JP4170696B2 - Method for producing adamantanes - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing adamantanes. More specifically, the present invention is a method for producing adamantanes using a solid catalyst, and does not require troublesome operations such as waste liquid treatment, and efficiently produces high-purity adamantanes while minimizing loss. The present invention relates to an industrially advantageous method for producing adamantanes.
[0002]
[Prior art]
Adamantane has a structure in which four cyclohexane rings are bonded in a cage shape, is a highly symmetric and stable compound, and adamantanes having such an adamantane skeleton exhibit a unique function. It is known to be useful as an agent, a raw material for agricultural pharmaceuticals or high-functional industrial materials.
As a method for producing this adamantane, a method of isomerizing a tricyclic saturated hydrocarbon compound having 10 or more carbon atoms is generally employed.
In this isomerization reaction, aluminum chloride is generally used as a catalyst.
For example, adamantane is obtained by catalytic isomerization of trimethylene norbornane (TMN) obtained by hydrogenating dicyclopentadiene (DCPD), and aluminum chloride is used industrially as the catalyst. .
Further, as a solid catalyst, a catalyst obtained by supporting an active metal such as platinum, rhenium, nickel and cobalt on a cation-exchanged zeolite by an impregnation method is known (Japanese Patent Publication No. 52-2909).
[0003]
When adamantanes are produced using aluminum chloride as a catalyst, it is necessary to use a large amount of the catalyst, and the catalyst forms a complex with heavy components during the reaction and cannot be reused.
Therefore, when this method is used, a large amount of waste aluminum is generated, and this waste treatment causes a problem of environmental pollution.
Further, when aluminum chloride is used, since the produced adamantane is colored, there is a problem that a decoloring step using recrystallization or activated carbon is necessary, and the post-treatment step is unavoidable.
On the other hand, in a method for producing adamantane using a catalyst in which an active metal such as platinum, rhenium, nickel and cobalt is supported by impregnation on cation-exchanged zeolite, the yield is low unless hydrogen chloride is allowed to coexist (TMN conversion 79 0.5%, adamantane selectivity 10.1%, adamantane yield 8.0%).
Therefore, hydrogen chloride is indispensable, and has a problem that it is necessary to use an expensive corrosion-resistant material because of the strong corrosiveness of hydrogen chloride.
[0004]
Therefore, in order to cope with such problems, the present inventors have conducted research and previously found an effective method for producing adamantanes using a metal-supported solid acid catalyst without using hydrogen chloride. (Japanese Patent Application No. 2000-375593).
However, in this method, although an isomerization catalyst and a method of using the catalyst in a reaction field have been proposed, an industrial adamantane production technique including separation and purification treatment of the produced adamantane is disclosed. It has not been.
[0005]
[Problems to be solved by the invention]
Under such circumstances, the present invention provides a method for producing adamantanes using a solid catalyst, without using hydrogen chloride for the isomerization reaction, and without requiring troublesome operations such as waste liquid treatment. It is an object of the present invention to provide an industrially advantageous method for producing adamantanes, which can efficiently produce products while minimizing loss.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have performed a specific step on the reaction product liquid obtained by isomerizing a tricyclic saturated hydrocarbon compound having 10 or more carbon atoms. We have found that the objective can be achieved.
The present invention has been completed based on such findings.
