JP3110485B2 - Method for producing partial oxide of alicyclic compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel cell system using an ion conductor provided with a catalyst electrode, to convert a corresponding partial oxide such as an alicyclic alcohol or an alicyclic ketone from an alicyclic compound and oxygen. The present invention relates to a method of extracting electric power energy as needed while manufacturing.

[0002]

BACKGROUND OF THE INVENTION A process for the production of cyclohexanol and / or cyclohexanone from cycloaliphatic compounds, in particular cyclohexane, by oxygen oxidation is disclosed in GB 967,341.
Nos. 975 and 710, Japanese Patents (Japanese Unexamined Patent Publication No.
No.168631), Japanese published patent (Japanese Patent Publication No. 1-334)
No. 55). According to these methods, the selectivity of cyclohexanone and / or cyclohexanol is generally low because direct contact of oxygen with cyclohexane is required under high temperature conditions. Alternatively, the conversion of cyclohexane must be suppressed to a very low level in order to maintain a high selectivity.In general, the conversion of cyclohexane is kept at a value of about several percent, which is extremely disadvantageous in terms of energy and economical. It can not be said.

[0003] On the other hand, attempts have been made to use a fuel cell system to produce various useful compounds and at the same time to extract electric current. However, a method for producing partial oxides of alicyclic compounds such as cyclohexanone and cyclohexanol has been proposed. Other than the invention of the present inventor in Japanese Patent Application No. 1-261494, it has not been known until now.

[0004]

SUMMARY OF THE INVENTION The present invention uses a fuel cell system to selectively convert a corresponding partial oxide such as an alicyclic alcohol and an alicyclic ketone from an alicyclic compound and oxygen by a single-step reaction operation. By manufacturing, it solves problems such as the complexity of the manufacturing process, the generation of a large amount of by-products, and the large consumption of energy in the conventional manufacturing method.In addition, it can be carried out under extremely mild conditions. Is to increase the economic efficiency, such as being able to produce at the same time,
As a result of further diligent studies from the inventor's patent application,
As a catalyst electrode to be brought into contact with oxygen and a fatty environmental compound, at least one kind of a halide of Group 7 metal and at least one kind of a halide of Group 1 metal in the periodic table.
By constituting from more than one kind and a conductive polymer material, a corresponding partial oxide of the alicyclic compound can be obtained very effectively, and a part of the alicyclic compound characterized by extracting power energy as necessary. A method for producing an oxide has been found.

It is an object of the present invention to provide an ion conductor provided with a catalyst electrode, in which one electrode is brought into contact with a hydrogen donor and the other electrode is brought into contact with an alicyclic compound and oxygen, and the fuel cell system is used for the alicyclic reaction. A method for producing a partial oxide of an alicyclic compound is characterized in that a corresponding partial oxide of the formula compound is obtained and, at the same time, power energy is extracted as necessary.

[0006]

The alicyclic compound used in the method of the present invention is a substituted or unsubstituted alicyclic hydrocarbon. For example, they are cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane and derivatives thereof, and examples of the substituent which these may have include an alkyl group, an alkoxy group, a sulfone group, and a halogen atom.

[0007] The oxygen used in the process of the invention need not be pure, but may be air or a mixture with other inert gases. In addition, in the method of the present invention, it is also possible to extract electric energy corresponding to the free energy of the reaction from the reaction system as needed. FIG. 1 shows a conceptual diagram of a fuel cell type reactor used for carrying out the method of the present invention.

An anode chamber 3 having an anode 1 or a cathode 2 composed of a catalyst electrode and a cathode chamber 4 are separated by an ion conductor 5, and the anode and the cathode are short-circuited by a lead wire 6. The catalyst electrode is preferably porous or sheet-like, but is not necessarily limited thereto.
7 is a stirrer. If necessary, a voltage can be applied between the anode and the cathode.

The catalyst electrode used in the method of the present invention is as follows. Various materials can be used for the anode (electrode in contact with the hydrogen donor), and in particular, at least one or more of various metals or compounds thereof are used. Preferably, at least one of a metal or metal compound
It is recommended that more than one species be used by mixing or carrying an electrically conductive material. Further, the cathode (that is, the electrode in contact with the alicyclic compound and oxygen) is at least one or more of the halides of Group 7 metals and at least one or more of the halides of Group 1 metals in the periodic table. It is recommended that the conductive material be composed of a conductive material and used, for example, by mixing or by supporting a metal halide on the conductive material.

