JPH069512A - Process for producing serinol or derivative thereof - Google Patents

Abstract

(57) [Summary] [Structure] A method for producing serinol or a derivative thereof, which comprises reductive amination of dihydroxyacetone in the presence of a supported catalyst composition containing only rhodium as a catalyst component, and palladium, platinum, A method for producing serinol or a derivative thereof, which comprises reductive amination of dihydroxyacetone in the presence of a supported catalyst composition containing, as a catalyst component, two or more components selected from the group consisting of rhodium, ruthenium and iridium. . [Effect] According to the production method of the present invention, the catalytic activity in the reductive amination reaction of dihydroxyacetone can be significantly improved, and in particular, by efficiently proceeding the reductive amination reaction in water, the corresponding amine The serinol or its derivative can be produced in high yield.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing serinol or a derivative thereof for converting a dihydroxyacetone into a corresponding amine, serinol or a derivative thereof in high yield by reductive amination. Serinol or its derivatives are extremely important as pharmaceuticals, intermediate raw materials for amino acids, moisturizers, and surfactants.

[0002]

Reductive amination reaction of dihydroxyacetone monomer having a carbonyl group is the most effective method for producing serinol. In order to allow the reductive amination reaction to proceed efficiently, the reaction conditions that take into consideration these physical properties of dihydroxyacetone are not stable to substances, and commercially available dihydroxyacetone has a dimer structure. is necessary. However, the conventional method does not take this point into consideration and is not always satisfactory. For example, German Patent Publication No. 2829916 describes reductive amination of dihydroxyacetone in an organic solvent in the presence of a catalyst such as nickel, cobalt, platinum, or palladium. Examples using a single precious metal catalyst are mentioned for the purpose. However, there is no specific description of the yield in all the examples of the publication, and its effect is unknown. Therefore, the inventors of the present invention have disclosed palladium, platinum,
When the catalytic activity of ruthenium, iridium, etc. was retested, the yields of palladium, platinum, ruthenium, and iridium were 3%, 28%, 1%, and 0.5%, respectively, when they were single,
The reductive amination activity was extremely low and it was not practical.

On the other hand, JP-A-62-169751 discloses that a commercially available dihydroxyacetone dimer, which is easily available, is used as a raw material for the reductive amination reaction, and the compound is reductively aminated in water in the presence of a nickel or cobalt catalyst. The novelty is based on the fact that the equilibrium is easily transferred to the dihydroxyacetone monomer having an effective carbonyl group as a raw material. Therefore, the inventors of the present invention made an additional test of this patent. However, when crystals of dihydroxyacetone dimer were dissolved in water to form an aqueous solution and a reductive amination reaction was carried out, the yield was about 40%. It was found that there is a problem that it takes a long time until the equilibrium with the dihydroxyacetone monomer side is established because the moving speed to the is slow. Further, in the example of the publication, nickel,
In the reductive amination reaction at a reaction temperature of 90 ° C. in the presence of a cobalt catalyst, the catalytic activity of such an element may be low, and the isomerization reaction and the polymerization reaction are likely to occur simultaneously, which is not always satisfactory. As is clear from the above, in order to produce serinol by the reductive amination reaction of the dihydroxyacetone monomer or its dimer, the reductive amination reaction should be carried out at the highest possible temperature at the lowest temperature in consideration of the physical properties of dihydroxyacetone. It is necessary to develop a low-temperature high-activity catalyst that can proceed, and the conventional catalyst has not yet been satisfactory.

[0004]

The inventors of the present invention have made extensive studies as to a catalyst which is excellent in catalytic activity at low temperature, has few side reactions, and can efficiently carry out reductive amination reaction in water. It has been found that by using a catalyst, dihydroxyacetone can be converted to the corresponding amine serinol or its derivatives in very high yields. That is, the inventors of the present invention, in advancing the development of the catalyst used in the present invention in order to solve the above problems, include palladium (Pd), platinum (Pt), rhodium (which are noble metal elements of Group 8 of the periodic table). The basic catalytic activities of Rh), ruthenium (Ru) and iridium (Ir) and the synergistic effect of using a plurality of these elements in combination were examined. As a result, when the reductive amination reaction was carried out by applying the supported catalyst composition used in the present invention to dihydroxyacetone in the presence of an aminating agent under mild conditions, the corresponding amine serinol or its derivative was obtained in high yield. Found something to give to. Moreover, it was found that under these conditions, the reductive amination reaction in water can proceed efficiently, and the present invention has been completed.