That is, the present invention
(1) In a method for producing adamantanes by isomerizing a tricyclic saturated hydrocarbon compound having 10 or more carbon atoms, (A) a reaction step of isomerizing a raw material, (B) adamantanes in a reaction product solution A concentration step for concentration; (C) a crystallization step for precipitating concentrated adamantanes; (D) a solid-liquid separation step for separating crystals of adamantanes from the crystallization slurry; and (E) adamantanes subjected to solid-liquid separation. And (F) a drying process for drying the crystals of the washed adamantanes, and a method for producing the adamantanes,
(2) The method for producing an adamantane according to (1), wherein the tricyclic saturated hydrocarbon compound having 10 or more carbon atoms is a compound obtained by hydrogenating a tricyclic unsaturated hydrocarbon compound having 10 or more carbon atoms,
(3) The method for producing adamantanes according to the above (1) and (2) using a solid catalyst in the reaction step of isomerization,
(4) In the concentration step, a flash column or a distillation column is used alone or in combination, and the concentration treatment is performed, and at least a part of the top liquid is reused as a solvent in the reaction step, or at least a part of the top liquid is used. A method for producing the adamantanes of the above (1) to (3) used as a recrystallization solvent in a crystallization step,
(5) The method for producing an adamantane according to the above (1) to (4), which uses cooling crystallization, evaporation crystallization, or a combination thereof as a crystallization operation in the crystallization step,
(6) A recrystallization step and a rewashing step are provided between the solid-liquid separation step, or between the washing step and the drying step, and at least part of the mother liquor generated in these steps is used as part of the solvent or raw material in the reaction step. Recycling or recycling to the concentration step or crystallization step and reuse, (7) The method for producing adamantanes according to (5) and (7) Reaction step, concentration step, crystallization step and solid liquid The method for producing adamantanes according to the above (1) to (6), wherein the separation step is operated batchwise or continuously, respectively.
Is to provide.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In the method for producing adamantanes of the present invention, the following steps, that is, (A) reaction step, (B) concentration step, (C) crystallization step, (D) solid-liquid separation step, (E) washing step, and (F) A drying process is performed.
The adamantane in the present invention is a hydrocarbon compound having an adamantane structure, and examples thereof include an adamantane alkyl-substituted product having a lower alkyl group such as a methyl group or an ethyl group in addition to adamantane.
Next, each step will be described.
[0008]
(A) Reaction step This reaction step is a step of producing adamantanes by isomerizing raw materials in a batch or continuous manner.
As the raw material, a tricyclic saturated hydrocarbon compound having 10 or more carbon atoms is used.
The tricyclic saturated hydrocarbon compound having 10 or more carbon atoms is particularly preferably a tricyclic saturated hydrocarbon compound having 10 to 15 carbon atoms, such as trimethylene norbornane [tetrahydrodicyclopentadiene], perhydroacetate. Examples thereof include naphthene, perhydrofluorene, perhydrophenalene, 1,2-cyclopentanoperhydronaphthalene, perhydroanthracene and perhydrophenanthrene.
Furthermore, the alkyl substituted body of these compounds, for example, 9-methyl perhydroanthracene, etc. are mentioned as a suitable thing.
The tricyclic saturated hydrocarbon compound having 10 or more carbon atoms is a tricyclic hydrocarbon having 10 or more carbon atoms such as dicyclopentadiene, acenaphthene, fluorene, phenalene, 1,2-cyclopentanonaphthalene, anthracene, phenanthrene and 9-methylanthracene. A cyclic unsaturated hydrocarbon compound can be easily obtained by hydrogenation using a hydrogenation catalyst.
The catalyst for hydrogenation used in this case is not particularly limited as long as it is a catalyst having hydrogenation activity, and for example, Raney nickel and platinum can be preferably mentioned.
Further, the type of the hydrogenation reactor is not particularly limited, and for example, a so-called fixed bed continuous reactor in which a catalyst is charged and a raw material is continuously supplied can be used, but is not limited thereto. In addition to the continuous type and the batch type, all types of normal solid-liquid contact type and solid-gas contact type can be used.
[0009]
The raw material compound may be supplied directly or together with the solvent.
Under the present circumstances, solvent ratio is about 0-10 mass parts normally with respect to 1 mass part of raw material compounds, Preferably it is 0-3 mass parts.
In addition, this hydrogenation reaction is an exothermic reaction, and the reaction product obtained here is directly supplied to the isomerization step, thereby minimizing the energy required for the temperature required for the isomerization reaction. Can do.
As conditions for this hydrogenation reaction, the reaction temperature is usually about 0 to 500 ° C., preferably 20 to 300 ° C., and the pressure is usually normal pressure to about 10 MPa, preferably 1 to 5 MPa, hydrogen / raw compound molar ratio. Is usually 2 or more.
