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WO1999008998A1 - Procede servant a preparer formamide - Google Patents

Procede servant a preparer formamide Download PDF

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Publication number
WO1999008998A1
WO1999008998A1 PCT/JP1998/003656 JP9803656W WO9908998A1 WO 1999008998 A1 WO1999008998 A1 WO 1999008998A1 JP 9803656 W JP9803656 W JP 9803656W WO 9908998 A1 WO9908998 A1 WO 9908998A1
Authority
WO
WIPO (PCT)
Prior art keywords
formamide
boiling
low
column
ammonia
Prior art date
Application number
PCT/JP1998/003656
Other languages
English (en)
Japanese (ja)
Inventor
Tadashi Irizawa
Kazumoto Ogura
Hidetake Togawa
Mikiyoshi Kawaragi
Akira Tsunemi
Original Assignee
Mitsubishi Rayon Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Rayon Co., Ltd. filed Critical Mitsubishi Rayon Co., Ltd.
Publication of WO1999008998A1 publication Critical patent/WO1999008998A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines

Definitions

  • the present invention relates to a method for producing formamide by reacting methyl formate with ammonia.
  • Formamide is an industrially useful substance as a solvent, a raw material for organic synthesis, a raw material for pharmaceuticals, and the like.
  • JP-B-38-28757 describes that adding a catalytic amount of water to methyl formate and introducing ammonia increases the reaction rate.
  • JP-A-3-68544 describes a method for producing formamide from methyl formate and ammonia using a basic catalyst.
  • the method using water or a basic catalyst as a catalyst has a problem in that formamide produced is hydrolyzed and formic acid and ammonium are by-produced.
  • the following is a method for continuously producing formamide from methyl formate and ammonia.
  • JP-A-5-2-14-21010 cools a part of the liquid withdrawn from the reactor and reacts it with methyl formate and gaseous ammonia sprayed from a nozzle. Is supplied to a reactor again to react methyl formate with ammonia gas at a low temperature to produce formamide.
  • JP-A-57-1506448 describes a method for continuously producing formamide from methyl formate and ammonia while recovering methanol as a reaction by-product. These documents do not describe the reduction of diformamide by-produced in generated formamide.
  • JP-A-6-340600 describes a method for producing formamide in the presence of at least 20% by weight of alcohol with respect to methyl formate. Methods such as the addition of alcohols are not efficient because they are reaction by-products that should be removed from the product.
  • the present invention has been made in view of the above-mentioned problems of the prior art, and has an object to formally produce formamide by reacting methyl formate with ammonia. It is an object of the present invention to provide a method capable of efficiently producing formamide by reducing impurities such as diformamide, formic acid, and ammonia generated during distillation and purification of a target product.
  • the present inventors have conducted intensive studies on the above problems, and as a result, in a method for producing formamide from methyl formate and ammonia, by performing a continuous reaction in the presence of formamide and free ammonia, The by-product of diformamide is suppressed, and the liquid extracted from the bottom of the product distillation column is circulated and supplied to the reaction tank or low-boiling separation column to recover formamide in the bottom liquid, and The present inventors have found that the yield of the desired formamide is improved by changing the diformamide therein to formamide, and completed the present invention.
  • the present invention relates to a method for producing formamide by reacting methyl formate and ammonia, comprising the following steps: 1) Methyl formate and ammonia in a reaction vessel in the presence of formamide in a molar ratio of ammonia / methyl formate> 1.
  • the gist of the present invention is a method for producing formamide, which involves removing formamide from the top of a product distillation column and 5) circulating and supplying the high-boiling liquid separated from the bottom of the column to a reaction tank or low-boiling separation column.
  • FIG. 1 is a view showing one embodiment of the production process of the present invention.
  • the reaction between methyl formate and ammonia is carried out in the presence of formamide. Therefore, before starting the reaction by supplying methyl formate and ammonia, it is necessary to charge formamide into reaction vessel A in advance. A very small amount is sufficient, but it is preferably about 100 to 10% of the capacity of the reaction tank from the viewpoint of operability.
  • the concentration of formamide during the reaction is 30 to 99%, preferably 50 to 70%, as the concentration in the reaction solution. It is desired that the raw materials methyl formate and ammonia used in the method of the present invention have as high a purity as possible, but they may be industrial ones.
  • methyl formate 1 and ammonia 2 are simultaneously supplied to reaction vessel A at a high power, and the ratio is preferably such that ammonia is excess with respect to methyl formate.
  • Methyl formate> 1, preferably 0.1 to 5, more preferably 1.01 to 20.
  • the reaction temperature ranges from 10 to 60 ° C, preferably from 30 to 50 ° C.
