JP2002088030A - Method for producing diamine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a diamine by which the lowering of the catalyst activity can be reduced and the diamine can industrially advantageously be produced in high yield in the method for producing the diamine from a dialdehyde. SOLUTION: A reducing amination reaction of the dialdehyde is carried out in the presence of ammonia and hydrogen using a nickel catalyst supported on an inorganic oxide having >=1.0 mL/g total volume of pores having <=1 μm diameter.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a diamine useful as a raw material for various nylons and polyurethanes.

[0002]

2. Description of the Related Art By reductive amination of dialdehyde in the presence of a hydrogenation catalyst, ammonia, hydrogen and a solvent,
It is known that the corresponding diamines can be obtained, for example by (1) a process in which dialdehyde is fed to a reductive amination reactor at a rate substantially not greater than the rate of dialdehyde disappearance (US Pat. No. 2,636,051). See), (2)
A method of supplying an alcohol solution of dialdehyde to a reaction system in which a hydrogenation catalyst, a solvent, hydrogen and ammonia are present (see JP-A-5-17413), (3) mixing dialdehyde with a diluent such as alcohol A method is known in which a mixture prepared by suppressing the formation of hemiacetal by limiting the temperature at this time to a maximum of 5 ° C. is added to a reactor for reductive amination (see JP-A-7-69999).

There is also known a method for producing an aliphatic diamine, characterized in that (4) when an aliphatic dialdehyde is reacted with ammonia and hydrogen in a solvent, a nickel catalyst supported on an inorganic oxide is present. (Japanese Unexamined Patent Publication No.
-196586). In this method, from the viewpoint of the activity and the life of the catalyst, a nickel catalyst supported on an inorganic oxide having a pore volume of about 10 to about 100 nm and a pore volume of 0.1 to 0.5 ml / g is considered to be particularly excellent, In Example 10, the pore volume of about 10 to about 100 nm in diameter is 0.19 m
In a reaction using a nickel catalyst supported on diatomaceous earth at 1 / g, the diamine yield at the end of dialdehyde supply was 75.7%, and the dialdehyde supply when the catalyst was reused once. Diamine yield at the end is 7
It is 4.5%, which is almost the same as the initial reaction result. However, there is no mention of the reaction results when such a catalyst is reused further repeatedly or when it is continuously reacted for a long time.

[0004]

In the above method (1), an example using Raney nickel as a catalyst is described, but the yield of diamine is as low as 40% or less. (2)
In the method of the above, an example using Raney nickel as a catalyst is shown.However, when the present inventors tried a continuous reaction for reductive amination of dialdehyde using Raney nickel as a catalyst, the catalyst became more prolonged with the reaction time. It was observed that the activity was significantly reduced (see Comparative Example 2 in this specification).
In the method (3), in order to suppress the formation of hemiacetal, it is necessary to control the temperature with a refrigerant, which increases the facility load. Therefore, none of these methods is industrially advantageous for producing diamines from dialdehydes.

The present inventors have studied the method (4) diligently,
The diamine yield upon repeated reuse is 92% for the first time,
It was found that the tendency was to drop from 91% at the second time to 82% at the fifth time. Also, a diameter of about 10 to about 100 nm
When a continuous reaction of reductive amination of dialdehyde was attempted using a nickel catalyst supported on diatomaceous earth having a pore volume of 0.2 ml / g, the catalyst activity tended to decrease in about 10 hours of reaction. (See Comparative Example 1 in this specification). Industrially, the reaction performance does not decrease,
It is preferable from an economic viewpoint that the catalyst can be used continuously for a long period of time and that the catalyst can be reused repeatedly. For that purpose, it is required that the catalyst activity be maintained for a long period of time. Therefore, the method (4) still has room for improvement as an industrial production method of diamine. Accordingly, an object of the present invention is to provide a method for producing a diamine industrially and advantageously in a high yield by using a dialdehyde as a raw material, in which a decrease in catalytic activity is reduced.