The solid catalyst used in the isomerization reaction is not particularly limited, but a solid acid catalyst, particularly a metal-supported solid acid catalyst is preferable.
Examples of the metal species in the metal-supported solid acid catalyst include metals belonging to Groups 8 to 10 of the periodic table, more specifically, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum. It is mentioned as a suitable thing.
Among these metals, a solid acid catalyst supporting platinum is particularly preferable.
As the solid acid supporting these metals, various zeolites such as A-type zeolite, L-type zeolite, X-type zeolite, Y-type zeolite and ZSM-5, and metal oxides such as silica alumina, alumina and heteropolyacid are suitable. It is mentioned as a thing.
Among these solid acids, X-type zeolite and Y-type zeolite are particularly preferable.
[0010]
And about the method of manufacturing a metal carrying | support solid acid catalyst by using this zeolite as a support | carrier, it can obtain by carrying | supporting at least 1 type in the said metal on a zeolite by the ion exchange method or the impregnation method.
Here, in the case of the ion exchange method, the metal salt or metal complex aqueous solution of the above metal is brought into contact with the zeolite, the cation sites (H ⁻ , NH ₄ ^+, etc.) in the zeolite are ion exchanged, dried and then fired. Can be obtained.
Further, in the case of the impregnation method, the above metal salt or metal complex aqueous solution can be mixed with zeolite, evaporated to dryness using a rotary evaporator or the like, and impregnated and supported.
The form of the catalyst thus obtained may be either powdery or granular.
Further, the shape of the reactor used for the isomerization reaction is not particularly limited. For example, a so-called fixed bed continuous reactor in which a catalyst is charged and a raw material is continuously supplied can be used, but is not limited thereto. However, the present invention is not limited to the continuous type and the batch type, and any type of normal solid-liquid contact type and solid-gas contact type can be used.
[0011]
In this isomerization reaction, the hydride may be purified and used for the reaction, or may be used directly without purification.
In any case, it can be used together with a solvent. The solvent ratio at this time is usually about 0 to 10 parts by mass, preferably 0 to 3 parts by mass with respect to 1 part by mass of the hydride. When the hydride is used directly without being purified, a part of the solvent used in the hydrogenation step can be removed or newly added to adjust the solvent ratio.
As conditions for the isomerization reaction, the reaction temperature is usually about 150 to 500 ° C., preferably 200 to 400 ° C., and the pressure is usually atmospheric pressure to about 20 MPa, preferably 2 to 8 MPa. The reaction is performed in the presence of hydrogen. It is preferable to improve the yield.
[0012]
Furthermore, in the present invention, when the above-mentioned tricyclic saturated hydrocarbon compound having 10 or more carbon atoms is isomerized, the reaction is carried out in the presence of a monocyclic saturated hydrocarbon compound, an aromatic compound, water and / or alcohols. It can be performed.
Here, examples of the monocyclic saturated hydrocarbon compound to coexist include cyclopentane, cyclohexane, ethylcyclohexane, methylcyclohexane, and the like.
In particular, cyclohexane or ethylcyclohexane or a mixture thereof is suitable.
Examples of aromatic compounds include aromatic hydrocarbon compounds such as benzene, toluene, xylene, naphthalene and anthracene; oxygen-containing aromatic compounds such as phenol, benzaldehyde, benzoic acid, benzyl alcohol and anisole; aniline and nitrobenzene And nitrogen-containing aromatic compounds such as chlorobenzene and bromobenzene.
Among these aromatic compounds, aromatic hydrocarbon compounds such as benzene, toluene, xylene, naphthalene and anthracene are more preferable, and benzene is particularly preferable.
On the other hand, examples of alcohols include monohydric alcohols such as methyl alcohol, isopropyl alcohol, tert-butyl alcohol and benzyl alcohol, and polyhydric alcohols such as ethylene glycol and glycerin.
The addition amount of these coexisting compounds is not particularly limited and can be appropriately selected according to various situations.
