WO2012117976A1 - 脂環式カルボン酸の製造方法及び該方法に用いる触媒 - Google Patents
脂環式カルボン酸の製造方法及び該方法に用いる触媒 Download PDFInfo
- Publication number
- WO2012117976A1 WO2012117976A1 PCT/JP2012/054640 JP2012054640W WO2012117976A1 WO 2012117976 A1 WO2012117976 A1 WO 2012117976A1 JP 2012054640 W JP2012054640 W JP 2012054640W WO 2012117976 A1 WO2012117976 A1 WO 2012117976A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- ruthenium
- palladium
- acid
- carboxylic acid
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/08—Saturated compounds having a carboxyl group bound to a six-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/12—Saturated polycyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
- C07C2602/28—Hydrogenated naphthalenes
Definitions
- the present invention relates to a method for producing an alicyclic carboxylic acid and a hydrogenation catalyst for an aromatic ring of an aromatic carboxylic acid that can be suitably used in this method.
- the present invention relates to a method for producing an alicyclic carboxylic acid by hydrogenating an aromatic carboxylic acid in the presence of a noble metal catalyst.
- the catalyst of the present invention is more specifically a catalyst in which the hydrogenation catalyst co-supports ruthenium and palladium, and ruthenium and palladium are present in the form of particles containing both on the support surface, that is, the same
- the catalyst relates to the coexisting particles.
- Non-Patent Document 1 Non-Patent Document 2, Patent Document. 1, Patent Document 2.
- the rhodium catalyst is highly active as a hydrogenation catalyst for aromatic carboxylic acids, and has the advantage that the side reaction does not proceed and the selectivity of the product increases.
- rhodium has such excellent catalytic ability, there are some problems in industrialization. The first point is that it is very expensive, and the burden of initial investment for the catalyst becomes large during industrialization.
- the second point is that the rate of decrease in the activity of the catalyst is fast, and the activation operation must be frequently performed in order to use the catalyst for a long period of time.
- Patent Document 1 proposes a simpler process for industrialization.
- Ruthenium is an example of a precious metal that can hydrogenate aromatic carboxylic acids and is inexpensive.
- ruthenium catalysts when ruthenium catalysts are used for hydrogenation of aromatic carboxylic acids, it is known that not only aromatic ring hydrogenation, but also reduction of side chain carboxyl groups occurs. Becomes lower. Since the ruthenium catalyst is also used as a catalyst for reducing a carboxyl group to an alcohol, it is clear that the selectivity decreases (Non-patent Document 3).
- the object of the present invention is to use ruthenium, which is a relatively inexpensive noble metal, to develop a catalyst that has the same activity as a rhodium catalyst and does not cause a decrease in activity as seen in a rhodium catalyst, and is an industrially simple alicyclic carboxylic acid. Is to establish a manufacturing method.
- the present invention relates to the following methods for producing alicyclic carboxylic acids [1] to [9] and catalysts [10] to [13].
- [1] A method for producing an alicyclic carboxylic acid by hydrogenating an aromatic ring of an aromatic carboxylic acid, wherein a catalyst containing ruthenium and palladium is used as a catalyst.
- [2] The method for producing an alicyclic carboxylic acid according to [1], wherein the catalyst is a catalyst in which ruthenium and palladium are co-supported on a carrier.
- [3] The process for producing an alicyclic carboxylic acid according to [1] to [2], wherein one or more selected from water, methanol, ethanol, 1-propanol and 2-propanol is used as a reaction solvent for the hydrogenation reaction .
- [4] The method for producing an alicyclic carboxylic acid according to [1] to [2], wherein water is used as a reaction solvent for the hydrogenation reaction.
- [5] The method for producing an alicyclic carboxylic acid according to [2] to [4], wherein the catalyst carrier is one or a combination of two or more selected from activated carbon, alumina, zirconia, ceria, titania and silica.
- a ruthenium-palladium co-supported catalyst characterized in that ruthenium and palladium are present in the form of particles containing both on the support surface in a catalyst in which ruthenium and palladium are co-supported.
- the ruthenium-palladium co-supported catalyst according to [10] wherein the ruthenium-palladium co-supported catalyst is a hydrogenation catalyst.
- the catalyst in the present invention shows the same activity as the rhodium catalyst, and the activity reduction that is a problem of the rhodium catalyst is not seen. Therefore, the activation operation is not necessary, and the alicyclic carboxylic acid is produced by a very simple process industrially. Can be manufactured. Moreover, the reduction reaction of the carboxyl group seen in the case of a ruthenium catalyst is suppressed, and the hydrogenation reaction of the aromatic ring proceeds with high selectivity.
- Example 2 shows a transmission electron microscope image (Z-contrast: magnification of 500,000 times) of a ruthenium-palladium co-supported catalyst produced in Example 21.
- FIG. The transmission electron microscope image (transmission electron image: magnification of 500,000 times) of the ruthenium-palladium co-supported catalyst produced in Example 21 is shown.
- the transmission electron microscope image (Z-contrast: magnification of 1 million times) of the ruthenium-palladium co-supported catalyst produced in Example 22 is shown.
- the transmission electron microscope image (transmission electron image: Magnification 1 million times) of the ruthenium-palladium co-supported catalyst produced in Example 22 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 21 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 21 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 21 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 21 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 21 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 21 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 21 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 21 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 21 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 21 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 21 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 22 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 22 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 22 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 22 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 22 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 22 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 22 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 22 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 22 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 22 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 22 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 22 is shown.
- grains seen by the transmission electron microscope image of the ruthenium-palladium co-supported catalyst manufactured in Example 22 is shown.
- the aromatic carboxylic acid used in this reaction is not particularly limited as long as it is a compound having a carboxyl group in the aromatic ring, and known aromatic carboxylic acids can be used.
- aromatic carboxylic acid those represented by the general formula (1), (2) or (3) can be used.
- aromatic monocarboxylic acids such as benzoic acid; phthalic acid, isophthalic acid, terephthalic acid, 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2, 3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4, Aromatic dicarboxylic acids such as 4'-biphenyldicarboxylic acid; aromatic tricarboxylic acids such as hemimellitic acid, trimellitic acid, trimesic acid, 1,2,4-naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid; Melofuanic acid,
- aromatic tetracar examples include boronic acid; aromatic pentacarboxylic acid such as benzenepentacarboxylic acid; aromatic hexacarboxylic acid such as benzenehexacarboxylic acid, and the like. These may be used alone or in appropriate combination of two or more.
- aromatic dicarboxylic acids having 2 to 4 carboxyl groups in the benzene ring aromatic tricarboxylic acids, and aromatic tetracarboxylic acids are preferable.
- aromatic acid, isophthalic acid, terephthalic acid, trimellitic acid, Trimesic acid and pyromellitic acid are preferable, and trimellitic acid, trimesic acid, and pyromellitic acid are more preferable. These may be used alone or in appropriate combination of two or more.
- a reaction solvent is suitably used for the hydrogenation reaction in the present invention, and the reaction solvent is not particularly limited as long as it dissolves the aromatic carboxylic acid and does not inhibit the reaction.
- alcohols such as water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, diethyl ether, diisopropyl ether, n-butyl ether, cyclopentyl methyl ether , Ethers such as tert-butyl methyl ether and THF, esters such as methyl acetate and ethyl acetate, and ketones such as acetone and methyl ethyl ketone.
- water, methanol, ethanol, 1-propanol and 2-propanol are preferable, and water is more preferable. These may be used alone or in admixture of two or more.
- the aromatic carboxylic acid may be dissolved or suspended in a solvent, and the concentration is not particularly limited.
- the specific concentration of the aromatic carboxylic acid is preferably 1 to 50% by weight, more preferably 2 to 40% by weight, and still more preferably as the aromatic carboxylic acid based on the total of the aromatic carboxylic acid and the solvent. 2 to 20% by weight.
- the catalyst containing ruthenium and palladium used in the hydrogenation reaction is not limited as long as ruthenium and palladium coexist in the catalyst.
- Specific examples include a catalyst obtained by mixing a catalyst supporting ruthenium and a catalyst supporting palladium, and a catalyst co-supporting ruthenium and palladium on a carrier, preferably a catalyst co-supporting ruthenium and palladium on a carrier.
- ruthenium-palladium co-supported catalyst that exists in the form of particles including both on the surface of the carrier, that is, ruthenium and palladium coexist in the same particle. Ruthenium and palladium coexist in the same particle and are close to each other, thereby exhibiting high activity and selectivity for hydrogenation of the aromatic ring of aromatic carboxylic acid.
- the size of the particles in which ruthenium and palladium coexist on the support surface of the ruthenium-palladium co-supported catalyst is not particularly limited as long as ruthenium and palladium coexist. In general, it is known that when the size of the supported metal particles is large, the outer surface area of the particles becomes small, and the supported metal is not efficiently used for the reaction. Similarly, in the ruthenium-palladium co-supported catalyst of the present invention, when the size of the particles in which ruthenium and palladium coexist is large, the outer surface area of the particles becomes small, and the supported ruthenium and palladium are not efficiently used in the reaction. .
- a smaller particle size is preferred, preferably 1-50 nm, more preferably 1-15 nm. This particle size can be easily measured by a method such as a transmission electron microscope.
- the particles are preferably composed of ruthenium and palladium.
- the production method of the catalyst containing ruthenium and palladium used in the hydrogenation reaction is not limited as long as ruthenium and palladium can coexist in the same particle on the support surface as long as ruthenium and palladium can coexist in the catalyst. It is also possible to add a third component in addition to palladium.
- Specific examples of the preparation method include an ion exchange method, an impregnation method, and a deposition method, and the impregnation method and the deposition method are preferable.
- the order in which ruthenium and palladium are supported on the carrier is not particularly limited. Specifically, a method of simultaneously supporting, a method of sequentially supporting, and the like can be mentioned. After containing ruthenium and palladium in the catalyst, it is possible to appropriately perform drying, firing and reduction according to the preparation method.