  • the reaction solution 3 thus obtained is withdrawn from the reaction vessel A, fed to the middle stage of the low-boiling separation column B1, and distilled under normal pressure and a bottom temperature of 60 to 120 ° C.
  • the low-boiling fraction mainly composed of methanol is removed from the top of the system by distillation, and incinerated or sent to a methanol recovery system.
  • a liquid mainly composed of formamide (low-boiling liquid 1) 5 is taken out from the bottom of the column and supplied to the middle stage of the next product distillation column C.
  • a low-boiling separation column B2 may be further added between the low-boiling separation column B1 and the product distillation column C.
  • the pressure is 133 to 26,66 Pa (l to 200 To rr)
  • the top temperature is 5 to 40 ° C
  • the bottom temperature is 90 to (1) Distill at 30 ° C, remove low-boiling fraction mainly composed of methanol from the top of the column by distillation, and send to incineration or methanol recovery system.
  • a liquid containing formamide as the main component (low-boiling liquid 2) 7 is taken out from the bottom of the column and supplied to the middle stage of the product distillation column C.
  • the pressure is preferably 13 to 6,665 Pa (0.1 to 50 To rr)
  • the top temperature is 90 to 110 ° C
  • the bottom temperature is 100. Distillation is performed under conditions of ⁇ 140 ° C to obtain the product formamide II from the top of the column.
  • the following operation is performed for the purpose of reducing diformamide and improving the yield of formamide.
  • the bottom liquid extracted from the bottom of the product distillation column C is divided into a high boiling separated liquid of 1/20 to 19Z20 amount and the remaining bottom liquid, and the former high boiling separated liquid is used as a reaction tank. Recirculate to A.
  • this high-boiling liquid 10 is supplied to the low-boiling separation tower B1 together with the reaction product 3 containing about 0.1 to 2% of free ammonia.
  • an intermediate tank may be provided between the reaction tank A and the low-boiling distillation column B1, and the reaction product liquid 3 and the high-boiling separation liquid 10 may be mixed and then supplied to the low-boiling distillation column B1. .
  • the reaction product liquid 3 may be mixed and the mixture may be supplied to the low-boiling separation tower B1.
  • the amount of ammonia added is 1 mole or more, preferably 2 to 30 moles, per mole of diformamide.
  • the addition of ammonia may be performed in the following steps.
  • the liquid removed from the bottom of the low-boiling separation tower B 1 (low-boiling separation liquid 1) 5 or the liquid removed from the bottom of the low-boiling separation tower B 2 (low-boiling separation liquid 2) ⁇ Is added in an equimolar amount or more, preferably 2 to 30 times by mol, relative to diformamide, and the resulting mixture is supplied to the next step.
  • Formamide having a low impurity content such as diformamide can be obtained in high yield.
  • Formamide was manufactured by the manufacturing process shown in FIG.
  • a continuous reaction was carried out at 40 to 45 ° C and normal pressure.
  • the reaction product solution withdrawn from the reaction tank (3) (155 kg / H) was composed of 57.4% formamide, 40.9% methanol, and 0.9% ammonia. , 0.8% of methyl formate, and below the lower limit of detection of diformamide (about 10 ppm), and the reaction conversion was 99.0% (vs. methyl formate).
  • This reaction product 3 and the bottom liquid ⁇ ⁇ extracted from the bottom of the product distillation column C (formamide 94%, water 0.01%, ammonia formate 0.15%, and diformamide 4.3%) 3/4 volume of the high boiling separation liquid 10 3 1 kg / H and supply it to the middle stage of the low boiling separation column B 1 at 186 kg / H, normal pressure, top temperature 56 ° C, maintain a steady state at the bottom temperature of 110 ° C, remove low-boiling components mainly composed of methanol from the top of the column by distillation, and remove low-boiling separated liquid mainly composed of formamide from the bottom of the column. 1 3 2 kg / H was taken out.
  • the yield of product formamide was 93%, its composition was 99.9% formamide, 0.05% methanol, and methyl formate, formic acid, and diformamide were below the lower detection limit (about 10 pm).
  • the product formamide yield was 93%, its composition was 99.9% formamide, 0.05% methanol, and methyl formate, formic acid, and diformamide were below the detection limit (about 10 PPm). .
  • Example 1 was repeated except that 0.37 kg_ / H of ammonia was blown into the liquid (low-boiling liquid 1) ⁇ ⁇ (containing 0.3% diformamide) taken out from the bottom of low-boiling separation tower B1. By performing the same operation, a product formamide was obtained.
  • the product formamide yield is 93%, its composition is 99.9% formamide, 0.05% methanol, and methyl formate, formic acid and diformamide are below the detection limit (about 10 ppm). there were.
  • the reaction product 3 was withdrawn from the reaction tank A and analyzed.
  • formamide 56.1%, methanol 40.0%, ammonia 0.3%, methyl formate 3.2% And diformamide was 2,500 ppm.
  • the present invention can be used for the production of industrially useful formaldehyde as a solvent, a raw material for organic synthesis, a raw material for pharmaceuticals and the like.