[0013]
(B) Concentration step In this concentration step, the isomerization reaction product liquid obtained in the isomerization step is subjected to a concentration treatment by using a flash tower or a distillation tower alone or in combination in a batch or continuous manner, and a solvent is obtained. And light by-products (impurities) are removed and concentrated in the next crystallization step to a concentration that allows efficient crystallization.
In this concentration step, light gas such as unreacted hydrogen is usually removed by a flash tower, and concentration is completed in one distillation tower.
And it concentrates so that it may become normally 10-50 mass% as a density | concentration of adamantane, Preferably it is 20-40 mass%.
If the concentration rate is too low, the recovery efficiency of adamantanes in the crystallization process is deteriorated. On the other hand, if the concentration rate is too high, impurities are also relatively concentrated, and impurities are incorporated into the adamantanes in the crystallization step. It becomes easy.
The light fraction obtained from the top of the column can be used partially or entirely as a solvent for the isomerization reaction step, and optionally the hydrogenation reaction step, to minimize the use of a new reaction solvent. The raw materials and reaction middle distillates contained therein or adamantanes can be recycled and utilized.
Moreover, a new recrystallization solvent can be suppressed to the minimum by using a part or all of the tower top liquid as a recrystallization solvent in the next crystallization step.
The amount recycled to the reaction step and the amount used as the recrystallization solvent should be adjusted as appropriate depending on the concentration of adamantane and other impurities in the fraction obtained from the top of the column, or the flow rate balance in the process. Thus, a product with the target purity can be obtained efficiently.
[0014]
(C) Crystallization step This crystallization step is a step of crystallizing adamantanes batchwise or continuously from the concentrated liquid obtained in the concentration step.
As the crystallization operation, general cooling crystallization, evaporation crystallization, or a combination thereof can be used.
The operation temperature in the crystallization operation depends on the concentration of adamantanes in the concentrate.
In the case of continuous crystallization, it is usually about -20 to 50 ° C, preferably 0 to 30 ° C. If this temperature is less than −20 ° C., a large amount of energy is consumed for cooling, and if it exceeds 50 ° C., the solubility of adamantane in the solvent is large, and the recovery efficiency of adamantane may be reduced.
In any other crystallization method, for the same reason, the temperature at which the solubility of adamantanes is about 0.5 to 25% by mass, preferably 5 to 15% by mass is the final temperature in the crystallization step. It is advantageous to do so.
If impurities that cause quality problems are incorporated in a single crystallization, they can be recrystallized immediately after crystallization, or recrystallized after the solid-liquid separation process and washing process, which are subsequent processes. The solid-liquid separation step and the washing step can be repeated a plurality of times.
[0015]
(D) Solid-liquid separation step This solid-liquid separation step is a step of separating the adamantane crystals and the solvent precipitated in the crystallization step in a batch or continuous manner.
As the solid-liquid separation operation, a general method using a filter cloth or a sintered metal can be used.
At that time, a part of the separated mother liquor is generally discharged out of the system in order to suppress the concentration of impurities.
Then, the remaining part or the whole is recycled to the concentration step and the crystallization step, thereby suppressing the loss of adamantanes to the minimum, or the isomerization reaction step, and optionally the hydrogenation reaction step solvent or By using it as a part of the raw material, no new solvent is required, and the raw material and reaction middle distillate or adamantanes contained in the light fraction can be recycled and used.
The degree of solid-liquid separation is such that the liquid content in the separated crystal cake is about 50% by mass or less, preferably 5 to 30% by mass.
The amount of mother liquor discharged from the system and the amount of recirculation can be efficiently targeted by appropriately adjusting the concentration of adamantanes and other impurities contained in the mother liquor and the flow rate balance in the process. A product of purity can be obtained.
[0016]
(E) Washing step This washing step is a step of washing and removing a solvent that has not been sufficiently removed by the solid-liquid separation using a washing solvent.
As the washing solvent, most organic solvents can be used, but polar solvents such as alcohols, ketones and carboxylic acids having low solubility are preferable so as not to reduce the recovery efficiency of adamantanes.
Further, when the washed adamantane is directly treated in the subsequent drying step, a low boiling point solvent that is easy to dry is preferable, and a solvent having a normal boiling point of 150 ° C. or lower is preferable.