- the amount of ruthenium and palladium contained in the catalyst there is no limit to the amount of ruthenium and palladium contained in the catalyst.
- the catalyst used for the hydrogenation reaction is increased.
- the catalyst used for the hydrogenation reaction may be decreased.
- the total content of ruthenium and palladium is preferably 0.5 to 10% by weight, more preferably 0.5 to 5% by weight.
- the total supported amount of ruthenium and palladium can be measured by fluorescent X-ray analysis or the like.
- the ratio of ruthenium and palladium in the metal contained in the catalyst is not limited as long as ruthenium and palladium coexist in the catalyst. Specifically, the ratio of ruthenium and palladium is preferably 1 to 99% by weight, more preferably 10 to 90% by weight, and still more preferably 20 to 80% by weight.
- the catalyst support is not particularly limited as long as it can support ruthenium and palladium, and the support shape (for example, powder or molded product) and the physical properties of the support (for example, specific surface area and average pore diameter) are not limited.
- Specific examples include activated carbon, alumina, zirconia, ceria, titania, silica, silica alumina, zeolite, chromium oxide, tungsten oxide, ion exchange resin, and synthetic adsorbent.
- activated carbon, alumina, zirconia, ceria, titania, and silica are preferable, and these can be used alone or in admixture of two or more.
- the particle size (average particle size) of the carrier is preferably 1 ⁇ m to 300 ⁇ m when the reaction is performed in a suspended bed, and 0.3 mm to 10 mm when the reaction is performed in a fixed bed.
- the amount of catalyst used in the hydrogenation reaction is not limited, and may be appropriately determined so as to achieve the desired reaction time in consideration of the content of ruthenium and palladium and the amount of aromatic carboxylic acid used in the reaction.
- the reaction can be carried out in the temperature range of 40 to 150 ° C., preferably in the temperature range of 40 to 100 ° C.
- the hydrogen pressure of the hydrogenation reaction is not particularly limited. If the hydrogen pressure is low, the reaction rate decreases, and the time required for completing the hydrogenation reaction increases. Conversely, if the hydrogen pressure is high, the hydrogenation reaction is completed. Although the time required is shortened, the investment in the apparatus such as the breakdown voltage specification of the apparatus increases. Specifically, the hydrogenation reaction can be carried out in the range of 1 to 15 MPa, preferably 5 to 10 MPa.
- the hydrogenation reaction is not limited to batch or continuous reaction formats. If the target production amount is small, a batch-type manufacturing process may be constructed, and if the production amount is large, a continuous production process may be constructed.
- the catalyst containing ruthenium and palladium used for the hydrogenation reaction does not show a significant decrease in activity for each reaction in the batch system, it can be reused without the activation of the catalyst.
- continuous operation is performed for 1000 hours or more (in the case of a catalyst in which ruthenium and palladium are co-supported with ruthenium and palladium existing in the form of particles containing both on the support surface, 5000 hours or more). However, there is no significant decrease in activity.
- the hydrogenation reaction using the ruthenium-palladium co-supported catalyst in which the ruthenium and palladium of the present invention are present in the form of particles containing both on the support surface is the amount of the above aromatic carboxylic acid, the amount of the catalyst.
- Example 1 Trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.0 g in a 30 ml SUS316 autoclave, 1.0 wt% Ru-4.0 wt prepared by a known method (deposition method described on page 40 of Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis) % Pd / carbon powder catalyst 0.5g and water 10g were charged. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. It was confirmed that the reaction was completed with no hydrogen absorption 0.5 hours after the start of temperature increase.
- trimellitic acid When the reaction product is derivatized into a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid is 100% and the selectivity for hydrogenated trimellitic acid (1,2,4-cyclohexanetricarboxylic acid) is 98.6. % (Mol%).
- Example 2 A 30 ml SUS316 autoclave was charged with 1.0 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.5 wt% Ru-2.5 wt% Pd / carbon powder catalyst 0.5 g prepared in the same manner as described in Example 1, and 10 g of water. It is. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. It was confirmed that the reaction was completed with no hydrogen absorption 0.5 hours after the start of temperature increase. When the reaction product was derivatized into a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100%, and the selectivity for hydrogenated trimellitic acid was 96.9% (mol%).
- trimellitic acid manufactured by Tokyo Chemical Industry Co., Ltd.
- Example 3 A 30 ml SUS316 autoclave was charged with 1.0 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.0 wt% Ru-1.0 wt% Pd / carbon powder catalyst 0.5 g prepared in the same manner as described in Example 1, and 10 g of water. It is. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. It was confirmed that the reaction was completed with no absorption of hydrogen in 0.6 hours from the start of temperature increase. When the reaction product was derivatized into a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100%, and the selectivity for trimellitic hydride was 97.2% (mol%).
- trimellitic acid manufactured by Tokyo Chemical Industry Co., Ltd.
- Ru-1.0 wt% Pd / carbon powder catalyst 0.5 g prepared in the same manner as described in Example 1, and 10 g of water. It is.
- Example 4 A 300 ml SUS316 autoclave was charged with 20 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2 g of 4.0 wt% Ru-1.0 wt% Pd / carbon powder catalyst prepared in the same manner as described in Example 1, and 120 g of water. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with an electromagnetic stirring blade. After 1.2 hours from the start of temperature increase, hydrogen absorption disappeared and it was confirmed that the reaction was completed. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100%, and the selectivity for trimellitic hydride was 94.2% (mol%).
- Example 5 A 30 ml SUS316 autoclave was charged with 1.5 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.5 wt% Ru-2.5 wt% Pd / carbon powder catalyst 0.3 g prepared in the same manner as described in Example 1, and 9 g of water. It is. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. After 1.8 hours from the start of temperature increase, hydrogen absorption disappeared and it was confirmed that the reaction was completed. When the reaction product was derivatized into a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100%, and the selectivity for trimellitic hydride was 95.1% (mol%).
- trimellitic acid manufactured by Tokyo Chemical Industry Co., Ltd.
- Example 6 A 30 ml SUS316 autoclave was charged with 1.5 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.5 wt% Ru-2.5 wt% Pd / alumina powder catalyst prepared in the same manner as described in Example 1, and 9 g of water. It is. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. After 1.7 hours from the start of temperature increase, hydrogen absorption disappeared and it was confirmed that the reaction was completed. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100%, and the selectivity for trimellitic hydride was 94.2% (mol%).
- Example 7 A 30 ml SUS316 autoclave was charged with 1.5 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.3 g of 2.5 wt% Ru-2.5 wt% Pd / zirconia powder catalyst prepared in the same manner as described in Example 1, and 9 g of water. It is. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. After 2.0 hours from the start of temperature increase, hydrogen absorption disappeared and it was confirmed that the reaction was completed. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100%, and the selectivity for trimellitic hydride was 93.3% (mol%).
- Example 8 A 30 ml SUS316 autoclave was charged with 1.5 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.5 wt% Ru-2.5 wt% Pd / ceria powder catalyst 0.3 g prepared in the same manner as described in Example 1, and 9 g of water. It is. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. After 1.6 hours from the start of temperature increase, hydrogen absorption disappeared and it was confirmed that the reaction was complete. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100% and the selectivity for trimellitic hydrogenated was 92.7% (mol%).
- trimellitic acid manufactured by Tokyo Chemical Industry Co., Ltd.
- Example 9 A 200 ml SUS316 autoclave was charged with 6 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.2 g of 2.5 wt% Ru-2.5 wt% Pd / titania powder catalyst prepared in the same manner as described in Example 1, and 36 g of water. . The pressure was increased to 9 MPa with hydrogen, and the temperature was raised to 55 ° C. while stirring with an electromagnetic stirring blade. After 1.5 hours from the start of temperature increase, hydrogen absorption disappeared and it was confirmed that the reaction was completed. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100%, and the selectivity for trimellitic hydride was 94.0% (mol%).
- Example 10 Trimellitic acid (Tokyo Chemical Industry Co., Ltd.) 6g in a 200ml SUS316 autoclave, 2.5g% Ru-2.5wt% Pd / silica powder catalyst 1.2g prepared by a known method (impregnation method described on page 49 of Catalyst Preparation Chemistry) , 36g of water was charged. The pressure was increased to 9 MPa with hydrogen, and the temperature was raised to 50 ° C. while stirring with an electromagnetic stirring blade. After 2.0 hours from the start of temperature increase, hydrogen absorption disappeared and it was confirmed that the reaction was completed. When the reaction product was derivatized into a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100%, and the selectivity for trimellitic hydride was 94.1% (mol%).
- Example 11 A 300 ml SUS316 autoclave was charged with 20 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.0 wt% Ru-1.0 wt% Pd / titania powder catalyst 4.0 g prepared in the same manner as described in Example 1, and 120 g of water. . The pressure was increased to 8 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with an electromagnetic stirring blade. After the temperature was raised to 60 ° C., hydrogen absorption disappeared in 2.0 hours, and it was confirmed that the reaction was complete.
- trimellitic acid manufactured by Tokyo Chemical Industry Co., Ltd.
- 1.0 wt% Ru-1.0 wt% Pd / titania powder catalyst 4.0 g prepared in the same manner as described in Example 1, and 120 g of water.
- the pressure was increased to 8 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with an electromagnetic stirring blade. After the temperature was raised to 60 ° C., hydrogen absorption disappeared
- Example 12 A 200 ml SUS316 autoclave was charged with 6 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.0 wt% Ru-1.0 wt% Pd / titania powder catalyst 3.0 g prepared in the same manner as described in Example 1, and 36 g of water. . The pressure was increased to 9 MPa with hydrogen, and the temperature was raised to 50 ° C. while stirring with an electromagnetic stirring blade. After 1.3 hours from the start of temperature increase, hydrogen absorption disappeared and it was confirmed that the reaction was completed. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100%, and the selectivity for trimellitic hydride was 94.4% (mol%).
- trimellitic acid manufactured by Tokyo Chemical Industry Co., Ltd.