That is, the gist of the present invention is (1) in the presence of a supported catalyst composition containing only rhodium as a catalyst component,
A method for producing serinol or a derivative thereof, which comprises reductive amination of dihydroxyacetone, and (2) containing two or more kinds of components selected from the group consisting of palladium, platinum, rhodium, ruthenium and iridium as a catalyst component. It relates to a process for producing serinol or a derivative thereof, which comprises reductive amination of dihydroxyacetone in the presence of a supported catalyst composition.

The supported catalyst composition in the present invention is a composition composed of a catalyst component and a catalyst carrier. In the catalyst composition, (1) Rh alone using only Rh is used as the catalyst component. Aspect and (2) Pd, Pt, Rh, R
There is an embodiment of a combination using two or more kinds of catalyst elements selected from the group consisting of u and Ir.

Examples of the combination mode using two or more catalyst elements include a combination of two-component catalysts and a combination of multi-component catalysts of three or more components. As a combination of two-component catalysts, Rh.Pt, Rh.Pd, Rh.Ru, Rh.
Ir, Pt / Pd, Pt / Ru, Pt / Ir, Pd / R
u, Pd · Ir, Ru · Ir and the like are mentioned, but not particularly limited, but in the present invention, Pd
By using as a main component a catalyst such as Rh, Pt, Ru or Ir, a high catalytic activity can be obtained. Also,
When Pt is used as the main component in combination with Rh, Pd, Ru or Ir, high catalytic activity can be obtained as in the case of using other catalyst in combination with Pd. Specifically, Pd ・ R
h, Pd / Ru, Pd / Ir, Pt / Rh, Pt / R
Suitable examples include u and Pt.Ir. Also,
More preferably, especially Pd.Rh, Pd.Ru, Pt.
A combination of Rh and Pt.Ru can be mentioned as one showing extremely high catalytic activity. In this case, Pd
A catalyst composition using a small amount of Rh or Ru or a catalyst composition using Pt in combination with a small amount of Rh or Ru is particularly effective.

In the present invention, the two-component catalyst is used as a basic catalyst, and among Pd, Pt, Rh, Ru and Ir, elements other than the elements used as the two-component catalyst are used in combination as the third component to obtain catalytic activity. May be further improved. When such three kinds of catalyst elements are used in combination (three-component catalyst), for example, Pd / Pt / R
h, Pd / Pt / Ru, Rh / Pt / Ru and Rh /
Pd / Ru, etc. are effective. Further, in addition to these as the third component, if one or more rare earth elements, copper, nickel, cobalt, silver, gold, etc. are used in combination, the catalytic activity and the catalyst durability may be improved. Furthermore, a multi-component catalyst of three or more components may be used as appropriate. These three-component or multi-component catalysts can overwhelm the active function of conventional catalysts, especially when the reductive amination reaction of dihydroxyacetone is carried out in water.

As the catalyst carrier in the supported catalyst composition used in the present invention, one or more kinds usually used, for example, one or more selected from the group consisting of activated carbon, alumina, silica and zeolite can be used. Further, other examples include molecular sieves. Above all, activated carbon is particularly effective in that a highly dispersed catalyst can be prepared. When activated carbon is used, it is preferable to use one having a high surface area, and it is preferable to use one having physical properties such as BET specific surface area, pore volume, and ash content in specific ranges. Since the BET specific surface area has a great influence on the high dispersibility of the catalyst component,
It should be 300 m ² / g or more, preferably 600 m
² / g or more, more preferably 1000 m ² / g or more, and particularly preferably 1200 m ² / g or more. BE
If the T specific surface area is less than 300 m ² / g, the reaction of the present invention cannot proceed efficiently. Further, the pore volume of activated carbon is preferably about 0.3 cc / g to 1.5 cc / g, and if it is outside this range, the catalytic activity may decrease. Ash content should be as low as possible 1
It may be 5% by weight or less. Preferably 5% by weight or less,
It is more preferably 2% by weight or less, and if it exceeds 15% by weight, the catalytic activity may decrease.

