JPS6044044A - Internal shortcircuit battery type catalyst for oxidizing or reducing organic compound - Google Patents

Abstract

PURPOSE:To provide an internal shortcircuit battery type catalyst easy to separate a reaction product and an electrolyte, by bonding a mixture, consisting of an electron conductive powder available in electrolytic reduction, an electron conductive powder available in electrolytic oxidation and an ion exchange resin with a fluorine contained resin. CONSTITUTION:An electron conductive powder available in the electrolytic reduction of an oxidant, an electron conductive powder available in the electrolytic oxidation of a reductant and an ion exchange resin in a powdery form or a short fibriform coming to an ion conductor are mixed. The obtained mixture is mixed with distilled water and a fluorine contained resin such as polytetrafluoroethylene is added thereto as a binder to perform kneading. After drying, the kneaded mixture is molded by a hot press method. When this catalyst is rehydrated, the ion exchange resin functions as a solid electrolyte. This catalyst is suitable for the oxidative or reductive reaction of the org. compound in an aqueous solution.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to internally shorted cell catalysts. For more details, see Electron conductor powder effective for electrolytically reducing oxidizers and Electron conductor powder effective for electrolytically oxidizing reductants/i- Electron conductor powder Ion exchange resin powder as an ion conductor bt
, < is characterized by being made by adhering a mixture of Il and MIfl with a binder made of fluororesin. .

Many chemical reactions are redox reactions. 1',
) There is an oxidation reaction r in which the W element is oxidized, and there is a reaction in which the oxidized form is reduced)! This is the original reaction.

The electrochemical reaction in any electrochemical device is an oxidation reaction. That is, electrochemical station 1
4, there is always an electrolyte at the cathode and anode, but all hornsode reactions)! The anode reaction is a J-beta oxidation reaction.

The difference between a normal chemical reaction and an electrochemical reaction is that in the former case,
At least in the child's 1-1-, no exchange of electrons occurs, whereas in the rear right, exchange of electrons occurs and current flows through the external circuit. However, even though it is a normal chemical reaction, when viewed microscopically, there are many cases where the reaction mechanism can be better understood by explaining it as an electrochemical reaction or an electrochemical reaction. . For example, when activated carbon is reacted with oxygen and carbon dioxide in the lower right of the presence of water using a catalyst, sulfuric acid is produced.This reaction is apparently a normal contact IL reaction, but it is microscopic. Generally speaking, in the oxygen adsorption litite of activated carbon, the following electrolytic reduction reaction of oxygen occurs: 1・'2Q,・1211′
) Activated carbon's adsorption 1 is S.
O;,1211;40 +SO,,2-+41-(" +2e-(2)) An electrolytic oxidation reaction occurs, and the total is 1,' 202 +
802 +1” 20→11. : 804 (3) It is clear that the following reaction occurs.
In the heat, an oxygen-dioxide cell is formed, which can be internally shorted with activated carbon that conducts electrons. In this case, in the early stage of the reaction, sulfurous acid produced by dissolving dioxide in water acts as a supporting electrolyteff! After the reaction of formula (2) has progressed, sulfuric acid is the main ingredient! You can think of it as working as an r-electrolyte.

In addition, for example, in the Japanese Patent Publication No. 5 (1-40305@), when an aqueous solution of 1-lium sulfide is reacted with air using activated carbon treated with water repellent treatment as a catalyst, elemental sulfur and sodium hydroxide are produced. This reaction (equation 6) can be explained as a combination of the electrolytic oxidizing acid 1.8, doku!)) electrolytic reduction reaction of the following equation (4).

52---) SO+2e-C4) 21120+02 +4e--+ 4011 (5)2
Nil,: S + 2112 0 102-+ 28
n+ 4N, 1Oll (6) In addition, L citation example (, 2 (
I,lii) has not been explained/I-(jHowever, in this reaction, N12S is added to the reaction V, and after the reaction of equation (5) has proceeded to a certain extent, (L, water) It is possible to explain the reaction as occurring when an internal short-circuit occurs in an activated carbon battery using sodium oxide as a supporting electrolyte.

In this way, if we talk about electron conduction t9 using 1 carbon as a heterogeneous catalyst, we can see that there is a chemical reaction [゛, but microscopically, As an example of an electrochemical reaction, for example, endurance nn 52-31
H1823'3 L: kl, the following are listed.

(a) Sulfuric acid of sulfuric acid J1-S.
Oxidation to 11-lium, ([1) J in air, ferrous sulfate: or ferrous ammonium sulfate to ferrous sulfate! i′J
11\ oxidation, (c) oxidation of hyde [1 quinone to quinedrone with air, (d) oxidation of phenol with air, (e) oxidation of benzal Yd with air
Oxidation to acid, (to) reduction of nitric acid 1R to hydrogen gas to silver.