- Example 13 A reaction tube made of SUS316 having an inner diameter of 17 mm ⁇ and a length of 320 mm was packed with 10 g (25 ml) of 1.0 wt% Ru-1.0 wt% Pd / spherical silica catalyst prepared in the same manner as described in Example 10. Under the conditions of a temperature of 80 ° C. and a hydrogen pressure of 8 MPa, a trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 2% by weight aqueous solution was allowed to flow at 30 g / hr and hydrogen was allowed to react at 1.8 L / hr. When 1400 hours had elapsed from the start of the reaction, no reduction in the conversion of trimellitic acid was observed, maintaining 89% from the beginning of the reaction. During this period, the selectivity for trimellitic hydrogenated was around 94% (mol%).
- Example 14 A 200 ml SUS316 autoclave was charged with 6 g of pyromellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.2 g of 2.5 wt% Ru-2.5 wt% Pd / titania powder catalyst prepared in the same manner as described in Example 1, and 36 g of water. . The pressure was increased to 9 MPa with hydrogen, and the temperature was raised to 50 ° C. while stirring with an electromagnetic stirring blade. It was confirmed that hydrogen absorption disappeared in 3.0 hours from the start of temperature increase and the reaction was completed.
- the conversion of pyromellitic acid is 100% and hydrogenated pyromellitic acid (1,2,4,5-cyclohexanetetracarboxylic acid) is selected.
- the rate was 94.5% (mol%).
- Example 15 A 30 ml SUS316 autoclave was charged with 1.5 g of trimesic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.5 wt% Ru-2.5 wt% Pd / titania powder catalyst 0.3 g prepared in the same manner as described in Example 1, and 9 g of water. . The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. In 1.4 hours from the start of temperature increase, hydrogen absorption disappeared and it was confirmed that the reaction was completed.
- trimesic acid manufactured by Tokyo Chemical Industry Co., Ltd.
- the pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. In 1.4 hours from the start of temperature increase, hydrogen absorption disappeared and it was
- trimesic acid When the reaction product is derivatized into a methyl ester and analyzed by gas chromatography, the conversion rate of trimesic acid is 100% and the selectivity for hydrogenated trimesic acid (1,3,5-cyclohexanetricarboxylic acid) is 93.0% ( Mol%).
- Comparative Example 1 A 300 ml SUS316 autoclave was charged with 20 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.6 g of 5.0 wt% Ru / carbon powder catalyst prepared in the same manner as described in Example 1, and 120 g of water. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 100 ° C. while stirring with an electromagnetic stirring blade. Hydrogen absorption continued even after 8.2 hours had passed after the temperature was raised to 100 ° C, but the reaction was stopped. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 87.1% and the selectivity for trimellitic hydride was 60.4% (mol%).
- Comparative Example 2 A 30 ml SUS316 autoclave was charged with 1.0 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.5 g of 5.0 wt% Pd / carbon powder catalyst prepared in the same manner as described in Example 1, and 10 g of water. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. Although the absorption of hydrogen continued even after 3 hours from the start of temperature increase, the reaction was stopped. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 77.0%, and the selectivity for hydrogenated trimellitic acid was 96.3% (mol%).
- Comparative Example 3 A 30 ml SUS316 autoclave was charged with 1.5 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.3 g of 5.0 wt% Ru / titania powder catalyst prepared in the same manner as described in Example 1, and 9 g of water. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. Although the absorption of hydrogen continued even after 3 hours from the start of temperature increase, the reaction was stopped. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 8.6% and the selectivity for trimellitic hydride was 70.5% (mol%).
- Comparative Example 4 A 30 ml SUS316 autoclave was charged with 1.5 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.3 g of 5.0 wt% Pd / titania powder catalyst prepared in the same manner as described in Example 1, and 9 g of water. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. Although the absorption of hydrogen continued even after 3 hours from the start of temperature increase, the reaction was stopped. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 9.2%, and the selectivity for hydrogenated trimellitic acid was 79.3% (mol%).
- Comparative Example 5 A 300 ml SUS316 autoclave was charged with 20 g of trimellitic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 5.0 g Rh / carbon powder catalyst 1.6 g made by N Chemcat, and 120 g water. The pressure was increased to 8 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with an electromagnetic stirring blade. After the temperature was raised to 40 ° C., hydrogen absorption disappeared in 4.0 hours, and it was confirmed that the reaction was complete. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100% and the selectivity for trimellitic hydrogenated was 97.2% (mol%). The reaction was repeated under the same conditions without activating the recovered catalyst, but no hydrogen absorption was observed, and the conversion of trimellitic acid was 0%.
- Comparative Example 6 A reaction tube made of SUS316 having an inner diameter of 17 mm ⁇ and a length of 320 mm was packed with 10 g (18 ml) of 2.0 wt% Ru / granular carbon catalyst prepared in the same manner as described in Example 1. Under the conditions of a temperature of 60 ° C. and a hydrogen pressure of 5 MPa, a trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 2% by weight aqueous solution was flowed at 30 g / hr and hydrogen was allowed to react at 1.8 L / hr. At 20 hours from the start of the reaction, the conversion of trimellitic acid was 22%, and the selectivity for hydrogenated trimellitic acid was 86% (mol%).
- a trimellitic acid manufactured by Tokyo Chemical Industry Co., Ltd.
- Comparative Example 7 A reaction tube made of SUS316 having an inner diameter of 17 mm ⁇ and a length of 320 mm was packed with 10 g (18 ml) of 2.0 wt% Ru / spherical alumina catalyst prepared in the same manner as described in Example 1. Under the conditions of a temperature of 60 ° C. and a hydrogen pressure of 5 MPa, a trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 2% by weight aqueous solution was flowed at 30 g / hr and hydrogen was allowed to react at 1.8 L / hr. At 6 hours from the start of the reaction, the conversion of trimellitic acid was 23%, and the selectivity for hydrogenated trimellitic acid was 88% (mol%).
- a trimellitic acid manufactured by Tokyo Chemical Industry Co., Ltd.
- Example 21 0.647 g of ruthenium chloride n hydrate (manufactured by Wako Pure Chemical Industries) and 0.417 g of palladium chloride (manufactured by Wako Pure Chemical Industries) were dissolved in water.
- silica gel Caract Q50, manufactured by Fuji Silysia Chemical Co., Ltd., particle size 75-150 ⁇ m
- ruthenium-palladium co-supported catalyst 2.5 wt% Ru-2.5 wt% Pd / SiO 2 .
- 1 and 2 show transmission electron microscope images of the ruthenium-palladium co-supported catalyst prepared by this method. The size of the particles present on the support surface was 3-50 nm. The results of analyzing the coexistence state of ruthenium and palladium in the particles by EDX are shown in FIGS. The average value of the ruthenium / palladium molar ratio contained in the particles was 1.
- Example 22 Ruthenium acetylacetonate complex (manufactured by Aldrich) and palladium acetate (manufactured by Kojima Chemical) were used as the metal source, and the solvent was changed to acetonitrile. Thereafter, a ruthenium-palladium co-supported catalyst was prepared by the method according to Example 21. (2.5 wt% Ru-2.5 wt% Pd / SiO 2). 3 and 4 show transmission electron microscope images of the ruthenium-palladium co-supported catalyst prepared by this method. The size of the particles present on the support surface was 1-15 nm. The results of analyzing the coexistence state of ruthenium and palladium in the particles by EDX are shown in FIGS. The average value of the ruthenium / palladium molar ratio contained in the particles was 1.
- Example 23 Ruthenium chloride n hydrate (manufactured by Wako Pure Chemical Industries) 0.323 g and palladium chloride (manufactured by Wako Pure Chemical Industries) 0.208 g were dissolved in water. Water and 1 g of NaOH (manufactured by Wako Pure Chemical Industries, Ltd.) were added to 5 g of titania (manufactured by Wako Pure Chemical Industries, Ltd.) to make the total weight 100 g and heated in a water bath. After raising the temperature of the aqueous solution to about 80 ° C., an aqueous solution containing ruthenium chloride and palladium chloride was added over 60 minutes. When about 60 minutes had elapsed after completion of the addition, the mixture was cooled and the ruthenium-palladium co-supported catalyst (2.5 wt% Ru-2.5 wt% Pd / TiO 2 ) was recovered by filtration.
- the ruthenium-palladium co-supported catalyst 2.5 wt
- Example 24 6 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared in a 200 ml SUS316 autoclave by the method described in Example 21. A 2.5 wt% Ru-2.5 wt% Pd / silica catalyst 1.2 g and water 36 g were charged. The pressure was increased to 9 MPa with hydrogen, and the temperature was raised to 50 ° C. while stirring with an electromagnetic stirring blade. After 2.0 hours from the start of temperature increase, hydrogen absorption disappeared and it was confirmed that the reaction was completed.
- trimellitic acid manufactured by Tokyo Chemical Industry Co., Ltd.
- trimellitic acid When the reaction product is derivatized to the methyl ester form and analyzed by gas chromatography, the conversion of trimellitic acid is 100%, and the selectivity for hydrogenated trimellitic acid (1,2,4-cyclohexanetricarboxylic acid) is 94.1. It became mol%.
- Example 25 A 200 ml SUS316 autoclave was charged with 5 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.5 wt% Ru-2.5 wt% Pd / silica catalyst 0.5 g prepared by the method described in Example 22, and 60 g of water. The pressure was increased to 9 MPa with hydrogen, and the temperature was raised to 50 ° C. while stirring with an electromagnetic stirring blade. It was confirmed that hydrogen absorption disappeared in 1.0 hour from the start of temperature increase and the reaction was completed. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100%, and the selectivity for hydrogenated trimellitic acid was 96.6 mol%.
- Example 26 6 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared in a 200 ml SUS316 autoclave by the method described in Example 23. A catalyst was charged with 1.2 g of 2.5 wt% Ru-2.5 wt% Pd / titania powder catalyst and 36 g of water. The pressure was increased to 9 MPa with hydrogen, and the temperature was raised to 55 ° C. while stirring with an electromagnetic stirring blade. After 1.5 hours from the start of temperature increase, hydrogen absorption disappeared and it was confirmed that the reaction was completed. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100% and the selectivity for hydrogenated trimellitic acid was 94.0 mol%.