In order to further facilitate the method of the present invention, it is preferable to use an electrode molded using a binder in addition to these components.
The method of the present invention is not limited to only these methods.

As the conductive polymer material used in the present invention, it is generally preferable to use a carbonaceous substance such as graphite because of its low cost, availability and good electrical conductivity. Various binders can be used as a binder for forming the electrode, but it is preferable to perform hot press molding using Teflon resin powder from the viewpoint of easiness of molding. However, it is understood that the invention is not limited to only these materials and methods.

The periodic table in the meaning of the method of the present invention is the International Union of Pure and Applied Chemistry, revised version of the Nomenclature for Inorganic Chemistry (198).
9 years), and as a catalyst electrode used in the method of the present invention, the anode is implemented using at least one kind of metal or metal compound, which constitutes the metal or metal compound. In this periodic table, metals are group 3, group 4, group 5, group 6, group 7, group 8,
Group 9, 10, 11 and 12 metals.

Specifically, the group III metal is represented by the element symbol S
a metal represented by c, La, Y, Ac, etc .; a Group 4 metal is a metal represented by an element symbol Ti, Zr, Hf; and a Group 5 metal is an element symbol V, Nb, Ta. And the Group 6 metals include elemental symbols Cr,
A metal represented by Mo, W, a Group 7 metal is a metal represented by an element symbol Mn, Re, and a Group 8 metal is a metal represented by an element symbol Fe, Ru, Os;
Group 9 metals are metals represented by the element symbols Co, Rh and Ir, and Group 10 metals are the element symbols Ni, Pd and
Pt is a metal represented by element symbols Cu, Ag and Au as Group 11 metals, and metals represented by element symbols Zn, Cd and Hg as Group 12 metals. Further, when these metals are used as compounds in the positive electrode in the method of the present invention, they are used as halides, nitrates, sulfates, oxides, hydroxides, phosphates and / or ammonium salts of these metals. It is recommended to use. In the method of the present invention, an anode is prepared using at least one of these metals or metal compounds. Further, as the cathode, a mixture of at least one kind of a halide of a Group 7 metal in the periodic table and at least one kind of a halide of a Group 1 metal is used. The halides of these metals include chlorides, bromides, iodides and the like, and these are used together with the above-mentioned conductive polymer materials.

The ionic conductors used in the method of the present invention include protonic acids such as phosphoric acid, sulfuric acid and hydrochloric acid, heteropolyacids, solid electrolytes known as proton conductors such as H-montmorillonite and zirconium phosphate, and SrCe.
A perovskite-type solid solution having O3 as a base can be used. Further, those based on a fluorine-containing polymer such as perfluorocarbon, into which one or more cation exchange groups such as a sulfone group or a carboxylic acid group are introduced, for example, Nafion (registered trademark of DuPont) can also be used. . A liquid such as phosphoric acid can be used by impregnating it with silica wool, or can be used with an ion-permeable filter or membrane.

The hydrogen donor used in the method of the present invention generally refers to a substance which can be oxidized by an anode electrode to generate protons (hydrogen cations). Specific examples include hydrogen molecules, alcohols, hydroquinones, and saturated hydrocarbons.

The hydrogen donor supplied as a raw material to the anode chamber is usually supplied as a gas or a liquid. If necessary, it may be dissolved in an inert medium or water and brought into contact with the electrode in a liquid phase. Further, it may be used as a mixture with an inert gas such as nitrogen, helium, and argon.

The alicyclic compound to be supplied to the cathode chamber is supplied in a gaseous or liquid state, but oxygen or an oxygen-containing substance may be used in a gaseous state or further diluted with a suitable solvent or gas. it can. Also,
It can also be used by dissolving or suspending it in a polar medium such as water. In order to make the reaction proceed smoothly,
In other words, to make contact with the catalyst electrode effective,
Vigorous stirring is desirable. The reaction temperature is usually -20
C. to 200.degree. C., but more preferably -5 to 150.degree.

According to the method of the present invention, the reaction is generally carried out at normal pressure, but may be carried out under increased or reduced pressure as required. The reaction products, such as partial oxides such as alcohols and ketones, can usually be separated and purified from the reaction product liquid by a method such as distillation to obtain a high-quality target product.

[0019]

EXAMPLES Hereinafter, the method of the present invention will be described in more detail with reference to examples. However, these are exemplary, and the method of the present invention is not limited to the examples.