Examples of such solvents include methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, diethyl ketone, acetic acid and carbon tetrachloride.
The washing operation temperature is usually in the range from room temperature to the boiling point of the washing solvent, preferably -20 to 50 ° C.
[0017]
(F) Drying step This drying step is a step of drying the crystals of the washed adamantanes obtained in the washing step.
For this drying treatment, a general drier used industrially such as a reduced pressure type and a heating type can be used.
The drying method may be either a continuous type or a batch type.
Since the purpose of the drying treatment is to remove the washing solvent, the operating conditions vary depending on the type of solvent used in the washing step, but the pressure is usually normal pressure or lower, preferably 5 to 101 kPa, The temperature is not higher than the boiling point of the washing solvent, preferably 20 to 60 ° C.
In this way, it is possible to efficiently produce high-purity adamantanes while minimizing loss, without requiring troublesome operations such as waste liquid treatment.
[0018]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Preparation Example 1 Preparation of Metal-Supported Solid Acid Catalyst 235 g of Y-zeolite that had been subjected to sodium ion exchange was stirred and suspended in 2000 g of pure water, and a dilute nitric acid aqueous solution was added thereto to adjust the pH of the suspended slurry to 5.5. did.
Next, a solution prepared by dissolving 246 g of lanthanum nitrate hexahydrate in 500 g of warm water was gradually mixed with the suspension slurry.
Thereafter, the mixture was heated to 90 ° C. and stirred for 30 minutes, followed by filtration and washing, and then the washed cake was dried at 110 ° C. overnight and further calcined at 600 ° C. for 3 hours.
228 g of ammonium sulfate was added to a slurry obtained by stirring and suspending the fired powder in 2000 g of pure water again, followed by stirring at 95 ° C. for 30 minutes, followed by filtration and washing.
This washed cake was again suspended in 2000 g of water, and the same ion exchange operation was continued twice.
Then, after drying at 110 ° C. overnight, this was placed in a tubular container and steamed at 510 ° C. for 30 minutes under 100% steam.
Subsequently, the obtained powder was suspended in 2000 g of pure water, 32 g of 25% by mass sulfuric acid was slowly added, and then heated at 95 ° C. for 30 minutes.
Then, after carrying out filtration washing | cleaning, this was again suspended in 2000 g of pure waters, 180 g of 1.71 mass% tetraammineplatinum chloride aqueous solution was added, and it stirred at 60 degreeC for 30 minutes.
This was filtered and washed, and then dried at 110 ° C. overnight to obtain a catalyst comprising La-containing Y-type zeolite carrying 0.87% by mass of platinum by ion exchange.
[0019]
Example 1
(1) Reaction / concentration step 20 g of the catalyst obtained in Preparation Example 1 was filled in a stainless steel reaction tube and calcined at 300 ° C. for 3 hours in an air stream.
After purging with nitrogen, hydrogen reduction was performed at 300 ° C. for 2 hours under normal pressure and hydrogen stream.
Thereafter, supply of a mixed solution of decalin and trimethylene norbornane (TMN) in a mass ratio of 2: 1 and hydrogen was started, and continuously under conditions of 300 ° C., 5 MPa, WHSV 2.4 h ⁻¹ , hydrogen / TMN molar ratio 2. The isomerization reaction was performed.
The concentration of adamantane in the reaction product solution was 7% by mass.
1000 g of the reaction product solution was concentrated by vapor distillation at 15 stages until the adamantane concentration was 26% by mass.
The concentrate contained 15% by mass of unreacted TMN and 59% by mass of other impurities.
[0020]
(2) Purification step The concentrated liquid obtained in (1) above was used as a crystallization raw material, and 180 g thereof was charged into a flask and stirred and dissolved at 120 ° C.
While continuing the stirring, the mixture was slowly cooled to 10 ° C. for crystallization to obtain a slurry in which adamantane was precipitated.
Next, this slurry was filtered through a 70 μm glass filter, and 60 g of the obtained filter cake was washed with 35 g of isopropanol.