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

Abstract

Procédé servant à préparer formamide par réaction de formate de méthyle avec ammoniac, ce qui consiste (1) à effectuer la réaction de formate de méthyle avec ammoniac dans un réacteur en présence de formamide selon un rapport molaire entre ammoniac et formate de méthyle supérieur à 1, (2) à introduire le mélange réactionnel dans une colonne de séparation pour des substances à ébullition basse afin de supprimer par distillation une fraction à ébullition basse par le sommet de la colonne, (3) à extraire le liquide résiduel du fond de la colonne et à l'introduire dans une colonne de distillation de produit, (4) à extraire formamide depuis le sommet de la colonne de distillation de produit et (5) à évacuer la fraction de liquide à ébullition élevée depuis le fond de la colonne, puis à faire circuler et à introduire ladite fraction dans le réacteur ou dans la colonne de séparation pour des substances à ébullition basse.
PCT/JP1998/003656 1997-08-18 1998-08-18 Procede servant a preparer formamide WO1999008998A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9/235489 1997-08-18
JP23548997 1997-08-18

Publications (1)

Publication Number Publication Date
WO1999008998A1 true WO1999008998A1 (fr) 1999-02-25

Family

ID=16986818

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1998/003656 WO1999008998A1 (fr) 1997-08-18 1998-08-18 Procede servant a preparer formamide

Country Status (2)

Country Link
CN (1) CN1125810C (fr)
WO (1) WO1999008998A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114853570A (zh) * 2022-05-13 2022-08-05 山东阿斯德科技有限公司 一种处理甲酰胺生产装置中废水的方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105237428B (zh) * 2015-10-22 2017-07-11 宿迁新亚科技有限公司 一种抑制聚合物生成的甲酰胺生产工艺
CN109761841B (zh) * 2019-01-30 2022-05-20 上海阿拉丁生化科技股份有限公司 一种光谱级甲酰胺的制备工艺

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52142010A (en) * 1976-05-22 1977-11-26 Basf Ag Method of continuous preparation of formamide
JPS57150648A (en) * 1981-02-19 1982-09-17 Basf Ag Continuous manufacture of formamide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52142010A (en) * 1976-05-22 1977-11-26 Basf Ag Method of continuous preparation of formamide
JPS57150648A (en) * 1981-02-19 1982-09-17 Basf Ag Continuous manufacture of formamide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114853570A (zh) * 2022-05-13 2022-08-05 山东阿斯德科技有限公司 一种处理甲酰胺生产装置中废水的方法

Also Published As

Publication number Publication date
CN1125810C (zh) 2003-10-29
CN1267280A (zh) 2000-09-20

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