- Example 27 Pyromellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 5 g in a 200 ml SUS316 autoclave was prepared by the method described in Example 22. 0.5 g of 2.5 wt% Ru-2.5 wt% Pd / silica catalyst and 60 g of water were charged. The pressure was increased to 9 MPa with hydrogen, and the temperature was raised to 50 ° C. while stirring with an electromagnetic stirring blade. After 2.0 hours from the start of temperature increase, hydrogen absorption disappeared and it was confirmed that the reaction was completed.
- the conversion of pyromellitic acid is 100% and hydrogenated pyromellitic acid (1,2,4,5-cyclohexanetetracarboxylic acid) is selected.
- the rate was 96.1 mol%.
- Example 28 Pyromellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 6 g in a 200 ml SUS316 autoclave was prepared by the method described in Example 23. A catalyst was charged with 1.2 g of 2.5 wt% Ru-2.5 wt% Pd / titania powder catalyst and 36 g of water. The pressure was increased to 9 MPa with hydrogen, and the temperature was raised to 50 ° C. while stirring with an electromagnetic stirring blade. It was confirmed that hydrogen absorption disappeared in 3.0 hours from the start of temperature increase and the reaction was completed. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of pyromellitic acid was 100% and the selectivity for hydrogenated pyromellitic acid was 94.5 mol%.
- Example 29 In a 30 ml SUS316 autoclave, 1.5 g of trimesic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared by the method described in Example 23. A 2.5 wt% Ru-2.5 wt% Pd / titania powder catalyst 0.3 g and water 9 g were charged. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. In 1.4 hours from the start of temperature increase, hydrogen absorption disappeared and it was confirmed that the reaction was completed.
- trimesic acid manufactured by Tokyo Chemical Industry Co., Ltd.
- trimesic acid When the reaction product is derivatized into a methyl ester and analyzed by gas chromatography, the conversion rate of trimesic acid is 100% and the selectivity for hydrogenated trimesic acid (1,3,5-cyclohexanetricarboxylic acid) is 93.0 mol% It became.
- Example 30 In a 200 ml SUS316 autoclave, 5 g of trimesic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared by the method described in Example 22. 0.5 g of 2.5 wt% Ru-2.5 wt% Pd / silica catalyst and 60 g of water were charged. The pressure was increased to 9 MPa with hydrogen, and the temperature was raised to 50 ° C. while stirring with an electromagnetic stirring blade. It was confirmed that hydrogen absorption disappeared in 1.0 hour from the start of temperature increase and the reaction was completed. When the reaction product was derivatized into a methyl ester and analyzed by gas chromatography, the conversion of trimesic acid was 100% and the selectivity for hydrogenated trimesic acid was 96.1 mol%.
- Example 31 A 300 ml SUS316 autoclave was prepared by 20 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) according to the method described in Example 23. A 2.5 wt% Ru-2.5 wt% Pd / titania powder catalyst 4.0 g and water 120 g were charged. The pressure was increased to 8 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with an electromagnetic stirring blade. After the temperature was raised to 60 ° C., hydrogen absorption disappeared in 2.0 hours, and it was confirmed that the reaction was complete.
- trimellitic acid manufactured by Tokyo Chemical Industry Co., Ltd.
- Example 32 15 ml of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared in a 300 ml SUS316 autoclave by the method described in Example 21. A 2.5 wt% Ru-2.5 wt% Pd / silica catalyst (3.0 g) and water (120 g) were charged. The pressure was increased to 8 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with an electromagnetic stirring blade. After the temperature was raised to 60 ° C., hydrogen absorption disappeared in 2.0 hours, and it was confirmed that the reaction was complete.
- Example 33 A reaction tube made of SUS316 having an inner diameter of 17 mm ⁇ and a length of 320 mm was prepared by the method described in Example 21. Packed with 10 g (25 ml, particle size 1.40-2.36 mm) of 1.0 wt% Ru-1.0 wt% Pd / crushed silica catalyst. Under the conditions of a temperature of 60 ° C. and a hydrogen pressure of 8 MPa, a 6% by weight aqueous solution of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was flowed at 15 g / hr and hydrogen was allowed to react at 0.9 L / hr. When 5500 hours passed from the start of the reaction, no reduction in the conversion rate of trimellitic acid was observed, and 99% or more was maintained from the beginning of the reaction. The selectivity of hydrogenated trimellitic acid during this period remained around 94 mol%.
- Example 34 A 200 ml SUS316 autoclave was prepared in the same manner as described in Example 22 with 5 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.). 0.5 g of 2.5 wt% Ru-2.5 wt% Pd / alumina catalyst and 60 g of water were charged. The pressure was increased to 9 MPa with hydrogen, and the temperature was raised to 50 ° C. while stirring with an electromagnetic stirring blade. After 1.2 hours from the start of temperature increase, hydrogen absorption disappeared and it was confirmed that the reaction was completed. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100% and the selectivity for trimellitic hydride was 96.2 mol%.
- Example 35 Trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.5 g in a 30 ml SUS316 autoclave was prepared in the same manner as described in Example 21. A 2.5 wt% Ru-2.5 wt% Pd / zirconia powder catalyst (0.3 g) and water (9 g) were charged. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. After 2.0 hours from the start of temperature increase, hydrogen absorption disappeared and it was confirmed that the reaction was completed. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100% and the selectivity for trimellitic hydride was 94.2 mol%.
- Example 36 Trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.5 g in a 30 ml SUS316 autoclave was prepared in the same manner as described in Example 23. A 2.5 wt% Ru-2.5 wt% Pd / ceria powder catalyst 0.3 g and water 9 g were charged. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. After 1.6 hours from the start of temperature increase, hydrogen absorption disappeared and it was confirmed that the reaction was complete. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100%, and the selectivity for hydrogenated trimellitic acid was 92.7 mol%.
- Example 37 In a 30 ml SUS316 autoclave, 1.0 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared in the same manner as described in Example 23. 1.0 g% Ru-4.0 wt% Pd / carbon powder catalyst 0.5 g and water 10 g were charged. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. It was confirmed that the reaction was completed with no hydrogen absorption 0.5 hours after the start of temperature increase. When the reaction product was derivatized to a methyl ester form and analyzed by gas chromatography, the conversion of trimellitic acid was 100% and the selectivity for hydrogenated trimellitic acid was 98.6 mol%.
- Example 38 In a 30 ml SUS316 autoclave, 1.0 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared in the same manner as described in Example 23. 2.5 g of Ru-2.5 wt% Pd / carbon powder catalyst 0.5 g and water 10 g were charged. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. It was confirmed that the reaction was completed with no hydrogen absorption 0.5 hours after the start of temperature increase. When the reaction product was derivatized into a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100% and the selectivity for trimellitic hydride was 96.9 mol%.
- Example 39 In a 30 ml SUS316 autoclave, 1.0 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared in the same manner as described in Example 33. 4.0 wt% Ru-1.0 wt% Pd / carbon powder catalyst 0.5 g and water 10 g were charged. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. It was confirmed that the reaction was completed with no hydrogen absorption in 0.6 hours from the start of the temperature increase. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 100% and the selectivity for trimellitic hydrogenated was 97.2 mol%.
- Comparative Example 22 A 300 ml SUS316 autoclave was charged with 20 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.2 g of 5.0 wt% Pd / alumina powder catalyst (manufactured by NEM Chemcat), and 120 g of water. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 100 ° C. while stirring with an electromagnetic stirring blade. Even after 14.0 hours had passed since the temperature was raised to 100 ° C., hydrogen absorption continued but the reaction was stopped. When the reaction product was derivatized to a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 11.8% and the selectivity for trimellitic hydride was 30.2 mol%.
- Comparative Example 24 A 200 ml SUS316 autoclave was prepared in the same manner as described in Example 22 with 5 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.). A 2.5 wt% Pd / silica powder catalyst 0.5 g and water 60 g were charged. The pressure was increased to 9 MPa with hydrogen, and the temperature was raised to 50 ° C. while stirring with an electromagnetic stirring blade. Even after 2 hours had passed since the temperature was raised to 50 ° C., hydrogen absorption continued but the reaction was stopped. When the reaction product was derivatized into a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 6.7%, and the selectivity for hydrogenated trimellitic acid was 69.8 mol%.
- Comparative Example 28 In a 30 ml SUS316 autoclave, 1.0 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared in the same manner as described in Example 23. A 2.5 wt% Ru-2.5 wt% Pt / carbon powder catalyst (0.5 g) and water (10 g) were charged. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. Although the absorption of hydrogen continued even after 3 hours from the start of temperature increase, the reaction was stopped. When the reaction product was derivatized into a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 25.0% and the selectivity for hydrogenated trimellitic acid was 88.0 mol%.
- Comparative Example 30 In a 30 ml SUS316 autoclave, 1.0 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared in the same manner as described in Example 23. 2.5 g Pd-2.5 wt% Pt / carbon powder catalyst 0.5 g and water 10 g were charged. The pressure was increased to 10 MPa with hydrogen, and the temperature was raised to 60 ° C. while stirring with a stirrer chip. Although the absorption of hydrogen continued even after 3 hours from the start of temperature increase, the reaction was stopped. When the reaction product was derivatized into a methyl ester and analyzed by gas chromatography, the conversion of trimellitic acid was 45.0%, and the selectivity for hydrogenated trimellitic acid was 96.7 mol%.
- Comparative Example 35 A 300 ml SUS316 autoclave was charged with 20 g of trimellitic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.6 g of 5.0 wt% Rh / carbon powder catalyst (manufactured by N.E. Chemcat), and 120 g of water. The pressure was increased to 8 MPa with hydrogen, and the temperature was raised to 40 ° C. while stirring with an electromagnetic stirring blade. After the temperature was raised to 40 ° C., hydrogen absorption disappeared in 4.0 hours, and it was confirmed that the reaction was complete.
