JP3067834B2 - Catalyst device for redox reaction and method of using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst device effective for a redox reaction, a redox method using the catalyst device, a method for searching for a catalyst effective for a redox reaction using the catalyst device, and a novel redox reaction. Regarding the catalyst. The invention is used to produce industrial chemicals useful in the chemical industry.

[0002]

2. Description of the Related Art Many useful chemicals are produced by a redox reaction using a catalyst, and there is a constant demand for a more efficient reaction method and the development of an effective catalyst. Conventionally, in order to find a catalyst or catalyst component that is effective for an oxidation-reduction reaction, a metal or a metal compound considered to be effective is mixed by an appropriate method to form a catalyst, and the reaction result is provided by actual reaction. It has been evaluated and its effectiveness has been confirmed by trial and error. However, most of the industrially used catalysts are not single components, but consist of various metals or metal compounds. Therefore, it is necessary to determine which component of redox reaction and how effective each component is. It was difficult to do. As a result, the development of a new catalyst has required a great deal of labor, time and money.

[0003]

The present invention relates to a novel catalytic device effective for a redox reaction, and a redox reaction method using the same. Furthermore, the present invention relates to a method for efficiently developing a catalyst in a redox reaction, which has conventionally been performed by trial and error and requires a great deal of labor, time and cost, and a novel catalyst based on the result.

[0004]

SUMMARY OF THE INVENTION According to the present invention, a catalyst material comprising a heterogeneous metal and / or a heterogeneous metal compound is present on a portion of a proton conductor material which is separated from each other, and these are externalized with a conductive material. The present invention relates to a redox reaction catalyst device having a short-circuited structure, a method for using the same, and a novel redox reaction catalyst derived from the results. The catalyst device of the present invention has the structure shown in FIG. The catalyst device is composed of four main elements, a catalyst element A, a catalyst element B, a proton conduction element, and an electron conduction element.
It functions as a single redox reaction catalyst device. The catalyst element A and the catalyst element B are present at portions separated from each other on the proton conducting element, and both are short-circuited by the electron conducting element, and the physical properties such as voltage and current between the two elements are measured as necessary, or Voltage and current can also be extracted. Examples of the substance forming the proton conductive element used in the method of the present invention include proton acids such as phosphoric acid, sulfuric acid, and hydrochloric acid; and solids known as proton conductors such as H-mordenite, H-montmorillonite, and zirconium phosphate. An electrolyte, a perovskite-type solid solution containing SrCeO3 as a base, or the like can be used. Further, a base comprising a fluoropolymer such as perfluorocarbon, into which one or two cation exchange groups such as a sulfonate group or a carboxylate group are introduced, for example, Nafion (Du Pont) (Registered trademark) can also be used. A liquid such as phosphoric acid can be used by impregnating it with silica wool or the like, or can be used with an ion-permeable filter or membrane.

The metal and / or metal compound to be present as the catalyst element A or the catalyst element B on the proton conducting element differs depending on the applied oxidation-reduction reaction, but various metals and / or metal compounds can be used. For example,
As shown in the examples, when performing a partial oxidation reaction of Wacker-type olefin, palladium, platinum, rhodium,
Metals such as ruthenium, iridium, osmium gold and / or compounds thereof can be used. Examples of such metal compounds include metal halides, metal nitrates, metal sulfates, metal oxides, metal phosphates, metal ammonium compounds, metal acetylacetones, metal acetates, metal carbonyl compounds, and the like. These metals and / or metal compounds can be used by being mixed or supported on a conductive substance, for example, graphite, activated carbon, carbon whisker or the like. Furthermore, various binders, for example, Teflon or the like can be mixed and heated and used. They may be used in combination with each other, but they must not be the same except when a voltage is externally applied.

[0006] The electron conductive element used for short-circuiting the catalytic element A and the catalytic element B used in the present invention is not particularly limited, and does not affect the reaction to be applied.
Any substance that can conduct electric current can be used, and generally, a copper wire, a gold wire, a platinum wire, or the like is used. Various oxidation-reduction reactions can be performed using the catalyst device element of the present invention. For example, it can be carried out by installing the catalyst device element of the present invention in an appropriate reactor and bringing the oxidizing substance and the reducing substance as raw materials into contact with each other under appropriate conditions. The raw material may be a gas, a liquid, or a mixture thereof. The reaction conditions such as reaction temperature, reaction pressure and reaction time are not particularly limited, and are determined by the oxidation-reduction reaction to be performed. For example, when the partial oxidation reaction of olefins is carried out using the catalyst device of the present invention, the olefins of the reducing compound used as a raw material, such as ethylene, propylene, and butene, which are usually used in Wacker-type reactions, Either can be used. They may be diluted with an inert gas, if necessary, or dissolved in a suitable solvent or water, and brought into contact with the catalyst device.