[0006]

Means for Solving the Problems The present inventors have found that in the reductive amination reaction of dialdehyde in the presence of a nickel catalyst supported on an inorganic oxide, the pore volume of the inorganic oxide and the catalytic activity are reduced. As a result of examining the relationship, the total volume of pores having a diameter of 1 μm or less of the inorganic oxide was 1.0 ml /
Using a nickel catalyst of at least g, surprisingly, it has been found that diamines can be produced industrially advantageously with high yield with little reduction in catalytic activity even when a long-time continuous reaction is carried out. Reached.

That is, the present invention provides a method for producing a corresponding diamine by reacting a dialdehyde with ammonia and hydrogen in a solvent in the presence of a nickel catalyst supported on an inorganic oxide. Is a method for producing a diamine, wherein the total volume of pores having a diameter of 1 μm or less is 1.0 ml / g or more.

[0008]

DETAILED DESCRIPTION OF THE INVENTION As the inorganic oxide, for example, silica, alumina, silica-alumina, diatomaceous earth, magnesia, calcia, titania, zirconia, niobium oxide,
Inorganic oxides commonly used as catalyst carriers such as lanthanum oxide or mixtures thereof are mentioned. Among them, silica, alumina, silica-alumina, diatomaceous earth or a mixture thereof is preferred. These inorganic oxides may include alkali metal, alkaline earth metal, phosphorus oxides or mixtures thereof. The catalyst metal is mainly nickel, but may be modified with one or more metals such as cobalt, iron, copper, manganese, chromium, silver, molybdenum, rhenium, palladium, rhodium, ruthenium, and platinum. The loading amount of the metal component is preferably in the range of 10 to 80% by weight based on the total weight of the catalyst,
More preferably, it is in the range of 20 to 70% by weight. The ratio of nickel to the metal component is preferably in the range of 80 to 100%, more preferably 90 to 100%.

In the above-mentioned inorganic oxide constituting the nickel catalyst, the total volume of pores having a diameter of 1 μm or less needs to be 1.0 ml / g or more. By using a nickel catalyst supported on an inorganic oxide that satisfies such conditions, a reduction in catalytic activity in the reductive amination reaction of dialdehyde is small, and stable operation for a long time can be performed. The upper limit of the total volume of the pores having a diameter of 1 μm or less of the inorganic oxide is not particularly limited, but is usually in a range of 1.0 to 5.0 ml / g.
It is preferably in the range of 1.0 to 2.5 ml / g.

[0010] The diameter and volume of the pores present in the inorganic oxide can be measured, for example, by mercury intrusion porosimetry. In this measurement method, the pore diameter is determined from the injection pressure of mercury, and the pore volume is determined from the change in the amount of static electricity through the amount of mercury injected. As used herein, pore diameter and pore volume values refer to values obtained by mercury intrusion porosimetry. The present inventors analyzed the pore diameter and the pore volume of the nickel catalyst using an autopore III9420 manufactured by Shimadzu Corporation-Micrometrics Co., Ltd., which is a mercury intrusion porosimeter. Is equivalent to about 1206.6 kPa (175.0 psia) as a mercury injection pressure. Therefore, the pore volume of 1 μm or less in diameter means the sum of the pore volumes measured in the range of the pressure or more. I do. In addition,
Even when a nickel catalyst supported on an inorganic oxide is used as a measurement sample, the volume occupied by the metal particle size of the supported nickel or a metal component containing nickel as a main component is smaller than the pore volume of the inorganic oxide. Since it is sufficiently small, it hardly affects the measured values of the pore diameter and the pore volume in the above-mentioned measuring method, and the obtained measured values are the pore diameter and the pore volume of the inorganic oxide. It can be measured.

The nickel catalyst used in the present invention is commercially available and readily available, and includes, for example, a nickel-alumina catalyst (5329P) commercially available from NE Chemcat (refer to the specification herein). Refer to Reference Example 1). Further, the nickel catalyst used in the present invention, using an inorganic oxide having the above pore volume as a carrier,
It can also be prepared by a known method such as a precipitation method or an impregnation method. These catalyst preparation methods are described in, for example, Catalyst Course Vol. 5, Catalyst Design (Kodansha, published on December 10, 1985), pp. 39-43, and Catalyst Experiment Manual (Maki Shoten, published on July 31, 1971), 305-305. It is described in detail on page 340.