In any case, microscopically, the internal battery of the z777 battery, 0
A chemical reaction is progressed by the interaction customer 1! -J- In order to achieve this, it is essential that the catalyst be a solid that exhibits electronic conductivity, and that a supporting electrolyte coexist (false).

Conventionally, the supporting electrolyte has been used for each individual reaction, depending on whether it is an inorganic acid or alkali hydroxide that is the starting material before the reaction, or a reaction product that is formed together with the V line (of the reaction). It can be said that it was appropriated. On the other hand, in the chemical reaction of Irlj3, in general, neither the starting material nor the reaction product exhibits ionic conductivity and does not function as an electrolyte, so a separate inorganic supporting electrolyte is used. It becomes necessary to mix in.

5- However, when an inorganic supporting electrolyte is added, it becomes a problem that the desired reaction product and the inorganic supporting electrolyte must be separated after one reaction is completed.

The present invention aims to solve such problems, and provides an electron conductor powder that is effective in electrolytically oxidizing an oxidized cup, and an electron conductor powder and ions that are effective in electrolytically oxidizing a reductant. The ion-exchange resin powder used as a conductor is characterized by being made by binding a mixture with Chisen-Kon blue with a binder made of fluororesin.It is used for fermentation or reduction of organic compounds. It provides a catalyst for this.

In other words, with such a catalyst, as long as the ion exchange resin is hydrated, the ion exchange resin can be used as a solid electrolyte.
- Therefore, using this catalyst to cause a chemical reaction, 19
The separation 1 between the reaction product and the electrolyte becomes quite easy. J This catalyst is a heterogeneous catalyst including an electrolyte.

On the other hand, the catalyst according to the present invention itself retains the electrolyte.
Since it can be regarded as an internally short-circuited complete battery, it will be defined as 6-[Definition of internally short-circuited battery type catalyst 1 etc.].

Such a clear/j catalyst stage revision thought (, 1, conventionally -)
I: 3゜Electron 11 used in this internal short-circuit battery type catalyst A; Powder monthly rate which has power and shows catalytic activity -U
fil, of course it varies depending on the purpose of use4(]-Criru/l
<, usually (J metal, carbon or carbon) ↑)
Lotus IQ 1. 'l l, etc. are suitable, but some spindle p1 oxides or perodiskii type 1~ type citrates, metal acids 11c, metal borides, etc. with <i or <'L electron conductivity are suitable. In some cases, c1 compounds can be used.

Alternatively, it is possible to use a material such as silica, which itself has electron conductivity, with a metal added to it. others,
These powders exhibit catalytic activity and powders that do not exhibit catalytic activity.
``Move toward electron conductivity'', Una44 'J'l
There is also an effective frying platform for mixing.

Furthermore, I jj this electronic transmission IJt'4, catalytic disease t'
It is very effective to make the powder showing l by using a mixture of different materials that have selectivity for the ψ elementary reaction of the oxidant and the oxidation reaction of the reductant. You can also make it into powder.

Internal cavity, 0 set Other configurations of battery-type catalysts (I) Some ion exchange trees N[7 and C are available in cation exchange type and anion exchange type (1!).Cation exchange type The resin is based on a fluorine-containing polymer such as U k: 1, sulfuric acid, divinylbenron copolymer, or 1.1 perfluorocarbon, and is added with sulfuric acid, carboxylic acid groups, or both. Although the introduced one is suitable, the present invention (31
It is not limited to these. Ions (or hydrogen ions) that move through the resin through the 1° arc Δn exchange tree 11, polystyrene mother core (5:, anthonium salt, amine 0, diethylene j7 min J: Exchange amine with % I! 1;! and introduce I this 6 with aluminum potassium (-QJI I
Hydroxyl ion transfer type dojinogo 1-) using 1'1 BoJ
-1゜These (A exchange resins (J5, 6 in powder form) are suitable (L-shaped ones are suitable). The short fibrous ones are those with a diameter of 1.5 mm and a length of several 1 m or less.

Whether to use a cation exchange resin or a 2-A crosslinked resin must be selected depending on the reaction system to be treated.

Internal short-circuit battery type catalyst b excellent configuration + A PI 7
A certain fluororesin binder has electron conductivity 111 and has catalytic activity to bind the powder and -(A exchange tree flli), while internal short circuits 'rIi repel the pond-type catalyst. 5'4'Hl has the function of imparting aqueous properties.
"C.Fj, i.e. internal short circuit battery type catalyst 1.;1,
A liquid reactant and a gaseous reactant are used as starting materials to carry out a reaction, but if the internal short-circuited cell catalyst/I<11 is completely hydrophilic, the liquid reactant is coated with 1'1'. Sa4
′;, whereas adsorption sites for gaseous reactants are lost, if there is partial water repellency, adsorption sites for gas 1 reactant and adsorption sites 1 for liquid reactants are eliminated.
- If both of these conditions are ensured, the -C1 reaction tends to proceed more smoothly.