[0007] As a raw material of the oxidizing compound, any compound capable of reacting with hydrogen on the catalyst of the present invention can be used, but oxygen or air is generally used. In addition, aldehydes, nitro compounds,
By supplying a reducible compound such as an aromatic compound to obtain an olefin oxidation product, alcohols, amino compounds and saturated hydrocarbon compounds can be produced at the same time. Further, according to the present invention, power energy can be extracted by utilizing a current flowing between the catalyst element A and the catalyst element B or a voltage between the two elements as necessary. If necessary, an external voltage can be applied between the two electrodes to promote the reaction.

Further, by using the catalyst device of the present invention, it is possible to efficiently search for a catalyst effective for the intended oxidation-reduction reaction. That is, various combinations of metals and / or metal compounds used for the catalyst element A or the catalyst element B of the present invention are installed under the desired reaction conditions,
A voltmeter or ammeter or other measuring device is connected between the electron conducting elements, and a catalytic element A and a catalytic element B
By measuring the voltage, current, and other physical property values between them, it is possible to determine which metal or combination of metal compounds is effective. For example, the reaction rate of the target reaction can be evaluated based on the current value, and the activity ability of the combination of both elements as a catalyst can be evaluated based on the voltage value. The resulting combination of metal and / or metal compound can be used to design a new catalyst according to the concept of the redox catalyst model diagram shown in FIG. That is, a novel catalyst for a redox reaction can be produced by allowing the above-mentioned different kinds of metals and / or metal compounds to be in contact with each other on a proton conductor material to enable electron transfer.

[0009]

EXAMPLES Hereinafter, the method of using the catalyst device of the present invention will be described with reference to examples, but the present invention is not limited thereto, and can be widely applied by various methods under conditions satisfying the purpose of the present invention. it can.

Examples 1 to 5 As shown in FIG. 1, 85% of a disk-shaped silica wool (thickness: 1.0 mm, diameter: 21 mm) was used as a proton conductor.
Using a phosphoric acid aqueous solution, 50 mg of graphite powder, 5 mg of Teflon powder, and 20 mg of palladium black powder were well mixed as catalyst element A on one of the disks, and then attached into a sheet by hot pressing, On the other hand, 50 mg of graphite powder, 5 mg of Teflon powder and 20 mg of metal powder shown in Table 1 were similarly molded and attached as the catalyst element B. After connecting the catalyst element A and the catalyst element B with a gold wire, mixed gas of ethylene, oxygen and water vapor at normal pressure and a reaction temperature of 40 ° C. to 100 ° C. at a flow rate of 16 ml / min, 4 ml / min and 5 ml / min, respectively. And a partial oxidation reaction of ethylene was performed. A steady state was reached about 2 hours after the start of supply of the raw material gas. Steady state results and catalyst element AB without short circuit
The voltage between them is shown in Table 1. In Examples 4 and 5, carbon dioxide was added in addition to acetaldehyde in an amount of 0.1% each.
07 and 1.30 μmol / min.

[0011]

[Table 1] Table 1 Example Catalyst element B Ataldehyde Current value Voltage of metal generation rate without short circuit (μmol / min) (mA) (mV) ───────────────────────────── １1 ruthenium 2.33 5.2 236 2 rhodium 2.03 5.0 205 3 osmium 1.37 1.8 160 4 iridium 1.85 2.8 103 5 platinum 0.55 5.2 -108 か ら From the results in Table 1, the production of acetaldehyde by oxidation of ethylene Catalysts for palladium and ruthenium,
It can be seen that a combination of rhodium, asmium and iridium is effective.