When activated carbon is used as the catalyst carrier, it may be derived from any raw material such as coconut shell, coal-based, peat carbon-based, or petroleum pitch-based, but especially palm with a low ignition residue or low ash content. Shell type and petroleum pitch type are effective. The activated carbon may be activated by either steam activation or chemical activation, but chemical activation, which has a high activation effect, may be more effective as a carrier.
As the activated carbon as the catalyst carrier used in the present invention, a commercially available product may be used as it is, but a suitable pretreatment,
For example, it may be used after adjusting the pore distribution or reducing the ash content by acid treatment or the like. Examples of commercially available granular and powdered activated carbon used in the present invention include Takeda Pharmaceutical Co., Ltd.
Granular Shirasagi series (WH, Sx, KL) and powdered activated carbon typified by carborafine, Nippon Norit Co., Ltd.
Granular activated carbon (ROX, RAX, DARCO, C, E
LORIT) and powder products (AZO, PN, ZN)
Etc.), beaded shaped activated carbon (BA) of Kureha Chemical Industry Co., Ltd.
C), and super activated carbon having an ultra-high surface area manufactured by Osaka Gas Co., Ltd. Γ-alumina is effective as the alumina.
In addition, when silica, zeolite, molecular sieve or the like is used as a catalyst carrier, ordinary ones can be used.

In preparing the supported catalyst composition of the present invention, examples of raw materials for the catalyst component Rh include rhodium chloride, rhodium acetate, rhodium acetylacetone, rhodium nitrate, and an ammonia complex of rhodium.
Examples of raw materials for the catalyst component Pt include chloroplatinic acid and platinum ammonia complex. Examples of the raw material of the catalyst component Pd include palladium chloride, palladium nitrate, palladium acetate, palladium acetylacetone, and an ammonia complex of palladium. Examples of the raw material of the catalyst component Ru include ruthenium chloride, ruthenium acetylacetone, and an ammonia complex of ruthenium. Examples of the raw material for the catalyst component Ir include iridium chloride, iridium nitrate, and iridium acetylacetone. In addition to the catalyst of the present invention, cobalt, nickel, copper, silver,
When gold or the like is used in combination, the catalytic activity may be improved. In this case, examples of the raw material for the catalyst component cobalt include cobalt acetate, cobalt nitrate, cobalt acetylacetone and the like. Examples of raw materials for the catalyst component nickel include nickel chloride, nickel acetate, nickel nitrate, nickel acetylacetone, and the like. Examples of the raw material of the catalyst component copper include copper chloride, copper nitrate, copper acetate, copper acetylacetone, and the like. Examples of raw materials for the catalyst component silver include silver nitrate, silver chloride, and silver acetate. Examples of raw materials for the catalyst component gold include gold chloride and gold bromide.

The supported catalyst composition of the present invention is obtained by supporting Rh alone or by supporting two or more kinds of catalyst components on a single carrier, or two or more kinds of supported catalysts of each catalyst element. There are two modes in which a mixed catalyst is formed by mixing. In order to support Rh alone or two or more kinds of catalyst components on a single carrier as the supported catalyst composition in the present invention, known impregnation methods, co-impregnation methods, co-precipitation methods, ion exchangers and the like are known. It can be easily prepared by a method.
For example, in order to prepare a Rh.Pd two-component catalyst using activated carbon as a carrier by the coprecipitation method, a uniform hydrochloric acid acidic aqueous solution of palladium chloride and rhodium chloride is prepared and supported on activated carbon at room temperature. After completion of the supporting treatment, a caustic aqueous solution is added to make the solution basic without removing the aqueous solution, and the catalyst component is precipitated as hydroxide to be fixed on the carrier. After that, the catalyst component is subjected to reduction treatment with a reducing agent such as formalin, sodium borohydride, hydrazine, etc., washed with water and then filtered for use. The obtained catalyst may be used as a water-containing product or may be used as a dried product. Alternatively, after carrying out the catalyst component supporting treatment, the excess aqueous solution may be evaporated to dryness and dried, and hydrogen may be reduced to activate the catalyst.
In the above loading method, two or more types of carriers may be loaded at the same time, and two or more types of catalyst components may be loaded on each single support.