As a fluororesin binder, -C is the starting material. = (From the meaning of "I", especially polytetrafluoride 1'i = 1-1 non is 7iu 38, but this price is limited to 11J
].

The shape of the internal short-circuit battery type catalyst (1, granular, sheet-like, cylindrical, honeycomb, etc.) is also possible. (It is also effective to increase the mechanical strength by molding the catalyst δ (b-formation 4A l'il mixture into metal silk) or by expanding it into one piece with the metal.) There is a 4f lift.

Since water is essential, the internal short-circuit battery-type catalyst kl+ according to the present invention is particularly suitable for reactions such as avoiding oxidation of compound (11) in aqueous solution with oxygen, or reducing IJ to hydrogen. However, it is thought that its uses will expand in the future.

In some cases, it is more suitable to supply water in the form of steam. However, internally shorted battery-type catalysts contain ion-exchange resin, so if inorganic ions coexist,
This is inconvenient because ion substitution occurs and the ions transferred in the ion exchange resin become hydrogen ions or other than 10-A-1 hydroxyl ions, so it is preferable to apply this method to reaction systems that do not contain ion-free ions. .

By the way, there are many reactions in which the ion exchange resin itself can act as a catalyst.
It means +. For example, for example, if the exchange resin is 1
, formation and hydrolysis of esters, acetals, 7' amides, etc., hydration to nitrile, ■ poxy (catalyst for reaction with 7. Also, anionic hybrid 11) j is used as a catalyst for aldol condensation reactions, etc. be done.

On the other hand, the internal 9′, *4I8 electric i according to the present invention
T! ! Ion exchange resin as a substitute catalyst (: 1) Since it is responsible for the conductive bamboo, 4 (as in, the ion exchange resin itself functions as a catalyst.)
(There should be a distinction between si and ir-pan.

On the other hand, recently, using a catalyst in which metal R supports a transition metal on an ion-exchange resin, reduction of benzyl 1 x benzoin has been carried out. There are also reports that it can be generated.

However, these conventional catalysts [eyes, ion exchange resin itself f) <, J of the present invention
A acts as an electrolyte (1, not a catalyst), and furthermore, J of the present invention is effective for electrolytic oxidation, and is effective for electrolytic reduction of metals. The catalysts of the present invention (J, clearly Tatsumi Nata Mu no Tomii: ``It's 7-be.

An embodiment of the present invention will now be described in detail.

Examples: Platinum black powder 109 with an average diameter of 20 I!, graphitized carbon black 20 with an average particle diameter of 10 liters, and a sulfinic acid group introduced into a styrene-divinylbenvin nonapolymer with an average particle diameter of Sft. Ion exchange resin powder 5
Add 10ml of distilled water to the mixture well mixed with g,
l+ (f J, (mixture 1, solids content is 60%
Added 31111 of an aqueous suspension of polytetra-1-di-1-non, thoroughly kneaded, and vacuum-dried for 4 days. Then, pellets with a diameter of 3 m and a quality of 5 ml/l were molded at 80°C using a hot press method. . A <t, C internally shorted battery type catalyst was manufactured.

Next, pour one knot of this internally shorted battery type catalyst into one part of methanol.
01, into a mixed solution consisting of water 1001111,
Blow air into this mixed solution at room temperature. As a result, formaldehyde was analyzed after 1 hour and it was found that it was mixed with methanol. The oxidation rate of HillI was 54%.

Comparative Example When a similar experiment was carried out in the above example using a catalyst containing 1% ion exchange +s·+ fat, the oxidation rate of methanol to formaldehyde was 7%.

In other words, in the conventional example, the oxidation of methanol does not progress much due to a mere catalytic reaction (41), but it is clear that the oxidation of methanol progresses more when an internally shorted battery type catalyst is used as in the present invention. .

In the example described in 1.2 above, the electrolytic oxidation reaction of methanol mainly occurs at the contact interface between the platinum platter powder and the ion exchange resin, and the electrolytic reduction of ill element occurs at the contact interface between the titified carbon black and the ion exchange resin. 13- occurs at the contact area between platinum black and graphitized carbon,
Short circuit current flows.

The present invention provides a completely new catalyst stage for the oxidation or reduction of organic compounds.
Based on the concept of t'JI'rI t'JI'rI tangled battery type catalyst all-provided type catalyst 4-

Claims (1)

[Claims] An electron conductor powder effective for electrolytically reducing an oxidant and an electron conductor powder effective for electrolytically oxidizing a reductant.
4. Ion exchange resin powder as a conductor can also be used as a fluororesin mixture. An internal short YIJ battery 1 (catalyst) for oxidizing or reducing a chemical compound characterized in that it is formed by concretions in a chemical-saving manner.