JP2006182708A - Manufacturing method of aliphatic nitrile - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of an aliphatic amine for obtaining the aliphatic amine at a low manufacturing cost. <P>SOLUTION: The manufacturing method of the aliphatic amine comprises manufacturing an aliphatic nitrile by reacting an aliphatic carboxylic acid, an aliphatic dicarboxylic acid or an alkyl ester of these (the alkyl group having 1-5 carbon atoms) with ammonia in the presence of titanium oxide sol and subsequently hydrogenating the aliphatic nitrile in the presence of a hydrogenation catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing an aliphatic nitrile capable of reducing production costs and a method for producing an aliphatic amine from an aliphatic nitrile produced by the method.

  As a method for producing an aliphatic nitrile, a method in which an aliphatic carboxylic acid or a derivative thereof is reacted with ammonia is generally known industrially. As a reaction form, there are a gas phase method and a liquid phase method.

  In Patent Document 1, an aliphatic carboxylic acid vaporized in advance using a Zr, Ta, Ga, In, Sc, Nb, Hf, Fe, Zn, or Sn oxide as a catalyst as a reaction in a gas phase method. Alternatively, a method of contacting a derivative thereof with ammonia at a temperature of 250 to 600 ° C. is disclosed.

  Patent Document 2 discloses a method of contacting an aliphatic carboxylic acid or its alkyl ester vaporized beforehand with ammonia at a temperature of 200 to 400 ° C. using zirconium oxide poisoned with a metal polyvalent cation. Yes.

  In Patent Document 3, a solid catalyst containing an oxide of at least one element selected from titanium and zirconium is used, and an aliphatic carboxylic acid having 2 to 8 carbon atoms and an alkyl ester thereof together with ammonia at 250 to 550 ° C. A method of manufacturing at temperature is disclosed.

  In the reactions of Patent Documents 1 to 3, it is necessary to vaporize the raw material fatty acid or fatty acid derivative, which has the disadvantage that it costs more energy than the liquid phase method.

  On the other hand, when the reaction is carried out by the liquid phase method, there is a wide range of methods in which the aliphatic carboxylic acid or its derivative is heated and dissolved in the presence of a catalyst and ammonia gas is blown into this to react in a batch or continuous manner. Has been done.

  Patent Document 4 discloses a method of reacting at 150 to 290 ° C. using iron or an iron compound. However, in this reaction, the catalyst elutes into the aliphatic carboxylic acid, and this eluate acts as an inhibitor of the reaction in a method for producing an aliphatic amine from the aliphatic nitrile by a hydrogenation reaction, for example. . Therefore, a new facility for separating and recovering the effluent is required, and the yield of the aliphatic nitrile is reduced, which is not preferable as a method for producing an aliphatic nitrile.

In Patent Document 5, the reaction temperature is not more than 300 ° C., and it is difficult for the reaction liquid to combine titanium oxide with an oxide of one or more elements selected from the group consisting of silicon, niobium, zirconium, tantalum, gallium and germanium. A manufacturing method using a soluble composite oxide is disclosed. This catalyst can certainly suppress elution into aliphatic carboxylic acids, but the alkoxides of these metals, which are raw materials for preparing the catalyst, are expensive, have insufficient reactivity, and there is room for improvement in the industry.
JP-A-4-208260 JP 10-195035 A JP 2002-284753 A JP 58-39653 A JP 2000-80069

  The present invention provides an industrially advantageous method for producing an aliphatic nitrile that has good reactivity and can reduce production costs, and a method for producing an aliphatic amine using the aliphatic nitrile as a raw material. Let it be an issue.

  The present invention provides an aliphatic nitrile that reacts an aliphatic carboxylic acid, an aliphatic dicarboxylic acid or an alkyl ester thereof (the alkyl group has 1 to 5 carbon atoms) with ammonia in the presence of a titanium oxide sol as a means for solving the problem. A manufacturing method is provided.

  According to the present invention, as another solution to the problem, the titanium oxide sol is dispersed in water (pH at 25 ° C. is 6 to 14), an organic solvent, or a mixed solvent of water and an organic solvent. A method for producing an aliphatic nitrile is provided.

  The present invention provides a method for producing an aliphatic amine in which the aliphatic nitrile obtained by the method according to claim 1 or 2 is hydrogenated in the presence of a hydrogenation catalyst as a means for solving another problem. To do.

  According to the present invention, since the titanium oxide sol is used, an aliphatic nitrile can be obtained with high reactivity and yield and at a lower production cost. By using this aliphatic nitrile as a raw material, high yield can be obtained. And an aliphatic amine can be obtained at a low production cost.

<Method for producing aliphatic nitrile>
The method for producing an aliphatic nitrile of the present invention is a method in which an aliphatic carboxylic acid, an aliphatic dicarboxylic acid or an alkyl ester thereof (the alkyl group has 1 to 5 carbon atoms) and ammonia are reacted in the presence of a titanium oxide sol. .