Further, in the supported catalyst composition of the present invention, in order to mix two or more kinds of supported catalysts of each catalytic element to form a mixed catalyst, a palladium-supported catalyst, a platinum-supported catalyst, a rhodium-supported catalyst, a ruthenium-supported catalyst and It can be easily obtained by physically mixing two or more kinds of desired supported catalysts from the iridium-supported catalyst so as to obtain a predetermined composition ratio. Further, two or more kinds of desired supported catalysts may be separately charged and used in the reaction system.

When a plurality of catalyst components are used in combination, the composition ratio between the catalyst elements varies depending on the combination of the elements.
In the case of a Pd two-component catalyst, Rh / Pd is a weight ratio of preferably 10 to 0.0001, particularly preferably 1 to 0.00.
01. The smaller the ratio of Rh to Pd, the greater the catalytic activity, but the ratio becomes too small and Rh / Pd
When the weight ratio is less than 0.0001, the catalytic activity is the same as in the case of Pd alone, and the synergistic effect due to the composite formation is not recognized. On the other hand, the ratio of Rh to Pd increases and Rh
When / Pd exceeds 10 by weight, decomposition of the product is likely to occur at the same time, which is disadvantageous in cost. Ru / Pd2
The same range is preferable for the component catalysts. On the other hand, Rh
In the case of a Pt two-component catalyst, the Rh / Pt weight ratio is preferably 10 to 0.0001, particularly preferably 1 to 0.000.
It is 1. The smaller the ratio of Rh to Pt, the greater the catalytic activity. However, if the ratio becomes too small and the Rh / Pt weight ratio is less than 0.0001, the catalytic activity is the same as that of Pt alone, and it depends on the combination. No synergistic effect is observed. On the other hand, the ratio of Rh to Pt increases and Rh /
When Pt exceeds 10 by weight, decomposition of the product is likely to occur at the same time, which is disadvantageous in cost. Further, in the case of a Ru / Pt two-component catalyst, the same range is preferable.

Further, the two-component catalysts Rh.Pd and R
h.Pt, Ru.Pd or Ru.Pt as a basic catalyst, and components other than the two-component catalyst (Pt, Pd, I
r, Rh, Ru), or cobalt, nickel, copper,
Even when one or more components such as silver and gold are used together, Rh / P
The weight ratio of d, Rh / Pt, Ru / Pd and Ru / Pt is preferably within the above range.

Rh which is the supported catalyst composition in the present invention
-Pd, Rh-Pt, Rh-Ir, Ru-Pd, Ru-
Two-component catalyst such as Pt, Ru / Ir, Rh / Pt / Pd,
Ru / Pt / Pd, Rh / Ru / Pt, Rh / Ru / P
In a three-component catalyst such as d, Pd expresses its remarkable hydrogen storage property and accelerates the hydrogenation step during the reductive amination reaction. On the other hand, Rh and Ru exhibit a hydrogen spillover effect to remarkably accelerate the hydrogenolysis step of the reductive amination reaction. By combining these two functions, a particularly remarkable improvement in catalytic activity is achieved. In order to exhibit the spillover effect derived from Rh and Ru and / or the hydrogen storage property derived from Pd in the supported catalyst composition of the present invention, a single component supported catalyst composed of these catalytic elements is physically mixed and used. More easily achieved. Alternatively, even when Rh, Ru, and Pd are mixed and used as a homogeneous solution at the stage of preparation in which these catalyst elements are supported on a single carrier, such effects can be exhibited. The hydrogen storage property and / or the spillover effect can be similarly exhibited in a catalyst composition composed of four or more components.

The amount of catalyst supported in the supported catalyst composition is 30.
˜0.1% by weight, preferably 10 to 0.5% by weight. If the supported amount is more than 30% by weight, it is disadvantageous in terms of cost and there is no particular advantage in catalytic activity. Further, if it is less than 0.1% by weight, the reaction cannot proceed efficiently.

The supported catalyst composition used in the present invention can be used in various reactors depending on its form. That is, when the supported catalyst composition is in the form of powder, it can be used in a batch reactor, a fluidized bed reactor, an injector reactor, etc., on the other hand, when a molded granular carrier or crushed carrier is used. Can be used in fixed bed reactors and the like. The amination reaction itself may be a batch system or a continuous system.

The reaction route from dihydroxyacetone to serinol in the present invention is considered as in the following formula (1). In this example, ammonia is used as the aminating agent, but the reaction proceeds similarly when a primary amine or a secondary amine is used instead of ammonia, and is converted into a corresponding serinol derivative.