33 g of washed crystals were charged into an eggplant flask and dried for 30 minutes while shaking with an evaporator having a pressure of 25 kPa and a temperature of 50 ° C.
When 28 g of dried crystals were collected and analyzed by gas chromatography, the purity was 98% by mass.
The impurities were 0.1% by mass for isopropanol and 2% by mass for TMN and other impurities in total.
The yield of high-purity adamantane relative to the raw material TMN was 8% by mass.
[0021]
Example 2
(1) Reaction / concentration step In Example 1 (1), instead of decalin, the tower top liquid and the crystallization mother liquor obtained at the time of concentration of the reaction product liquid in Example 1 were in a mass ratio of 3: 1. The isomerization reaction was performed in the same manner as in Example (1) except that the solution mixed in (1) was used.
The adamantane concentration in the reaction product solution was 8% by mass.
1000 g of the reaction product solution was concentrated by vapor distillation at 15 stages until the adamantane concentration was 28% by mass.
The concentrated solution contained 17% by mass of unreacted TMN and 55% by mass of other impurities.
(2) Purification step Crystallization, washing and drying were carried out in the same manner as in Example 1 (2).
When 33 g of dried crystals were collected and analyzed by gas chromatography, the purity was 98% by mass.
The impurities were 0.1% by mass for isopropanol and 2% by mass for TMN and other impurities in total.
The yield of high-purity adamantane relative to the raw material TMN was 14% by mass.
[0022]
【The invention's effect】
According to the present invention, in a method for producing adamantanes using a solid catalyst, hydrogen chloride is not used for the isomerization reaction, and troublesome operations such as waste liquid treatment are not required, and loss of high-purity adamantanes is minimized. It is possible to provide an industrially advantageous method for producing adamantanes that can be produced efficiently while limiting to the limit.

Claims (9)

In the method for producing adamantanes by isomerizing a tricyclic saturated hydrocarbon compound having 10 or more carbon atoms using a solid catalyst , (A) a reaction step for isomerizing the raw material, and (B) concentrating the reaction product liquid . A concentration step, (C) a crystallization step for precipitating the concentrated adamantanes, (D) a solid-liquid separation step for separating the crystals of the adamantane from the crystallization slurry, (E) crystals of the adamantanes separated by solid-liquid separation And (F) a drying process for drying the crystals of the washed adamantanes.   The method for producing an adamantane according to claim 1, wherein the tricyclic saturated hydrocarbon compound having 10 or more carbon atoms is a compound obtained by hydrogenating a tricyclic unsaturated hydrocarbon compound having 10 or more carbon atoms. The method for producing adamantanes according to claim 1 or 2, wherein a fixed bed continuous reactor is used in the isomerization reaction step.   In the concentration step, a flash tower or a distillation column is used alone or in combination, and concentrated, and at least a part of the top liquid is reused as a solvent in the reaction process, or at least a part of the top liquid is crystallized. The method for producing an adamantane according to any one of claims 1 to 3, wherein the adamantane is used as a recrystallization solvent.   The method for producing an adamantane according to any one of claims 1 to 4, wherein cooling crystallization, evaporation crystallization, or a combination thereof is used as a crystallization operation in the crystallization step.   A recrystallization step and a rewashing step are provided between the solid-liquid separation step, or between the washing step and the drying step, and at least part of the mother liquor generated in these steps is recycled as part of the solvent or raw material in the reaction step. Alternatively, the method for producing adamantane according to any one of claims 1 to 5, wherein the adamantane is recycled to the concentration step or the crystallization step and reused.   The method for producing an adamantane according to any one of claims 1 to 6, wherein the reaction step, the concentration step, the crystallization step, and the solid-liquid separation step are operated batchwise or continuously, respectively.   The method for producing an adamantane according to any one of claims 1 to 7, wherein the concentration is performed so that the concentration of the adamantane is 10 to 50% by mass in the concentration step.   The method for producing an adamantane according to any one of claims 1 to 8, wherein the crystallization step is performed at a temperature at which the solubility of the adamantane is 0.5 to 25% by mass.