  The titanium oxide sol used in the present invention is a suspension in which titanium oxide particles are dispersed in a dispersion medium, and particles having a diameter of about 1 to 500 nm are uniformly dispersed using a liquid as a dispersion medium.

  As such a titanium oxide sol, (I) a titanium oxide sol in which titanium oxide particles are dispersed in water (pH at 25 ° C. is 6 to 14), (II) a titanium oxide sol in which titanium oxide particles are dispersed in an organic solvent, (III) Any of titanium oxide sol in which titanium oxide particles are dispersed in a mixed solvent of water and an organic solvent may be used. The titanium oxide sol contains 1 to 25 parts by mass of oxides such as silicon, niobium and zirconium with respect to 100 parts by mass of titanium oxide as a component or promoter component that does not inhibit the reaction in the production method of the present invention. May be.

  Since titanium oxide particles have good reactivity, those having a particle size of 80% by mass or more of all particles are preferably 0.1 μm or less, and more preferably, particles having a particle size of 90% by mass or more of all particles are 0.1 μm or less. belongs to.

  The particle size distribution of titanium oxide is measured by a dynamic light scattering method. The measurement method is as follows. Prepare a sample diluted with water so that the titanium oxide particles are about 0.05 to 0.1% by mass in the measurement cell, and measure using PARTICLE SIZE SYSTEMS NICOMP 380ZLS (wavelength 532 nm (green)). The particle size distribution of volume weighted average is obtained by the method.

  5-20 mass% is preferable, as for content of the titanium oxide particle in a titanium oxide sol, 6-18 mass% is more preferable, and 8-15 mass% is further more preferable.

  The organic solvent as a dispersion medium is preferably an organic solvent having a high vapor pressure that can be distilled off at a temperature lower than the reaction temperature in the production method of the present invention, and alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol. And ethers such as diethyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane and 2-methoxyethanol, and ketones such as acetone and methyl ethyl ketone.

  The content of water when the dispersion medium is a mixture of water and an organic solvent is not particularly limited, and may be mixed at an arbitrary ratio as long as a stable dispersed sol is formed.

  The titanium oxide sol can be obtained by a known production method, for example, using an inorganic titanium salt such as titanium sulfate, nitrate, halide, etc. as a raw material, and removing acid radicals contained therein or adding an alkaline solution. A method obtained by adding titanium lactate to water for hydrolysis; a method for obtaining a sol by hydrolyzing titanium alkoxide by various means.

  The alkaline solution used in the production of the titanium oxide sol is preferably one that does not inhibit the reaction in the production method of the present invention or reduce the yield of the aliphatic nitrile, such as aqueous ammonia, ammonium bicarbonate, ammonium carbonate, etc. It can be illustrated. Moreover, the titanium oxide sol used in the present invention can also be obtained as a commercial product.

  The aliphatic carboxylic acid, aliphatic dicarboxylic acid or alkyl ester thereof (the alkyl group has 1 to 5 carbon atoms) used in the present invention is a linear or branched saturated or unsaturated fatty acid having 6 to 22 carbon atoms. An alkyl ester of an aliphatic monocarboxylic acid, dicarboxylic acid or aliphatic carboxylic acid (the alkyl group has 1 to 5 carbon atoms).

  Here, specific examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, propyl, and isopropyl, and methyl is particularly preferable. These aliphatic carboxylic acids, aliphatic dicarboxylic acids, or alkyl esters thereof (the alkyl group has 1 to 5 carbon atoms) can be used alone or in admixture of two or more.

  Specific examples of the aliphatic carboxylic acid and the aliphatic dicarboxylic acid include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, dimethyloctanoic acid, butyl hepetyl nonane. Acid, hexenoic acid, octenoic acid, decenoic acid, dodecenoic acid, tetradecenoic acid, hexadecenoic acid, octadecenoic acid, eicosenoic acid, docosenoic acid, adipic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, hexadecamethylene dicarboxylic acid, octadecanoic acid Examples include decamethylene dicarboxylic acid.

  Specific examples of the aliphatic carboxylic acid alkyl ester (the alkyl group has 1 to 5 carbon atoms) include methyl, ethyl, propyl, and isopropyl esters of the aliphatic carboxylic acid and the aliphatic dicarboxylic acid.

  The amount of ammonia used in the present invention is preferably 1 to 100 mol, more preferably 2 to 50 mol, and still more preferably 2 with respect to 1 mol of aliphatic carboxylic acid, aliphatic dicarboxylic acid or alkyl ester thereof. ~ 20 moles.

  The titanium oxide sol used as a catalyst is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and still more preferably 100 parts by mass of aliphatic carboxylic acid, aliphatic dicarboxylic acid or alkyl ester thereof. Is in the range of 0.1 to 10 parts by mass.

  The reaction in the method for producing an aliphatic nitrile of the present invention can be carried out in a batch, semi-batch, continuous, or fixed bed flow system using a suspended bed.

  For batch and semi-batch production methods, a method is used in which fatty acid is dissolved, a predetermined amount of catalyst is charged, the reaction tank is sufficiently purged with nitrogen, and then the temperature is raised to the reaction temperature and then ammonia gas is introduced. it can.