[0020]

[Chemical 1]

The dihydroxyacetone used in this reaction may be either a commercially available product or a product produced by catalytic oxidation of glycerin or the like. The product produced by the catalytic oxidation method is particularly effective because dihydroxyacetone is present in the monomer structure. When produced by catalytic oxidation or the like of glycerin, the starting glycerin can be produced by hydrolysis or transesterification of fats and oils.

As the aminating agent used in the amination reaction, ammonia or various primary amines or secondary amines can be used. The primary amine or secondary amine may be an aliphatic type, an alicyclic type, or an aromatic type, and may have a substituent on these. Examples of these primary amines or secondary amines include methylamine, dimethylamine, ethylamine, diethylamine, propylamine,
Dipropylamine, hexylamine, octylamine,
Decylamine, dodecylamine, tetradecylamine,
Hexadecylamine, octadecylamine, cyclohexylamine, benzylamine and the like can be mentioned. These amines have different usage forms depending on their molecular weights, but in the case of gaseous ammonia, methylamine, dimethylamine, ethylamine, etc., they are used in the gaseous form or diluted with a suitable solvent, for example, as an aqueous solution. Good. In the case of a liquid or solid amine having a long-chain alkyl group, it can be used as a liquid or diluted with a solvent.

In the present invention, the molar ratio of the aminating agent to dihydroxyacetone [aminating agent / dihydroxyacetone] may be in the range of 0.1 to 50, preferably 0.3 to 10, and more preferably 0. 5 to 3. If the molar ratio of the aminating agent is less than 0.1, the reaction rate is slow and it is not practical. On the other hand, when the molar ratio of the aminating agent exceeds 50, side reactions are likely to occur simultaneously, which is not practical.

In carrying out the reductive amination reaction of dihydroxyacetone using the supported catalyst composition of the present invention, dihydroxyacetone is diluted with an appropriate solvent that does not undergo the reductive amination reaction from the viewpoint of improving the reaction rate. It is preferable to use. Water is particularly effective as the solvent. The reason is that dihydroxyacetone is produced by catalytic oxidation of its starting material, glycerin, in water. In this case, the dihydroxyacetone supplied as an aqueous solution can be used as it is for the reductive amination reaction, which is a great merit in the process. The concentration of the aqueous solution of dihydroxyacetone may be in the range of about 90 to 1% by weight, preferably 70 to 1% by weight, more preferably 50 to 2% by weight. When diluted to less than 1% by weight, it becomes impractical. In addition to the above solvents, usual polar solvents such as methyl alcohol, ethyl alcohol, tetrahydrofuran, dimethylformamide and dimethylacetamide can be used.

In the reductive amination reaction of the present invention, the hydrogen pressure is usually in the range of 200 atm or less, preferably 60 atm or less. Even under normal pressure, the reaction can be sufficiently advanced by setting the reaction conditions. When the hydrogen pressure is higher than 200 atm, the decomposition reaction of the product is promoted and the yield of the product is significantly reduced.
Further, when the hydrogen pressure is below atmospheric pressure, the reaction rate is lowered and it is not always effective. The reductive amination reaction in the present invention is carried out in the coexistence of hydrogen. Further, instead of hydrogen, a compound such as sodium borohydride or hydrazine as a hydrogen generating agent may be used.

In the reductive amination of dihydroxyacetone using the supported catalyst composition of the present invention in the presence of an aminating agent and hydrogen, the molar ratio of hydrogen to dihydroxyacetone [hydrogen / dihydroxyacetone] is 0.1 to 400. In the range of 0.5, preferably 0.5
-100, more preferably 1-50. If the hydrogen molar ratio is less than 0.1, the reaction rate will be extremely slow and
If it exceeds, decomposition reactions are likely to occur simultaneously.