- trimellitic acid manufactured by Tokyo Chemical Industry Co., Ltd.
- 5.0 wt% Rh / carbon powder catalyst manufactured by N.E. Chemcat
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
[1]
芳香族カルボン酸の芳香環を水素化して脂環式カルボン酸を製造する方法であって、触媒としてルテニウムとパラジウムを含有する触媒を使用することを特徴とする、脂環式カルボン酸の製造方法。
[2]
触媒がルテニウムとパラジウムを担体に共担持している触媒である、[1]記載の脂環式カルボン酸の製造方法。
[3]
水素化反応の反応溶媒として、水、メタノール、エタノール、1-プロパノールおよび2-プロパノールから選ばれる1種または2種以上を使用する[1]~[2]記載の脂環式カルボン酸の製造方法。
[4]
水素化反応の反応溶媒として水を使用する[1]~[2]記載の脂環式カルボン酸の製造方法。
[5]
触媒の担体が活性炭、アルミナ、ジルコニア、セリア、チタニアおよびシリカから選ばれる1種または2種以上の組み合わせからなる[2]~[4]記載の脂環式カルボン酸の製造方法。
芳香族カルボン酸が一般式(1)、(2)または(3)であらわされる芳香族カルボン酸である[1]~[5]記載の脂環式カルボン酸の製造方法。
芳香族カルボン酸がフタル酸、イソフタル酸、テレフタル酸、トリメリット酸、トリメシン酸またはピロメリット酸である[1]~[5]記載の脂環式カルボン酸の製造方法。
[8]
芳香族カルボン酸がトリメリット酸、トリメシン酸またはピロメリット酸である[1]~[5]記載の脂環式カルボン酸の製造方法。
[9]
ルテニウムとパラジウムを担体に共担持した触媒が、ルテニウムとパラジウムが担体表面上に両者を含む粒子の形態で存在しているルテニウム-パラジウム共担持触媒である[2]記載の脂環式カルボン酸の製造方法。
[10]
ルテニウムとパラジウムを担体に共担持した触媒において、ルテニウムとパラジウムが担体表面上に両者を含む粒子の形態で存在していることを特徴とする、ルテニウム-パラジウム共担持触媒。
[11]
ルテニウム-パラジウム共担持触媒が水素化触媒である[10]記載のルテニウム-パラジウム共担持触媒。
[12]
ルテニウム-パラジウム共担持触媒が芳香族カルボン酸の芳香環の水素化触媒である[10]又は[11]記載のルテニウム-パラジウム共担持触媒。
[13]
担体が活性炭、アルミナ、ジルコニア、セリア、チタニアおよびシリカからなる群から選ばれる1種または2種以上の組み合わせからなる[10]~[12]のいずれかに記載のルテニウム-パラジウム共担持触媒。
具体的には水、メタノール、エタノール、1-プロパノール、2-プロパノール、1-ブタノール、2-ブタノール、2-メチル-1-プロパノールといったアルコール類、ジエチルエーテル、ジイソプロピルエーテル、n-ブチルエーテル、シクロペンチルメチルエーテル、tert-ブチルメチルエーテル、THFといったエーテル類、酢酸メチル、酢酸エチルといったエステル類、アセトン、メチルエチルケトンといったケトン類が挙げられる。中でも好ましいのは水、メタノール、エタノール、1-プロパノール、2-プロパノールであり、さらに好ましいのは水である。これらは単独で、または2種以上を適宜混合して使用することができる。
ルテニウム及びパラジウムを共担持させる場合は、ルテニウム及びパラジウムを担体に担持させる順序もとくに限定されない。具体的には同時に担持する方法、逐次に担持する方法等が挙げられる。
触媒にルテニウム及びパラジウムを含有させた後に、調製方法に応じて適宜乾燥、焼成、還元を行うことも可能である。
尚、本発明のルテニウムとパラジウムが担体表面上に両者を含む粒子の形態で存在しているルテニウム-パラジウム共担持触媒を触媒とする水素化反応は、上記の芳香族カルボン酸の量、触媒量、反応温度、水素圧力、反応形式を適宜組み合わせることで、目的の反応時間で目的とする選択率の脂環式カルボン酸の製造が可能となる。
なお、芳香族カルボン酸の転化率、脂環式カルボン酸の選択率は反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーにて分析して求めた。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)1.0g、公知の方法(Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis の40ページに記載の沈着法)で調製した1.0重量%Ru-4.0重量%Pd/カーボン粉末触媒0.5g、水10gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から0.5時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸(1,2,4-シクロヘキサントリカルボン酸)の選択率は98.6%(モル%)となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)1.0g、実施例1記載と同様な方法で調製した2.5重量%Ru-2.5重量%Pd/カーボン粉末触媒0.5g、水10gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から0.5時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は96.9%(モル%)となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)1.0g、実施例1記載と同様な方法で調製した4.0重量%Ru-1.0重量%Pd/カーボン粉末触媒0.5g、水10gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から0.6時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は97.2%(モル%)となった。
300mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)20g、実施例1記載と同様な方法で調製した4.0重量%Ru-1.0重量%Pd/カーボン粉末触媒2g、水120gを仕込んだ。水素で10MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら60℃に昇温した。昇温開始から1.2時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は94.2%(モル%)となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)1.5g、実施例1記載と同様な方法で調製した2.5重量%Ru-2.5重量%Pd/カーボン粉末触媒0.3g、水9gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から1.8時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は95.1%(モル%)となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)1.5g、実施例1記載と同様な方法で調製した2.5重量%Ru-2.5重量%Pd/アルミナ粉末触媒0.3g、水9gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から1.7時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は94.2%(モル%)となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)1.5g、実施例1記載と同様な方法で調製した2.5重量%Ru-2.5重量%Pd/ジルコニア粉末触媒0.3g、水9gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から2.0時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は93.3%(モル%)となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)1.5g、実施例1記載と同様な方法で調製した2.5重量%Ru-2.5重量%Pd/セリア粉末触媒0.3g、水9gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から1.6時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は92.7%(モル%)となった。
200mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)6g、実施例1記載と同様な方法で調製した2.5重量%Ru-2.5重量%Pd/チタニア粉末触媒1.2g、水36gを仕込んだ。水素で9MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら55℃に昇温した。昇温開始から1.5時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は94.0%(モル%)となった。
200mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)6g、公知の方法(触媒調製化学 49ページ記載の含浸法)で調製した2.5重量%Ru-2.5重量%Pd/シリカ粉末触媒1.2g、水36gを仕込んだ。水素で9MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら50℃に昇温した。昇温開始から2.0時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は94.1%(モル%)となった。
300mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)20g、実施例1記載と同様な方法で調製した1.0重量%Ru-1.0重量%Pd/チタニア粉末触媒4.0g、水120gを仕込んだ。水素で8MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら60℃に昇温した。60℃に昇温後2.0時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は93.5%となった。
回収した触媒に対して賦活をせずに、同条件で反応を繰り返し行った。反応7回までのトリメリット酸の転化率は100%、水素化トリメリット酸の平均選択率は93.6%(モル%)となった。
200mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)6g、実施例1記載と同様な方法で調製した1.0重量%Ru-1.0重量%Pd/チタニア粉末触媒3.0g、水36gを仕込んだ。水素で9MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら50℃に昇温した。昇温開始から1.3時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は94.4%(モル%)となった。
内径17mmφ、長さ320mmのSUS316製の反応管に、実施例10に記載と同様な方法で調製した1.0重量%Ru-1.0重量%Pd/球状シリカ触媒10g(25ml)を詰めた。温度80℃、水素圧力8MPaの条件下、トリメリット酸(東京化成工業社 製)2重量%水溶液を30g/hr、水素を1.8L/hrで流し反応させた。反応開始から1400時間経過時点でトリメリット酸の転化率の低下は見られず、反応初期から89%を維持していた。この間の水素化トリメリット酸の選択率は94%(モル%)前後を推移していた。
200mlのSUS316製オートクレーブにピロメリット酸(東京化成工業社 製)6g、実施例1記載と同様な方法で調製した2.5重量%Ru-2.5重量%Pd/チタニア粉末触媒1.2g、水36gを仕込んだ。水素で9MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら50℃に昇温した。昇温開始から3.0時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、ピロメリット酸の転化率は100%、水素化ピロメリット酸(1,2,4,5-シクロヘキサンテトラカルボン酸)の選択率は94.5%(モル%)となった。
30mlのSUS316製オートクレーブにトリメシン酸(東京化成工業社 製)1.5g、実施例1記載と同様な方法で調製した2.5重量%Ru-2.5重量%Pd/チタニア粉末触媒0.3g、水9gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から1.4時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメシン酸の転化率は100%、水素化トリメシン酸(1,3,5-シクロヘキサントリカルボン酸)の選択率は93.0%(モル%)となった。
300mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)20g、実施例1記載と同様な方法で調製した5.0重量%Ru/カーボン粉末触媒1.6g、水120gを仕込んだ。水素で10MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら100℃に昇温した。100℃に昇温後8.2時間経過しても水素の吸収は継続していたが反応を停止した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は87.1%、水素化トリメリット酸の選択率は60.4%(モル%)となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)1.0g、実施例1記載と同様な方法で調製した5.0重量%Pd/カーボン粉末触媒0.5g、水10gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から3時間経過しても水素の吸収は継続していたが反応を停止した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は77.0%、水素化トリメリット酸の選択率は96.3%(モル%)となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)1.5g、実施例1記載と同様な方法で調製した5.0重量%Ru/チタニア粉末触媒0.3g、水9gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から3時間経過しても水素の吸収は継続していたが反応を停止した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は8.6%、水素化トリメリット酸の選択率は70.5%(モル%)となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)1.5g、実施例1記載と同様な方法で調製した5.0重量%Pd/チタニア粉末触媒0.3g、水9gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から3時間経過しても水素の吸収は継続していたが反応を停止した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は9.2%、水素化トリメリット酸の選択率は79.3%(モル%)となった。
300mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)20g、エヌイーケムキャット製の5.0重量%Rh/カーボン粉末触媒1.6g、水120gを仕込んだ。水素で8MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら60℃に昇温した。40℃に昇温後4.0時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は97.2%(モル%)となった。
回収した触媒に対して賦活をせずに、同条件で反応を繰り返し行ったが、水素の吸収は見られず、トリメリット酸の転化率は0%だった。
内径17mmφ、長さ320mmのSUS316製の反応管に、実施例1に記載と同様な方法で調製した2.0重量%Ru/粒状カーボン触媒10g(18ml)を詰めた。温度60℃、水素圧力5MPaの条件下、トリメリット酸(東京化成工業社 製)2重量%水溶液を30g/hr、水素を1.8L/hrで流し反応させた。反応開始から20時間時点でトリメリット酸の転化率は22%、水素化トリメリット酸の選択率は86%(モル%)となった。
内径17mmφ、長さ320mmのSUS316製の反応管に、実施例1に記載と同様な方法で調製した2.0重量%Ru/球状アルミナ触媒10g(18ml)を詰めた。温度60℃、水素圧力5MPaの条件下、トリメリット酸(東京化成工業社 製)2重量%水溶液を30g/hr、水素を1.8L/hrで流し反応させた。反応開始から6時間時点でトリメリット酸の転化率は23%、水素化トリメリット酸の選択率は88%(モル%)となった。
塩化ルテニウムn水和物(和光純薬製)0.647gと塩化パラジウム(和光純薬製)0.417gを水に溶解させた。シリカゲル(キャリアクトQ50、富士シリシア化学製、粒径75-150μm)10gに塩化ルテニウムと塩化パラジウムを溶解させた水溶液を添加し、総重量を60gとした。アスピレーター減圧下、水浴で加熱し、水分を蒸発させて塩化ルテニウムと塩化パラジウムを担体に担持させた。その後150℃で2時間乾燥、空気雰囲気下400℃で4時間焼成、250℃で4時間気相水素還元を実施することでルテニウム-パラジウム共担持触媒(2.5重量%Ru-2.5重量%Pd/SiO2)を調製した。
この方法で調製したルテニウム-パラジウム共担持触媒の透過電子顕微鏡像を図1、図2に示す。担体表面上に存在する粒子のサイズは3-50nmとなった。この粒子中のルテニウム、パラジウムの共存状態をEDXにて分析した結果を図5、図6に示す。粒子に含まれるルテニウム/パラジウムモル比の平均値は1であった。
金属源をルテニウムアセチルアセトナート錯体(アルドリッチ社製)と酢酸パラジウム(小島化学薬品製)、溶媒をアセトニトリルに変更し、これ以降は実施例21に倣った方法でルテニウム-パラジウム共担持触媒を調製した(2.5重量%Ru-2.5重量%Pd/SiO2)。
この方法で調製したルテニウム-パラジウム共担持触媒の透過電子顕微鏡像を図3、図4に示す。担体表面上に存在する粒子のサイズは1-15nmとなった。この粒子中のルテニウム、パラジウムの共存状態をEDXにて分析した結果を図7、図8に示す。粒子に含まれるルテニウム/パラジウムモル比の平均値は1であった。
塩化ルテニウムn水和物(和光純薬製)0.323gと塩化パラジウム(和光純薬製)0.208gを水に溶解させた。チタニア(和光純薬製)5gに水とNaOH(和光純薬製)1gを添加し、総重量を100gにし、水浴で加熱した。水溶液の温度を80℃程度まで昇温後、塩化ルテニウムと塩化パラジウムを含む水溶液を60分かけて添加した。添加終了後、60分程度経過したら、冷却し、濾過でルテニウム-パラジウム共担持触媒(2.5重量%Ru-2.5重量%Pd /TiO2)を回収した。
200mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)6g、実施例21記載の方法で調製した。2.5重量%Ru-2.5重量%Pd/シリカ触媒1.2g、水36gを仕込んだ。水素で9MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら50℃に昇温した。昇温開始から2.0時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸(1,2,4-シクロヘキサントリカルボン酸)の選択率は94.1モル%となった。
200mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社 製)5g、実施例22記載の方法で調製した2.5重量%Ru-2.5重量%Pd/シリカ触媒0.5g、水60gを仕込んだ。水素で9MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら50℃に昇温した。昇温開始から1.0時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は96.6モル%となった。
200mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)6g、実施例23記載の方法で調製した。2.5重量%Ru-2.5重量%Pd/チタニア粉末触媒1.2g、水36gを仕込んだ。水素で9MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら55℃に昇温した。昇温開始から1.5時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は94.0モル%となった。
200mlのSUS316製オートクレーブにピロメリット酸(東京化成工業社製)5g、実施例22記載の方法で調製した。2.5重量%Ru-2.5重量%Pd/シリカ触媒0.5g、水60gを仕込んだ。水素で9MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら50℃に昇温した。昇温開始から2.0時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、ピロメリット酸の転化率は100%、水素化ピロメリット酸(1,2,4,5-シクロヘキサンテトラカルボン酸)の選択率は96.1モル%となった。
200mlのSUS316製オートクレーブにピロメリット酸(東京化成工業社製)6g、実施例23記載の方法で調製した。2.5重量%Ru-2.5重量%Pd/チタニア粉末触媒1.2g、水36gを仕込んだ。水素で9MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら50℃に昇温した。昇温開始から3.0時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、ピロメリット酸の転化率は100%、水素化ピロメリット酸の選択率は94.5モル%となった。
30mlのSUS316製オートクレーブにトリメシン酸(東京化成工業社製)1.5g、実施例23記載の方法で調製した。2.5重量%Ru-2.5重量%Pd/チタニア粉末触媒0.3g、水9gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から1.4時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメシン酸の転化率は100%、水素化トリメシン酸(1,3,5-シクロヘキサントリカルボン酸)の選択率は93.0モル%となった。
200mlのSUS316製オートクレーブにトリメシン酸(東京化成工業社製)5g、実施例22記載の方法で調製した。2.5重量%Ru-2.5重量%Pd/シリカ触媒0.5g、水60gを仕込んだ。水素で9MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら50℃に昇温した。昇温開始から1.0時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメシン酸の転化率は100%、水素化トリメシン酸の選択率は96.1モル%となった。
300mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)20g、実施例23記載の方法で調製した。2.5重量%Ru-2.5重量%Pd/チタニア粉末触媒4.0g、水120gを仕込んだ。水素で8MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら60℃に昇温した。60℃に昇温後2.0時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は93.5モル%となった。
回収した触媒に対して賦活をせずに、同条件で反応を繰り返し行った。反応7回までのトリメリット酸の転化率は100%、水素化トリメリット酸の平均選択率は93.6モル%となった。
300mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)15g、実施例21記載の方法で調製した。2.5重量%Ru-2.5重量%Pd/シリカ触媒3.0g、水120gを仕込んだ。水素で8MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら60℃に昇温した。60℃に昇温後2.0時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は94.6モル%となった。
回収した触媒に対して賦活をせずに、同条件で反応を繰り返し行った。反応13回までのトリメリット酸の転化率は100%、水素化トリメリット酸の平均選択率は94.3モル%となった。
内径17mmφ、長さ320mmのSUS316製の反応管に、実施例21記載の方法で調製した。1.0重量%Ru-1.0重量%Pd/破砕シリカ触媒10g(25ml、粒径1.40-2.36mm)を詰めた。温度60℃、水素圧力8MPaの条件下、トリメリット酸(東京化成工業社製)6重量%水溶液を15g/hr、水素を0.9L/hrで流し反応させた。反応開始から5500時間経過時点でトリメリット酸の転化率の低下は見られず、反応初期から99%以上を維持していた。この間の水素化トリメリット酸の選択率は94モル%前後を推移していた。
200mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)5g、実施例22記載と同様な方法で調製した。2.5重量%Ru-2.5重量%Pd/アルミナ触媒0.5g、水60gを仕込んだ。水素で9MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら50℃に昇温した。昇温開始から1.2時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は96.2モル%となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)1.5g、実施例21記載と同様な方法で調製した。2.5重量%Ru-2.5重量%Pd/ジルコニア粉末触媒0.3g、水9gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から2.0時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は94.2モル%となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)1.5g、実施例23記載と同様な方法で調製した。2.5重量%Ru-2.5重量%Pd/セリア粉末触媒0.3g、水9gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から1.6時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は92.7モル%となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)1.0g、実施例23記載と同様な方法で調製した。1.0重量%Ru-4.0重量%Pd/カーボン粉末触媒0.5g、水10gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から0.5時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は98.6モル%となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)1.0g、実施例23記載と同様な方法で調製した。2.5重量%Ru-2.5重量%Pd/カーボン粉末触媒0.5g、水10gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から0.5時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は96.9モル%となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)1.0g、実施例33記載と同様な方法で調製した。4.0重量%Ru-1.0重量%Pd/カーボン粉末触媒0.5g、水10gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から0.6時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は97.2モル%となった。
300mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)20g、5.0重量%Pd/アルミナ粉末触媒3.2g(エヌ・イー・ケムキャット製)、水120gを仕込んだ。水素で10MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら100℃に昇温した。100℃に昇温後14.0時間経過しても水素の吸収は継続していたが反応を停止した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は11.8%、水素化トリメリット酸の選択率は30.2モル%となった。
200mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)5g、実施例21記載と同様な方法で調製した。2.5重量%Ru/シリカ粉末触媒0.5g、水60gを仕込んだ。水素で8MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら100℃に昇温した。100℃に昇温後2時間経過しても水素の吸収は継続していたが反応を停止した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は54.9%、水素化トリメリット酸の選択率は82.7モル%となった。
200mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)5g、実施例22記載と同様な方法で調製した。2.5重量%Pd/シリカ粉末触媒0.5g、水60gを仕込んだ。水素で9MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら50℃に昇温した。50℃に昇温後2時間経過しても水素の吸収は継続していたが反応を停止した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率6.7%、水素化トリメリット酸の選択率は69.8モル%となった。
200mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)5g、実施例21記載と同様な方法で調製した。2.5重量%Ru/シリカ粉末触媒0.5g、実施例22記載と同様な方法で調製した2.5重量%Pd/シリカ粉末触媒0.5g、水60gを仕込んだ。水素で9MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら50℃に昇温した。50℃に昇温後2時間経過しても水素の吸収は継続していたが反応を停止した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率17.2%、水素化トリメリット酸の選択率は86.2モル%となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)1.0g、5.0重量%Ru/カーボン粉末(エヌ・イー・ケムキャット製)0.25g、5.0重量%Pd/カーボン粉末(エヌ・イー・ケムキャット製)0.25g、水10gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から3時間経過しても水素の吸収は継続していたが反応を停止した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は88.0%、水素化トリメリット酸の選択率は93.0モル%となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)1.5g、実施例23記載と同様な方法で調製した。2.5重量%Ru/チタニア粉末触媒0.15g、実施例23記載と同様な方法で調製した2.5重量%Pd/チタニア粉末触媒0.15g、水9gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から3時間経過しても水素の吸収は継続していたが反応を停止した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は49%、水素化トリメリット酸の選択率は87.0モル%となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)1.0g、実施例23記載と同様な方法で調製した。2.5重量%Ru-2.5重量%Pt/カーボン粉末触媒0.5g、水10gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から3時間経過しても水素の吸収は継続していたが反応を停止した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は25.0%、水素化トリメリット酸の選択率は88.0モル%となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)1.0g、実施例23記載と同様な方法で調製した。2.5重量%Ru-2.5重量%Ir/カーボン粉末触媒0.5g、水10gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から3時間経過しても水素の吸収は継続していたが反応を停止した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は10.0%、水素化トリメリット酸の選択率は78.4モル%となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)1.0g、実施例23記載と同様な方法で調製した。2.5重量%Pd-2.5重量%Pt/カーボン粉末触媒0.5g、水10gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から3時間経過しても水素の吸収は継続していたが反応を停止した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は45.0%、水素化トリメリット酸の選択率は96.7モル%となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)1.0g、実施例23記載と同様な方法で調製した。2.5重量%Pd-2.5重量%Ir/カーボン粉末触媒0.5g、水10gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から3時間経過しても水素の吸収は継続していたが反応を停止した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は14.0%、水素化トリメリット酸の選択率は89.4モル%となった。
30mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)1.0g、実施例21記載と同様な方法で調製した。2.5重量%Pd-2.5重量%Au/カーボン粉末触媒0.5g、水10gを仕込んだ。水素で10MPaまで昇圧し、スターラーチップで攪拌しながら60℃に昇温した。昇温開始から3時間経過しても水素の吸収は継続していたが反応を停止した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は76.0%、水素化トリメリット酸の選択率は96.2モル%となった。
200mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)6g、実施例23記載と同様な方法で調製した。2.5重量%Ru-2.5重量%Pt/チタニア粉末触媒1.2g、水36gを仕込んだ。水素で9MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら60℃に昇温した。昇温開始から2時間経過しても水素の吸収は継続していたが反応を停止した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は42%、水素化トリメリット酸の選択率は89.7モル%となった。
200mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)5g、実施例21記載と同様な方法で調製した。2.5重量%Pd-2.5重量%Pt/シリカ粉末触媒0.5g、水60gを仕込んだ。水素で9MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら50℃に昇温した。50℃に昇温後2時間経過しても水素の吸収は継続していたが反応を停止した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率10.5%、水素化トリメリット酸の選択率は83.9モル%となった。
300mlのSUS316製オートクレーブにトリメリット酸(東京化成工業社製)20g、5.0重量%Rh/カーボン粉末触媒(エヌ・イー・ケムキャット製)1.6g、水120gを仕込んだ。水素で8MPaまで昇圧し、電磁式攪拌羽根で攪拌しながら40℃に昇温した。40℃に昇温後4.0時間で水素の吸収がなくなり、反応が完結したことを確認した。反応生成物をメチルエステル体に誘導体化後、ガスクロマトグラフィーで分析すると、トリメリット酸の転化率は100%、水素化トリメリット酸の選択率は97.2モル%となった。
回収した触媒に対して賦活をせずに、同条件で反応を繰り返し行ったが、水素の吸収は見られず、トリメリット酸の転化率は0%だった。
Claims (13)
- 芳香族カルボン酸の芳香環を水素化して脂環式カルボン酸を製造する方法であって、触媒としてルテニウムとパラジウムを含有する触媒を使用することを特徴とする、脂環式カルボン酸の製造方法。
- 触媒がルテニウムとパラジウムを担体に共担持している触媒である、請求項1記載の脂環式カルボン酸の製造方法。
- 水素化反応の反応溶媒として、水、メタノール、エタノール、1-プロパノールおよび2-プロパノールから選ばれる1種または2種以上を使用する、請求項1または2記載の脂環式カルボン酸の製造方法。
- 水素化反応の反応溶媒として水を使用する、請求項1または2記載の脂環式カルボン酸の製造方法。
- 触媒の担体が活性炭、アルミナ、ジルコニア、セリア、チタニアおよびシリカから選ばれる1種または2種以上の組み合わせからなる請求項2~4のいずれかに記載の脂環式カルボン酸の製造方法。
- 芳香族カルボン酸がフタル酸、イソフタル酸、テレフタル酸、トリメリット酸、トリメシン酸またはピロメリット酸である請求項1~5のいずれかに記載の脂環式カルボン酸の製造方法。
- 芳香族カルボン酸がトリメリット酸、トリメシン酸またはピロメリット酸である請求項1~5のいずれかに記載の脂環式カルボン酸の製造方法。
- ルテニウムとパラジウムを担体に共担持した触媒が、ルテニウムとパラジウムが担体表面上に両者を含む粒子の形態で存在しているルテニウム-パラジウム共担持触媒である請求項2記載の脂環式カルボン酸の製造方法。
- ルテニウムとパラジウムを担体に共担持した触媒において、ルテニウムとパラジウムが担体表面上に両者を含む粒子の形態で存在していることを特徴とする、ルテニウム-パラジウム共担持触媒。
- ルテニウム-パラジウム共担持触媒が水素化触媒である請求項10記載のルテニウム-パラジウム共担持触媒。
- ルテニウム-パラジウム共担持触媒が芳香族カルボン酸の芳香環の水素化触媒である請求項10又は11記載のルテニウム-パラジウム共担持触媒。
- 担体が活性炭、アルミナ、ジルコニア、セリア、チタニアおよびシリカからなる群から選ばれる1種または2種以上の組み合わせからなる請求項10~12のいずれかに記載のルテニウム-パラジウム共担持触媒。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12752352.0A EP2682380B1 (en) | 2011-03-01 | 2012-02-24 | Method for producing alicyclic carboxylic acid and catalyst used in same |
KR1020137025644A KR101904047B1 (ko) | 2011-03-01 | 2012-02-24 | 지환식 카르본산의 제조 방법 및 이 방법에 이용하는 촉매 |
CN201280021585.4A CN103502197B (zh) | 2011-03-01 | 2012-02-24 | 脂环族羧酸的制造方法及用于该方法的催化剂 |
US14/002,602 US9084985B2 (en) | 2011-03-01 | 2012-02-24 | Method for producing alicyclic carboxylic acid and catalyst used in same |
JP2013502297A JP6146301B2 (ja) | 2011-03-01 | 2012-02-24 | 脂環式カルボン酸の製造方法及び該方法に用いる触媒 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011043523 | 2011-03-01 | ||
JP2011-043523 | 2011-03-01 | ||
JP2012010130 | 2012-01-20 | ||
JP2012-010130 | 2012-01-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012117976A1 true WO2012117976A1 (ja) | 2012-09-07 |
Family
ID=46757913
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/054640 WO2012117976A1 (ja) | 2011-03-01 | 2012-02-24 | 脂環式カルボン酸の製造方法及び該方法に用いる触媒 |
Country Status (7)
Country | Link |
---|---|
US (1) | US9084985B2 (ja) |
EP (1) | EP2682380B1 (ja) |
JP (1) | JP6146301B2 (ja) |
KR (1) | KR101904047B1 (ja) |
CN (1) | CN103502197B (ja) |
TW (1) | TWI513683B (ja) |
WO (1) | WO2012117976A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014181199A (ja) * | 2013-03-19 | 2014-09-29 | Mitsubishi Gas Chemical Co Inc | 脂環式カルボン酸の製造方法 |
JP2015073960A (ja) * | 2013-10-10 | 2015-04-20 | 三菱瓦斯化学株式会社 | 芳香族カルボン酸類の水素化触媒およびその製造方法 |
JP2019030827A (ja) * | 2017-08-04 | 2019-02-28 | 独立行政法人国立高等専門学校機構 | パラジウム−ルテニウム複合微粒子を用いた触媒およびその製造方法 |