The above nickel catalyst may be in any shape such as powder, granule or column. Further, an oxide of a metal or phosphorus other than nickel that may be contained in the catalyst may be contained in the carrier to be used in advance,
It can be appropriately added during the catalyst preparation step.

The amount of nickel catalyst used can be varied according to the desired reaction rate, but is preferably in the range of 0.01 to 30% by weight based on the reaction mixture.
More preferably, it is in the range of 1 to 10% by weight. Such a catalyst may be used by suspending it in the reaction liquid phase or may be used as a fixed bed. Further, such a catalyst can be used for the reaction as it is, but it is preferable to use it after performing an activation treatment with hydrogen before the reaction.

Examples of the dialdehyde include straight-chains such as butanedial, hexanedial, octanedial, nonandial, decandial, undecandial, dodecandial, tetradecandial, hexadecandial, octadecandial, eicosantial and the like. Aliphatic dialdehydes; branched aliphatic dialdehydes such as 2-methyloctanedial, 2-methylnonandial, and 2,7-dimethyloctanedial;
-Cyclohexanedicarbaldehyde, 1,4-cyclohexanedicarbaldehyde, 3 (4), 8 (9) -tricyclo [5.2.1.0] decanedicarbaldehyde, 2
(3), alicyclic dialdehydes such as 5 (6) -bicyclo [2.2.1] heptane dicarbaldehyde; and aromatic dialdehydes such as terephthalaldehyde and isophthalaldehyde. Among these, carbon number 4 ~
A dialdehyde having 20 is preferred, a dialdehyde having 6 to 16 carbon atoms is more preferred, and a dialdehyde having 8 to 12 carbon atoms is particularly preferred.

These dialdehydes can be easily synthesized, for example, by hydroformylation of an unsaturated aldehyde having one less carbon atom or a diolefin having two less carbon atoms. Further, it can also be obtained by ozonolysis of a cyclic olefin having the same carbon number and subsequent reduction reaction, or reduction reaction of a dicarboxylic acid having the same carbon number.

The concentration of the dialdehyde is not particularly limited,
Usually, it is preferably in the range of 5 to 30% by weight based on the whole reaction solution. When the concentration of the dialdehyde is 5% by weight or less, the volumetric efficiency of the reaction is low, the productivity is low, and the recovery amount of ammonia and the solvent in the diamine separation / purification step is large, and the equipment burden is increased. Value tends to decrease. When the content is 30% by weight or more, the amount of by-products such as polymers in the reaction system tends to increase, and both the diamine yield and the catalytic activity tend to decrease.

Using the above dialdehydes as raw materials, the corresponding butanediamine, hexanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tetradecanediamine,
Linear aliphatic diamines such as hexadecanediamine, octadecanediamine, eicosanediamine; 2-methyloctanediamine, 2-methylnonanediamine, 2,7-
Branched aliphatic diamines such as dimethyloctanediamine; 1,3-cyclohexanedimethanamine, 1,4-cyclohexanedimethanamine, 3 (4), 8 (9) -tricyclo [5.2.1.0] de Candimethanamine, 2
(3) An alicyclic diamine such as 5 (6) -bicyclo [2.2.1] heptane dimethanamine; an aromatic diamine such as p-xylylenediamine and m-xylylenediamine are produced.

As the solvent, any solvent can be used as long as it dissolves the starting dialdehyde, product diamine and ammonia under the reaction conditions and does not adversely affect the reaction. For example, methanol, ethanol, 1-propanol, 2-propanol, Propanol, 1-butanol, isobutanol, tert-butanol, 1-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, te
alcohols such as rt-amyl alcohol, 1-hexanol, 1-heptanol, 1-octanol, 2-ethylhexanol and cyclohexanol; ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 2- Methyl-1,4
Diols such as -butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol and diethylene glycol; ethers such as tetrahydrofuran, 1,3-dioxane and 1,4-dioxane Or mixtures thereof. Among these, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, isobutanol, tert-butanol, 1-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,
Solvents having 5 or less carbon atoms, such as 4-butanediol, 1,5-pentanediol, tetrahydrofuran, 1,3-dioxane, and 1,4-dioxane, are preferred. Although there is no particular limitation on the amount of the solvent used, it is usually preferably in the range of 0.5 to 50 times the weight of the dialdehyde,
More preferably, it is in the range of 0 times by weight.