  In the production method using a continuous type or a fixed bed flow type, a dissolved aliphatic carboxylic acid, aliphatic dicarboxylic acid or their alkyl ester and ammonia gas are introduced after the catalyst is charged and heated to a reaction temperature. The method can be applied.

  The reaction pressure is usually slightly pressurized, but may be normal pressure. The reaction temperature is preferably 180 to 350 ° C, more preferably 230 to 320 ° C, still more preferably 250 to 300 ° C. The reaction time is preferably 1 to 15 hours, more preferably 1 to 10 hours, and further preferably 1 to 8 hours.

  In the production method of the present invention, a titanium oxide sol is used as a catalyst. However, since the titanium oxide sol hardly dissolves in the reaction solution, no special purification treatment is required. However, purification treatment such as distillation may be performed as necessary.

<Method for producing aliphatic amine>
The method for producing an aliphatic amine of the present invention is a method in which the aliphatic nitrile produced by the above method is used as a raw material and hydrogenation is performed using a hydrogenation catalyst. As described above, since the obtained aliphatic nitrile contains almost no titanium oxide sol, a hydrogenation reaction occurs efficiently and an aliphatic amine can be produced without purification such as a distillation step. However, a product purified by distillation may be used as a raw material.

  As the hydrogenation catalyst, a known hydrogenation catalyst such as a cobalt-based catalyst, a nickel-based catalyst, a copper-based catalyst, or a noble metal-based catalyst is used. Preferably, a catalyst mainly composed of nickel, cobalt and / or ruthenium, more preferably a Raney type catalyst is used, and aluminum, zinc, silicon or the like may be contained as another metal. In addition, these catalysts can contain a metal selected from chromium, iron, cobalt, manganese, tungsten, and molybdenum as a promoter.

  Further, as the hydrogenation catalyst, a complete solid catalyst or a supported solid catalyst such as nickel, cobalt, ruthenium or the like supported on aluminum oxide, titanium oxide, zirconium oxide, or magnesia / alumina can be used.

  The amount of the hydrogenation catalyst used is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the aliphatic nitrile.

  The reaction pressure is preferably a hydrogen pressure of 0.3 to 5 MPa, more preferably 1.0 to 4 MPa, and even more preferably 1.5 to 3 MPa. The reaction temperature is preferably 50 to 200 ° C., more preferably 80 to 170 ° C., further preferably 100 to 140 ° C., and the reaction temperature is raised continuously or stepwise when the hydrogenation reaction is taking place. Is preferred. The reaction time is preferably 1 to 15 hours, more preferably 1 to 12 hours, and further preferably 1 to 10 hours.

Example 1
A four-necked flask equipped with a stirrer, gas inlet tube, thermometer, and dehydrator contains titanium oxide sol dispersed in an aqueous ammonia solution (containing 97% by mass of titanium oxide particles of 20 nm or less. PH 10. Taki. 16.7 g (1.0 g as titanium oxide) of A-6 manufactured by Kagaku Co., Ltd. and 500 g of oleic acid (Lunac 0-A manufactured by Kao Co., Ltd.) were mixed, and ammonia at 1000 ml / min at a reaction temperature of 300 ° C Gas was introduced and reacted.

  The obtained reaction product was subjected to composition analysis by gas chromatography [gas chromatography apparatus: HEWLETT PACKARD Series 6890, column: HP-5 manufactured by J & W Scientific (column inner diameter × length: 0.25 mm × 60 m)]. The time from the introduction of ammonia gas until the amount of aliphatic amide produced below the detection limit in the above gas chromatography measurement was 3.1 hours. At that time, the amount of nitrile produced was 98.4%.

Example 2
After 450 g of the product obtained in Example 1, 1.6 g of Raney nickel catalyst, 0.9 g of 48% NaOH, and 7.8 g of ion-exchanged water were charged into the autoclave, the space in the autoclave was replaced with hydrogen, and the hydrogen pressure was 1.9 MPa. Then, the temperature was raised to 135 ° C. and reacted at this temperature for 3 hours.

The product was subjected to composition analysis by gas chromatography [gas chromatography apparatus: HEWLETT PACKARD, column: JHEWLETT PACKARD Ultra-2 (inner diameter × length: 0.53 mm × 15 m)], and the amount of stearylamine produced was measured. The yield was 0.1%.

Claims (3)

  A method for producing an aliphatic nitrile in which an aliphatic carboxylic acid, an aliphatic dicarboxylic acid or an alkyl ester thereof (the alkyl group has 1 to 5 carbon atoms) and ammonia are reacted in the presence of a titanium oxide sol.   The method for producing an aliphatic nitrile according to claim 1, wherein the titanium oxide sol is dispersed in water (pH of 6 to 14 at 25 ° C), an organic solvent, or a mixed solvent of water and an organic solvent. The manufacturing method of the aliphatic amine which performs the hydrogenation reaction of the aliphatic nitrile obtained by the method of Claim 1 or 2 in presence of a hydrogenation catalyst.