Example 6 Based on the results of Example 1, a catalyst having a structure in which the catalyst element A and the catalyst element B were brought into contact with each other without being separated from each other in Example 1 was produced. That is, 50 mg of graphite powder, 5 mg of Teflon powder, 20 mg of palladium black powder and 20 mg of ruthenium metal powder were mixed well on the same proton conductor as in Example 1 and then formed into a sheet by hot pressing. And contacted with ethylene, oxygen and water vapor in the same manner as in Example 1.
As a result, acetaldehyde was produced at a rate of 3.18 μmol / min in a steady state.

Comparative Example 1 A reaction was carried out in the same manner as in Example 6 except that ruthenium was not added and mixed. Little acetaldehyde is formed,
Even if detected, the amount was extremely small.

Comparative Example 2 A reaction was carried out in the same manner as in Example 6 except that palladium was not added and mixed. Little acetaldehyde is formed,
Even if detected, the amount was extremely small.

Comparative Example 3 A reaction was carried out in the same manner as in Example 6, except that no proton conductor was used. Acetaldehyde was scarcely produced, or was detected in an extremely small amount.

Examples 7 to 10 Using catalyst devices made in the same manner as in Examples 1, 2, 4 and 5, using propylene instead of ethylene,
The same reaction was performed. Table 2 shows the results in the steady state and the voltage without short-circuit.

[0017]

[Table 2] Table 2 Example Catalyst element B Acrolein Current value None Voltage of metal generation rate during short circuit (μmol / min) (mA) (mV) ────────────────────────────── {7 Ruthenium 0.45 3.5 3068 Rhodium 0.58 4.0 2469 Iridium 0.32 2.3 198 10 Platinum 0.42 1.8 73}で は In Example 9, 0.4% acetone was used in addition to acrolein.
1 μmol / min was produced. In other examples, the formation of acetone was extremely small. In each case, generation of carbon dioxide was very small.

[0018]

According to the present invention, a redox catalyst device having a novel structure is provided. Further, by using the catalyst device of the present invention, the oxidation-reduction reaction can be efficiently performed. Further, by using the catalyst device of the present invention, it is possible to efficiently search for a catalyst component effective for the oxidation-reduction reaction, and as a result, it becomes possible to design a new oxidation-reduction catalyst.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of an oxidation-reduction reaction catalyst device. FIG. 1 is a conceptual diagram in the case of oxidizing ethylene with an oxidation-reduction reaction catalyst device.

[Description of Signs] Catalyst element A Catalyst element B Proton conduction element Electronic conduction element Ammeter Voltmeter

FIG. 2 is a diagram of a catalyst model for an oxidation-reduction reaction. FIG. 2 is a diagram of a catalyst model when a new catalyst for an oxidation-reduction reaction is designed based on a search result for a catalyst using the catalyst device for oxidation-reduction reaction of FIG. It is.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI B01J 27/25 B01J 27/25 35/02 35/02 P C07C 47/07 C07C 47/07 47/22 47/22 G

Claims (11)

(57) [Claims] An oxidation-reduction reaction having a structure in which a catalyst material comprising at least one kind of a different metal and a metal compound is present in a portion of a proton conductor material separated from each other and externally short-circuited by a conductive material. For catalytic devices. 2. A redox reaction method comprising reacting an oxidizing substance with a reducing substance using the catalyst device according to claim 1. 3. Use of the catalyst device according to claim 1,
A method for finding a catalyst effective for a redox reaction, characterized by reacting an oxidizing substance with a reducing substance. 4. <br/> redox reaction using a catalyst device shown in claim 1 is an oxidation reaction of an olefin according to claim 2 or
Or 3 methods. 5. The method according to claim 4, wherein the olefin is ethylene or propylene. 6. The method according to claim 5, wherein the metal and the metal compound are at least one selected from the group consisting of palladium, ruthenium, rhodium, osmium, iridium and these metal compounds. 7. An oxidation-reduction reaction catalyst, wherein a catalyst substance comprising at least one selected from different metals and metal compounds is brought into contact with each other on a proton conductor substance. 8. A redox reaction method comprising reacting an oxidizing substance with a reducing substance using the catalyst according to claim 7. 9. The method according to claim 8, wherein the redox reaction is an olefin oxidation reaction. 10. The method according to claim 9, wherein the olefin is ethylene or propylene. 11. The metal and the metal compound are palladium,
The method according to claim 10, which is at least one selected from the group consisting of ruthenium, rhodium, osmium, iridium, and metal compounds thereof.