The amount of ammonia used is preferably in the range of 2 to 100 times, more preferably in the range of 5 to 50 times, and particularly preferably in the range of 10 to 30 times the mole of dialdehyde. preferable. When the amount of ammonia used is less than 2 mole times the dialdehyde, the yield of diamine tends to decrease, and when it is more than 100 mole times, the amount of unreacted ammonia is reduced. The equipment is oversized, which is practically disadvantageous.

The reaction temperature is preferably in the range of 40 to 200 ° C., more preferably in the range of 80 to 180 ° C., and particularly preferably in the range of 100 to 160 ° C. When the reaction temperature is lower than 40 ° C., the progress of the reaction tends to be extremely slow. When the reaction temperature is higher than 200 ° C., the amount of by-products such as a polymer increases and the yield tends to decrease.

The reaction pressure is not particularly limited, but is usually 2 to
It is preferably in the range of 20 MPa. In addition, hydrogen may be added so as to replenish the hydrogen consumed in the reaction,
The reaction may be performed while constantly flowing hydrogen.

The reaction can be carried out in either a batch system or a continuous system, but a method in which dialdehyde is fed into the reactor at a rate lower than the rate of hydrogenation, that is, when dialdehyde or a reaction intermediate is introduced into the reactor. It is recommended to supply the dialdehyde at such a rate that it does not accumulate.
In the case of a batch reactor, a nickel catalyst, a solvent, a solution obtained by dissolving dialdehyde or dialdehyde in a solvent in a reactor filled with ammonia and hydrogen,
A method of reacting while feeding at a rate lower than the hydrogenation rate is preferred. In the case of the continuous system, for example, a nickel catalyst, a solvent and a solution obtained by dissolving dialdehyde in a solvent filled with a solvent and hydrogen, and ammonia at a rate lower than the hydrogenation rate. A method of reacting while feeding is preferable. Note that the supply of the dialdehyde or the solution obtained by dissolving the dialdehyde in the solvent may be continuously performed at a constant rate or may be performed intermittently.

The separation of the catalyst from the reaction solution containing the catalyst is performed, for example, in the case of a continuous reaction, by providing a reaction solution extraction pipe having a metal sintered filter or a ceramic filter at the tip inside the reactor. Only the reaction solution can be withdrawn from the vessel and the catalyst can be retained in the reactor.

In the case of a batch reaction, after the reaction,
The catalyst can be separated by subjecting the reaction solution containing the catalyst to an operation such as filtration or centrifugation. The separated catalyst can be reused as it is or after being subjected to a solvent washing treatment or a hydrogen activation treatment, and then returned to the reactor.

The diamine can be obtained from the reaction solution after the separation of the catalyst by a general purification means. For example, after distilling off ammonia and the solvent, purification is performed by distillation or recrystallization.

[0026]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Reference Example 1 Method of Measuring Pore Volume of Catalyst The pore diameter and the pore volume of the nickel catalyst used in Example 1 and Comparative Example 1 were measured by using a mercury intrusion porosimeter manufactured by Shimadzu Corporation-Micrometrics Co., Ltd. It was measured using Autopore III9420. That is, 1
0.34 kPa to 311.8 MPa (1.5 to 4521
The pressure was changed in the range of 5.9 psia), the pressure was read from the pressure sensor at a pressure equilibrium time of 10 seconds, and the change in the amount of static electricity was read from the electrostatic detector. The pore volume was determined. 1μm diameter
The following pore volumes are from a pressure of 1206.6 kPa to 311.
It is a value calculated as the sum of pore volumes measured in the range of 8 MPa (175.0 to 4515.9 psia). Table 1 shows the measured values. In this measurement method,
A pore volume with a diameter of 100 nm to 10 nm is increased by a pressure of 13.0.
7 MPa to 137.3 MPa (1894.9 to 1991)
Calculated as the sum of the pore volumes measured in the range of 9.3 psia), and the values are also shown in Table 1.