In the reductive amination reaction of the present invention, the reaction temperature is usually in the range of 0 to 150 ° C, preferably about 0 to 100 ° C, more preferably about 20 to 80 ° C. When the reaction temperature exceeds 150 ° C., the decomposition reaction of the product is promoted and the yield of the product is significantly reduced. Further, if the reaction temperature is lower than 0 ° C, the reaction rate is remarkably reduced, which is not practical. Therefore, the supported catalyst composition used in the production method of the present invention is an optimum catalyst system for the synthesis of thermally unstable serinol and its derivatives. The reaction time varies depending on the reaction temperature, but is usually 1 to 20 hours, preferably 1 to 1
0 hours, particularly preferably 1 to 5 hours. After completion of the reaction, the target serinol or its derivative can be easily separated by appropriately using a method such as a chromatographic separation method, a crystallization separation method, a distillation separation method or an ion exchange method.

Thus, when the supported catalyst composition of the present invention is used to reductively aminate dihydroxyacetone in the presence of ammonia and hydrogen, the reactor as described above is treated with, for example, a 10% by weight aqueous solution of dihydroxyacetone. A catalyst may be added, and ammonia may be bubbled into the reactor together with hydrogen gas through a gas introduction pipe. Alternatively, when ammonia is used as ammonia water, it may be dropped into the reactor. Reaction temperature 0-150 ℃
And set the hydrogen pressure to 200 atm or less. The reaction conditions are preferably set so that the reaction time is 1 to 20 hours, and preferably the reductive amination reaction is completed within 10 hours. If the reaction time is excessively long, the product is likely to decompose, which is not preferable. As a result of performing the reductive amination reaction under the above conditions, serinol is produced in high yield as the produced amine. When carrying out in a fixed bed continuous system, the reaction can be carried out by charging a granular catalyst in a reaction tower and supplying a dihydroxyacetone solution and ammonia and hydrogen in a downward cocurrent, an upward cocurrent, or a countercurrent. it can.

As described above, one of the major characteristics of the reductive amination reaction of dihydroxyacetone by the production method of the present invention is that the reaction can proceed efficiently in water. This point brings a great process advantage since dihydroxyacetone is produced by oxidation of glycerin in water. That is, since the aqueous solution of dihydroxyacetone obtained by the oxidation of glycerin in water can be used as it is as a raw material for the reductive amination reaction, the reductive amination reaction according to the production method of the present invention can be directly performed without isolation of dihydroxyacetone. Can be used for Therefore, the merit is very large. These effects have never been achieved with conventional catalysts, and show how excellent the supported catalyst composition used in the present invention is.

As described above, the production method of the present invention makes it possible to significantly improve the catalytic activity in the reductive amination reaction of dihydroxyacetone by using the specific catalyst alone or in combination with a plurality of components as the catalytic component. In particular, it is characterized in that the reductive amination reaction in water can be efficiently progressed.

[0031]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 300 g of a 10% aqueous solution of dihydroxyacetone prepared by a catalytic oxidation reaction of glycerin, 18 g of a 25% aqueous ammonia solution, and 7.5 g of a 5% rhodium-supported carbon catalyst as a catalyst were charged into a 0.5 liter autoclave, and after hydrogen substitution. The temperature was raised to 60 ° C. at 0 gauge pressure, and then the hydrogen pressure was adjusted to 6 atm to carry out the reductive amination reaction. Hydrogen absorption was observed as the reaction proceeded, and the hydrogen absorption stopped after 4 hours. The catalyst was filtered off from the reaction completion product, and the product was quantified by an amino acid analyzer under the following conditions. As a result, the yield (mol%) of serinol was 91.3%,
It was found that the reductive amination reaction of dihydroxyacetone proceeded. Furthermore, the fact that the product is serinol was compared with that of the standard product and liquid chromatography-mass spectrometry (LC-MAS
Confirmed by S). Further, when a reductive amination reaction was similarly carried out using a commercially available dihydroxyacetone (a dimer of 99% by weight or more), serinol was produced at a yield of 63.5%. From this, it can be seen that the reactivity of dihydroxyacetone produced by the catalytic oxidation reaction (99% by weight or more of the monomer in dihydroxyacetone) is higher.

The activated carbon used as the carrier has a BET specific surface area of 1250 m ² / g, a pore volume of 0.36 cc / g and an ash content of 0.5% by weight. In addition, also in other Examples (Examples 2 to 12), this activated carbon was used as a carrier.