Example 1 Disk-shaped silica wool (thickness: 1.0 mm, diameter: 21 mm)
mm) containing an 85% phosphoric acid aqueous solution as an ion conductor membrane, and the anode is formed into a sheet by hot-pressing a mixture of 20 mg of platinum black powder, 70 mg of graphite powder, and 5 mg of Teflon powder. Further, the cathode was mixed with 50 mg of graphite powder and 5 mg of Teflon powder with a molar ratio of graphite (as carbon atoms): lithium chloride: manganese chloride of 98.7.
8: 1.0: 0.22, and a mixture of the mixture was formed by hot pressing as in the case of the anode. After charging 40 ml of cyclohexane into the cathode chamber using the reactor, steam and hydrogen were introduced into the anode chamber at an inflow rate of 21 ml / min of hydrogen gas containing 2.67% by volume of steam. Oxygen was supplied to the cathode chamber at an inflow rate of 10 ml / min, and a partial oxidation reaction of cyclohexane was carried out at 27 ° C. for 3 hours using the anode and the cathode in a closed circuit under a wire connection. As a result, 9.9 micromoles of cyclohexanol and 4.6 of cyclohexanone were obtained.
Micromoles formed.

Comparative Example 1 A partial oxidation reaction of cyclohexane was carried out in the same manner as in Example 1 except that the electrodes were open circuit (the electrodes were not connected) and all other conditions were the same as in Example 1. As a result, the reaction did not proceed, and cyclohexanol and cyclohexanone were not detected.

Comparative Example 2 A partial oxidation reaction of cyclohexane was carried out under the same conditions as in Example 1 except that both hydrogen gas and water vapor gas were supplied to the cathode chamber. As a result, formation of cyclohexanol and cyclohexanone was hardly recognized.

Comparative Example 3 Example 1 except that no lithium chloride was added to the cathode.
A partial oxidation reaction of cyclohexane was performed under the same conditions as described above. The result was only 3.9 micromoles of cyclohexanol and 1.4 micromoles of cyclohexanone, and the effect of the addition of lithium chloride was obvious.

[0024]

The method of the present invention is different from the conventional complicated and low selectivity methods such as the partial oxidation of cyclohexane, the partial oxidation of cyclohexene and the hydration of cyclohexene. By the direct one-step method, partial products such as alcohols and ketones corresponding to the alicyclic compound as a starting material can be produced while maintaining high product selectivity in addition to mild conditions. Further, no other auxiliary materials are required, and a large amount of side reaction products are not generated. In addition, the reaction can be carried out under extremely mild conditions, and there is no danger of explosion due to the direct mixing of oxygen and hydrogen, as compared with the conventional direct oxidation method using an alicyclic compound and oxygen. It also has many advantages, such as the ability to extract power energy with the product as needed.

[Brief description of the drawings]

 FIG. 1 is a conceptual diagram of a fuel cell reactor.

Fig. 1 Conceptual diagram of fuel cell type reactor

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Catalyst electrode (anode) 2 Catalyst electrode (cathode) 3 Anode chamber 4 Cathode chamber 5 Ion conductor 6 Lead wire 7 Stirrer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C07C 45/33 C07C 45/33 49/403 49/403 A C25B 5/00 C25B 5/00 // C07B 61/00 300 C07B 61 / 00 300 (58) Field surveyed (Int.Cl. ⁷ , DB name) C07C 27/12 310 C07C 29/50 C07C 35/08 C07C 45/33 C07C 49/403 C25B 5/00 C25B 3/00

Claims (2)

(57) [Claims] 1. An ion-conductive electrode provided with a catalyst electrode is contacted with a hydrogen donor, and the other electrode is contacted with an alicyclic compound and oxygen, and the corresponding partial oxidation of the alicyclic compound is performed by a fuel cell system. When obtaining alicyclic ketones or alicyclic alcohols, the catalyst electrode that comes into contact with the hydrogen donor is an electrode made of platinum and a conductive polymer material, and is brought into contact with the alicyclic compound and oxygen. The electrode is an electrode comprising a mixture of at least one or more halides of Group 7 metals and at least one or more halides of Group 1 metals in the periodic table and a conductive polymer material. A method for producing a partial oxide of an alicyclic compound. 2. The method according to claim 1, wherein the hydrogen donor is a hydrogen molecule.