamides to nitriles with a zirconia catalyst", CHEMISTRY AND INDUSTRY, vol. 24, 1986, pages 876 - 877 *
YOSHINAO NAKAGAWA: "Nitrile-rui o Dassuizai ni Mochiita Ceria Shokubai ni yoru Nisankatanso to Methanol kara no Tansan Dimethyl Gosei", DAI 110 KAI SHOKUBAI TORONKAI TORONKAI A YOKOSHU, 14 September 2012 (2012-09-14), pages 145 - 146 *

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