The measurement conditions of the amino acid analyzer are as follows. Analyzer: High-speed amino acid analyzer L-8500 type (manufactured by Hitachi Ltd.) Column: 4.6 mm I.D. D × 60 mmL Ammonia trap column: 4.6 mmI. D x 40m
mL Eluent: PF-KIT, 0.35 mL / min Detector: UV absorption, 570 nm

The LC-MASS measurement conditions are as follows. (1) Measurement model M-1000 type LC mass spectrometer (manufactured by Hitachi Ltd.) (2) HPLC conditions Column: GL-C611-S 7.8 mm ID × 30 m
mL Column temperature: 60 ° C. Eluent flow rate: 0.51 ml / min Sample injection amount: 2 μl (3) APCI (atmospheric pressure chemical ionization) conditions Atomizer temperature: 250 ° C. Desolvation chamber temperature: 400 ° C. Drift voltage: Positive ionization mode; 35V negative ionization mode; -35V

Example 2 The activities of various catalysts were compared under the same charging conditions and reaction conditions as in Example 1 except that the catalyst and the reaction time were 2 hours. In Examples 2 to 12, a 10% aqueous solution of dihydroxyacetone synthesized by the catalytic oxidation method of glycerin was used. That is, with respect to 7.5 g of 5% palladium-supported carbon catalyst as the catalyst first component, 0.5% of rhodium-supported carbon catalyst, 5% ruthenium-supported carbon catalyst, or 5% iridium-supported carbon catalyst as the catalyst second component was added. 1
5 g was added, and the effect of adding various catalyst second components having palladium as the catalyst first component was observed. As a result, the yield of serinol was 95.6% when the second catalyst component was rhodium, 92.3% when it was ruthenium, and 7% when it was iridium.
It was 2.3%. On the other hand, when 7.5 g of 5% palladium-supported carbon catalyst or 5% ruthenium-supported carbon catalyst was added and the activity of a single catalyst component was measured, the serinol yields were 5% and 1% for both catalysts, respectively. It was From the above, it was found that by combining the catalyst components, a catalyst activity extremely exceeding the activity of the single component catalyst was exhibited.

Example 3 Using a 5% platinum-supported carbon catalyst as the first component of the catalyst,
The same conditions as in Example 2 were used except that the second component of the catalyst was added. The amount of the catalyst first component added was 7.5 g, and the amount of the catalyst second component added was 0.15 g, which is the same amount as in Example 2. As a result, the yield of serinol was 98.9% when the second catalyst component was rhodium, 97.3% when it was ruthenium, and 62.8% when it was iridium. Since the yield of serinol is 42.0% when the 5% platinum-supported carbon catalyst alone is used as the first catalyst component, the combined effect of using two types of catalyst components in this case is also the same as in Example 2. Is expressed.

Example 4 7.5 g of 5% platinum-supported carbon catalyst was used as the first component of the catalyst, and 5% rhodium-supported carbon catalyst was used as the second component of the catalyst at 1/20, 1 / the amount of the platinum-supported carbon catalyst used. 50, 1 /
The reaction was carried out under the same conditions as in Example 2 except that 200 and 1/500 were used. The results are shown in Table 1, and as the amount of rhodium added decreases, the yield of serinol increases,
It can be seen that rhodium as the second component of the catalyst exhibits the hydrogen spillover effect.

Example 5 As a catalyst first component, 5% palladium-supported carbon catalyst 7.
5 g was used, and 5% of the ruthenium-supported carbon catalyst as the second component of the catalyst was used in half the amount of the palladium-supported carbon catalyst.
0, 1/50, 1/200, 1/500, except
The reaction was carried out under the same conditions as in Example 2. The results are shown in Table 1.
In this case as well, the yield of serinol increased as the amount of ruthenium added decreased, and the spillover effect was observed as in the case of rhodium of Example 4.

EXAMPLE 6 5% Palladium-supported carbon catalyst 7.5 as the first catalyst component
g, 0.15 g of 5% rhodium-supported carbon catalyst as the second catalyst component was used, and the reaction was carried out under the same conditions as in Example 2 except that the reaction was carried out at various reaction temperatures. The results are shown in Table 1 comparing the effects of reaction temperature.

[0040]

[Table 1]

Example 7 5% Palladium-supported carbon catalyst 7.5 as the first catalyst component
g, 5% rhodium-supported carbon catalyst as a second component of the catalyst 0.
Except for using 15 g and at various hydrogen pressures,
The reaction was carried out under the same conditions as in Example 2. The results are shown in Table 2 comparing the effects of reaction pressure.