[0028]

[Table 1]

Example 1 A 100 ml autoclave equipped with a magnetic stirrer, a needle valve, a pressure gauge, a gas and a raw material introduction pipe was positioned so that the reaction liquid overflowed to the outside of the autoclave when the amount of the reaction liquid exceeded 30 ml. The adjusted extraction tube was attached. A sintered filter (0.8 μm mesh) was attached to the tip of the extraction tube to extract only the reaction solution from the reaction solution containing the catalyst so that the catalyst could remain in the reactor. As shown in Reference Example 1, a nickel-alumina catalyst having a total pore volume of 1.6 ml / g having a diameter of 1 μm or less and a pore volume of 0.6 ml / g having a diameter of 100 nm to 10 nm was added to the autoclave as shown in Reference Example 1. E-Chemcat, 5329P) 0.37
g and 14.6 g of isoamyl alcohol.
The inside of the autoclave was replaced with hydrogen of Pa three times. next,
After pressurizing with 3 MPa of hydrogen and raising the temperature of the autoclave to 140 ° C., the total pressure in the autoclave was increased to 8.5 MPa with hydrogen.
The pressure was adjusted so as to be a, and the catalyst was reduced at this temperature for 4 hours. Cool the autoclave to room temperature,
After releasing the pressure of hydrogen, 9.0 g of ammonia was charged, and the pressure was again increased to 3 MPa with hydrogen, the temperature was raised to 140 ° C., and the total pressure in the autoclave was adjusted to 8.5 MPa with hydrogen. In this autoclave, 1,9-nonandial / 2-methyl-1,8-octanediol = 75 /
25 (molar ratio), a mixed solution of isoamyl alcohol and triethylene glycol dimethyl ether (added as an internal standard substance for gas chromatography measurement) (weight ratio: 5.9 g / 12.0 g / 1.0 g) was added to 1
8.9 g / h, hydrogen gas 10 l / h, ammonia 1
The reaction was fed at a rate of 0.9 g / hour to carry out a continuous reaction. The reaction solution overflowing from the extraction tube was led to a gas-liquid separation tube to separate ammonia, and the collected solution was sampled every hour and subjected to gas chromatography analysis to calculate the diamine yield. 1,9-nonanediamine and 2-methyl-1,
The total yield of diamine including 8-octanediamine was 94%, 93%, and 91% after 2 hours, 10 hours, and 20 hours from the start of the reaction.

Comparative Example 1 As shown in Reference Example 1, the catalyst had a total pore volume of 0.7 ml / g and a diameter of 1 μm or less, and a diameter of 100 nm to 10 n.
Nickel-diatomaceous earth catalyst having a pore volume of 0.2 ml / g (manufactured by Nikki Chemical Co., Ltd., N103LK) 0.45
A continuous reaction was carried out in the same manner as in Example 1 using the same reactor as in Example 1 except that g was used. 1,9
The combined yield of 2-nonanediamine and 2-methyl-1,8-octanediamine was 1 hour after the start of the reaction.
After 0 hour and 15 hours, 94%, 86%, 7% respectively
9%.

Comparative Example 2 As a catalyst, Raney nickel (manufactured by Degussa-Hüls,
A continuous reaction was carried out in the same manner as in Example 1 except that 0.37 g of BLM112W) was used. The combined yields of 1,9-nonanediamine and 2-methyl-1,8-octanediamine were 93%, 80%, and 65% after 2 hours, 10 hours, and 15 hours from the start of the reaction. Was.

[0032]

According to the present invention, a dialdehyde can be used as a raw material to reduce the catalytic activity and to produce a diamine in a high yield and industrially advantageous.

Continued on the front page F-term (reference) 4G069 AA03 AA12 BA01A BA01B BA02A BA03A BA04A BA05A BA06A BA15A BB02A BB02B BB04A BC09A BC42A BC55A BC68A BC68B CB25 CB77 EA01Y EA02Y EC08X EC08Y BAH40A56 BE56A56

Claims (1)

[Claims] 1. A method for producing a corresponding diamine by reacting a dialdehyde with ammonia and hydrogen in a solvent in the presence of a nickel catalyst supported on an inorganic oxide, wherein the inorganic oxide has a diameter of 1 μm or less. Wherein the total volume of the pores is 1.0 ml / g or more.