JP2019037982A (ja) * | 2018-11-29 | 2019-03-14 | 株式会社フルヤ金属 | 担持触媒 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015068161A1 (en) * | 2013-11-06 | 2015-05-14 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. | A method for storage and release of hydrogen |
CN106866415A (zh) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | 一种脂环族羧酸酯的制造方法 |
KR101883993B1 (ko) * | 2016-09-29 | 2018-07-31 | 롯데케미칼 주식회사 | 1,3-사이클로헥산디카르복시산의 제조 방법 |
CN113336623B (zh) * | 2020-03-03 | 2023-05-30 | 台湾中油股份有限公司 | 含双脂环族的二元醇制造方法 |
CN114100653B (zh) * | 2020-08-31 | 2024-03-08 | 台州学院 | 一种氮化物负载钯催化剂及其制备方法和应用 |
CN113083294A (zh) * | 2021-04-02 | 2021-07-09 | 绍兴绿奕化工有限公司 | 一种催化加氢催化剂及其制备方法和应用 |
CN115232001A (zh) * | 2021-04-25 | 2022-10-25 | 中国石油化工股份有限公司 | 氢化均苯四甲酸合成方法 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002020346A (ja) * | 2000-07-04 | 2002-01-23 | Mitsubishi Chemicals Corp | シクロヘキサンカルボン酸類の製造方法 |
CN1689698A (zh) * | 2004-04-29 | 2005-11-02 | 中国石油天然气股份有限公司 | 一种生产1,4-环己烷二甲酸二甲酯的催化剂 |
JP2006045166A (ja) | 2004-08-09 | 2006-02-16 | Nippon Steel Chem Co Ltd | 脂環式多価カルボン酸及びその酸無水物の製造方法 |
JP2006124313A (ja) * | 2004-10-28 | 2006-05-18 | Nippon Steel Chem Co Ltd | 脂環式多価カルボン酸及びその無水物の製造方法 |
JP3834836B2 (ja) | 1995-05-31 | 2006-10-18 | 新日本理化株式会社 | 脂環式ポリカルボン酸エステルの製造方法 |
JP2008063263A (ja) | 2006-09-06 | 2008-03-21 | Mitsubishi Gas Chem Co Inc | 水素化芳香族カルボン酸の製造方法 |
JP2009040717A (ja) * | 2007-08-08 | 2009-02-26 | Sumitomo Seika Chem Co Ltd | シクロヘキサンカルボン酸の製造方法 |
CN101450308A (zh) * | 2007-11-28 | 2009-06-10 | 中国石油化工股份有限公司 | 一种炭负载型贵金属催化剂及其制备方法 |
JP4622406B2 (ja) | 2004-09-15 | 2011-02-02 | 新日本理化株式会社 | 水素化芳香族ポリカルボン酸の製造方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE60221955T2 (de) * | 2001-12-28 | 2007-12-06 | Mitsubishi Gas Chemical Co., Inc. | Verfahren zur Herstellung von hydrierter aromatischer Polycarbonsäure und Verfahren zur Herstellung von hydriertem aromatischem Polycarbonsäureanhydrid |
DE10225565A1 (de) | 2002-06-10 | 2003-12-18 | Oxeno Olefinchemie Gmbh | Katalysator und Verfahren zur Hydrierung von aromatischen Verbindungen |
GB0227087D0 (en) * | 2002-11-20 | 2002-12-24 | Exxonmobil Chem Patents Inc | Hydrogenation of benzene polycarboxylic acids or derivatives thereof |
-
2012
- 2012-02-24 KR KR1020137025644A patent/KR101904047B1/ko active IP Right Grant
- 2012-02-24 EP EP12752352.0A patent/EP2682380B1/en active Active
- 2012-02-24 US US14/002,602 patent/US9084985B2/en active Active
- 2012-02-24 WO PCT/JP2012/054640 patent/WO2012117976A1/ja active Application Filing
- 2012-02-24 CN CN201280021585.4A patent/CN103502197B/zh active Active
- 2012-02-24 JP JP2013502297A patent/JP6146301B2/ja active Active
- 2012-03-01 TW TW101106711A patent/TWI513683B/zh active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3834836B2 (ja) | 1995-05-31 | 2006-10-18 | 新日本理化株式会社 | 脂環式ポリカルボン酸エステルの製造方法 |
JP2002020346A (ja) * | 2000-07-04 | 2002-01-23 | Mitsubishi Chemicals Corp | シクロヘキサンカルボン酸類の製造方法 |
CN1689698A (zh) * | 2004-04-29 | 2005-11-02 | 中国石油天然气股份有限公司 | 一种生产1,4-环己烷二甲酸二甲酯的催化剂 |
JP2006045166A (ja) | 2004-08-09 | 2006-02-16 | Nippon Steel Chem Co Ltd | 脂環式多価カルボン酸及びその酸無水物の製造方法 |
JP4622406B2 (ja) | 2004-09-15 | 2011-02-02 | 新日本理化株式会社 | 水素化芳香族ポリカルボン酸の製造方法 |
JP2006124313A (ja) * | 2004-10-28 | 2006-05-18 | Nippon Steel Chem Co Ltd | 脂環式多価カルボン酸及びその無水物の製造方法 |
JP2008063263A (ja) | 2006-09-06 | 2008-03-21 | Mitsubishi Gas Chem Co Inc | 水素化芳香族カルボン酸の製造方法 |
JP2009040717A (ja) * | 2007-08-08 | 2009-02-26 | Sumitomo Seika Chem Co Ltd | シクロヘキサンカルボン酸の製造方法 |
CN101450308A (zh) * | 2007-11-28 | 2009-06-10 | 中国石油化工股份有限公司 | 一种炭负载型贵金属催化剂及其制备方法 |
Non-Patent Citations (3)
Title |
---|
CHEMISTRY A EUROPEAN JOURNAL, vol. 15, 2009, pages 6953 - 6963 |
JOHN MEURIG THOMAS: "High-Performance Nanocatalysts for Single-Step Hydrogenations", ACCOUNTS OF CHEMICAL RESEARCH, vol. 36, no. 1, 2003, pages 20 - 30, XP055122661 * |
JOURNAL OF ORGANIC CHEMISTRY, vol. 31, 1966, pages 3438 - 3439 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014181199A (ja) * | 2013-03-19 | 2014-09-29 | Mitsubishi Gas Chemical Co Inc | 脂環式カルボン酸の製造方法 |
JP2015073960A (ja) * | 2013-10-10 | 2015-04-20 | 三菱瓦斯化学株式会社 | 芳香族カルボン酸類の水素化触媒およびその製造方法 |
JP2019030827A (ja) * | 2017-08-04 | 2019-02-28 | 独立行政法人国立高等専門学校機構 | パラジウム−ルテニウム複合微粒子を用いた触媒およびその製造方法 |
JP7017730B2 (ja) | 2017-08-04 | 2022-02-09 | 学校法人福岡工業大学 | パラジウム-ルテニウム複合微粒子を用いた触媒の製造方法 |
JP2019037982A (ja) * | 2018-11-29 | 2019-03-14 | 株式会社フルヤ金属 | 担持触媒 |
Also Published As
Publication number | Publication date |
---|---|
JP6146301B2 (ja) | 2017-06-14 |
KR101904047B1 (ko) | 2018-10-04 |
US9084985B2 (en) | 2015-07-21 |
EP2682380A1 (en) | 2014-01-08 |
TWI513683B (zh) | 2015-12-21 |
US20130338393A1 (en) | 2013-12-19 |
CN103502197B (zh) | 2015-04-01 |
CN103502197A (zh) | 2014-01-08 |
TW201245138A (en) | 2012-11-16 |
EP2682380A4 (en) | 2014-07-30 |
EP2682380B1 (en) | 2018-07-04 |
KR20140023912A (ko) | 2014-02-27 |
JPWO2012117976A1 (ja) | 2014-07-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6146301B2 (ja) | 脂環式カルボン酸の製造方法及び該方法に用いる触媒 | |
Feng et al. | Hydrogenation of levulinic acid to γ-valerolactone over Pd@ UiO-66-NH2 with high metal dispersion and excellent reusability | |
CN100409943C (zh) | 一种化学置换法制备纳米贵金属加氢催化剂的方法及应用 | |
JPH10306047A (ja) | 1,6−ヘキサンジオールの製造方法 | |
Ye et al. | Catalytic transfer hydrogenation of the C═ O bond in unsaturated aldehydes over Pt nanoparticles embedded in porous UiO-66 nanoparticles | |
JP6083270B2 (ja) | 脂環式カルボン酸の製造方法 | |
Feng et al. | Green oxidation of cyclohexanone to adipic acid over phosphotungstic acid encapsulated in UiO-66 | |
US10597344B2 (en) | Method for preparing 1,3-cyclohexanedimethanol | |
CN106866415A (zh) | 一种脂环族羧酸酯的制造方法 | |
JP6314411B2 (ja) | 芳香族カルボン酸類の水素化触媒およびその製造方法 | |
JP2007245068A (ja) | 貴金属含有触媒およびそれを用いたα,β−不飽和カルボン酸の製造方法 | |
JP6536270B2 (ja) | 多価置換ビフェニル化合物の製造方法及びそれに用いられる固体触媒 | |
JP5530074B2 (ja) | 複合体およびその製造方法 | |
JP4676887B2 (ja) | α,β−不飽和カルボン酸の製造方法、その触媒及びその製造方法 | |
JP6988642B2 (ja) | アリル化合物の異性化方法 | |
JP7188543B2 (ja) | アリル化合物の異性化方法 | |
TWI400228B (zh) | 對羧基苯甲醛氫化成對甲基苯甲酸之方法 | |
Li et al. | Chemoselective oxidation of bio-glycerol with nano-sized metal catalysts | |
JP5340705B2 (ja) | 貴金属含有触媒の製造方法、並びにα,β−不飽和カルボン酸及びα,β−不飽和カルボン酸無水物の製造方法 | |
JP6687813B2 (ja) | 1,3−シクロヘキサンジカルボン酸の製造方法 | |
JP2001097904A (ja) | 1,6−ヘキサンジオールの製造方法 | |
JP4014287B2 (ja) | 3−アシロキシシクロヘキセンの製造方法 | |
JP2005539078A (ja) | 光学的に純粋な(S)−β−ヒドロキシ−γ−ブチロラクトンの連続製造方法 | |
JP2001031622A (ja) | デカヒドロナフタレンジカルボン酸の製造方法 | |
JPH1160524A (ja) | 1,6−ヘキサンジオールの製造法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12752352 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2013502297 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14002602 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20137025644 Country of ref document: KR Kind code of ref document: A |