Example 8 0.63 g of palladium chloride as a raw material for the first catalyst component and 0.015 g of rhodium chloride as a raw material for the second catalyst component
Is uniformly dissolved in 100 ml of 1N hydrochloric acid, and activated carbon 7.
1 g was added and the supporting treatment was carried out at room temperature for 5 hours. After that, adjust the pH to 11 or higher with 1N sodium hydroxide, and
2 ml of a 5% formalin aqueous solution was added and reduction treatment was performed at 80 ° C. for 30 minutes. The obtained catalyst was about 7.
It was 5 g. The reductive amination reaction was performed in the same manner as in Example 2 except that the entire amount of this catalyst was used. As a result, the yield of serinol was 89.2%.

Example 9 5% Palladium-supported carbon catalyst 7.5 as the first catalyst component
g, and 5% ruthenium-supported carbon catalyst and 5% platinum-supported carbon catalyst were both used as the catalyst second component in an amount of 0.15 g, and the reductive amination reaction was carried out under the same reaction conditions as in Example 2. As a result, the yield of serinol was 99.8%.

Example 10 5% palladium-supported carbon catalyst 7.5 as the first catalyst component
g, a reductive amination reaction was carried out under the same reaction conditions as in Example 2 except that 0.15 g of a 5% ruthenium-supported alumina catalyst was used as the second component of the catalyst. As a result, the yield of serinol was 89.5%.

Example 11 A 20% aqueous solution of ethylamine (molar ratio of ethylamine to dihydroxyacetone is 1.10) was used as an aminating agent for the reductive amination reaction, and 7.5 g of a 5% palladium-supported carbon catalyst was used as a catalyst first component. 5% as the second component
The reductive amination reaction was carried out under the same reaction conditions as in Example 2 except that 0.15 g of the rhodium-supported carbon catalyst was used and the reaction temperature was 70 ° C. As a result, N-ethylserinol was produced as a corresponding reductive amination product in a yield of 78.3%.

Example 12 Ethanol solution of laurylamine (10% by weight concentration) 1
50 g, 10% dihydroxyacetone aqueous solution 75 g, 5% palladium-supported carbon catalyst 7.5 as the first catalyst component
g, 5% rhodium-supported carbon catalyst as a second component of the catalyst 0.
The reductive amination reaction was carried out under the same reaction conditions as in Example 2 except that 15 g was used. As a result, N-lauryl serinol was produced in a yield of 41.5%.

[0047]

[Table 2]

[0048]

According to the production method of the present invention, the catalyst activity in the reductive amination reaction of dihydroxyacetone can be significantly improved by using a specific catalyst as a catalyst component alone or in combination with a plurality of components. Particularly, by efficiently proceeding the reductive amination reaction in water, the corresponding amine serinol or its derivative can be produced in high yield, which is an industrially very useful method.

Claims (8)

[Claims] 1. A process for producing serinol or a derivative thereof, which comprises reductively aminating dihydroxyacetone in the presence of a supported catalyst composition containing only rhodium as a catalyst component. 2. Dihydroxyacetone is reductively aminated in the presence of a supported catalyst composition containing two or more components selected from the group consisting of palladium, platinum, rhodium, ruthenium and iridium as catalyst components. A method for producing serinol or a derivative thereof. 3. A supported catalyst composition comprising two or more components as a catalyst component, wherein two or more components selected from the group consisting of palladium, platinum, rhodium, ruthenium and iridium are supported on a single carrier. Or a mixed catalyst formed by mixing two or more supported catalysts selected from the group consisting of palladium-supported catalysts, platinum-supported catalysts, rhodium-supported catalysts, ruthenium-supported catalysts and iridium-supported catalysts. 2. The manufacturing method according to 2. 4. The method according to claim 1, wherein the carrier is one or more carriers selected from the group consisting of activated carbon, alumina, silica and zeolite. 5. The production method according to claim 1, wherein the reductive amination reaction is carried out in water. 6. The production method according to claim 2, wherein the catalyst component of the supported catalyst composition is palladium and rhodium. 7. The method according to claim 2, wherein the catalyst component of the supported catalyst composition is platinum and rhodium. 8. The method according to claim 2, wherein the catalyst component of the supported catalyst composition is palladium and ruthenium.