JPH07828A - Catalyst for reforming hydrocarbons - Google Patents

Abstract

PURPOSE:To prevent oils/fats and lubricants from becoming thermally polymerized at a high temperature by treating the surface of an inorganic base material and/or a metallic base material using a coating agent containing silver. CONSTITUTION:A coating composition comprises a carrier having a large specific surface area such as zeolite, silica gel, aluminosilicate mineral and aluminosilica gel so that the function of silver or silver ion is maximized, and a binding agent such as hydrolysable silane compound or tetraalkoxysilane and a zirconium compound. Further, the coat has a large area coverage filled with ultrafine particles, so that hydrocarbons as liquid become excited by catalyst reaction, and the radical generated by oxidation reaction is removed. Consequently, it is through that R-R(dimer) is prevented from develop and thereby flocculated molecules are fractionated. Thus a polymerization preventive effect is achieved by adding 0.3-10wt.% of reforming catalyst to hydrocarbons, and oils/fats or petroleum products can be prevented from becoming qualitatively deteriorated when used at a high temperature.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a catalyst for reforming hydrocarbons. More specifically, it eliminates radicals generated in the course of oxidative polymerization reaction and thermal polymerization reaction of hydrocarbons such as fats and oils and petroleum products to prevent molecular enlargement (polymer), and further, gasoline and light oil. The present invention relates to a solid-state reforming catalyst for finely dividing molecules of hydrocarbons such as petroleum products. Furthermore, specifically, it is possible to prevent the deterioration of edible oil due to frying, etc., and to significantly extend the life of edible oil, and to make the molecules of gasoline and light oil into fine molecules, enabling finer atomization. And a catalyst for reforming hydrocarbons capable of promoting complete combustion.

[0002]

2. Description of the Related Art Conventionally, in the case of fats and oils, natural compounds such as tocopherol, ascorbic acid and citric acid, or various synthetic compounds have been used as antioxidants that interfere with the reaction between hydrocarbons and oxygen and delay the oxidation. There are also
In the case of petroleum, there are 2,6-di-t-butyl-4methylphenol, 2,4-dimethyl-6-t-butylphenol, N, N'-diisopropyl-p-phenylenediamine, and the like. Is also a consumption type as an additive and has the purpose of preventing autoxidation at room temperature, and therefore has little effect of preventing thermal polymerization of oils and fats and lubricating oils at high temperatures.

For example, in the case of edible oil, when it is heated, a rapid thermal oxidation occurs at the contact surface with air, a peroxide is produced, a polymer is produced through a dimer, and the viscosity is increased. Then, when frying, a fine bubble is generated when a seed is put in, and it does not easily disappear (stuck phenomenon), and a harmful cyclic compound is also generated. The increase in viscosity impairs the heat transfer to seeds, which is the original purpose of oils and fats, and the oils and fats soak into the fried foods to make them oily and the flavor is deteriorated. However, nothing has been developed to prevent this.

Further, conventional gasoline and light oil produce radicals (ROO) generated during the oxidation reaction during storage or combustion.
However, the fine particles are not completely atomized because they are polymerized to make the molecules huge and produce a polymer to lower the combustion efficiency. For this reason, when the vehicle is idling, when traveling at constant speed / deceleration, or when traveling at high speed, the amount of hydrocarbons emitted is large, which is not preferable in terms of environmental hygiene.
There are also problems such as not being economical.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, in which radicals generated in the processes of oxidative polymerization reaction and thermal polymerization reaction of hydrocarbons such as fats and oils and petroleum products. Eliminates and enlarges molecule (polymer)
It is an object of the present invention to provide a catalyst for reforming hydrocarbons, which is capable of suppressing the above-mentioned problems and further making the molecules of petroleum products such as gasoline into fine molecules. More specifically, the present invention prevents deterioration of edible oil due to fried food,
The life of edible oil can be greatly extended, and the molecules of gasoline and light oil can be made into fine molecules to enable finer atomization to promote complete combustion, which is excellent in heat resistance and hydrocarbons. It is an object of the present invention to provide an efficient and inexpensive hydrocarbon reforming catalyst that does not elute into compounds.

[0006]

DISCLOSURE OF THE INVENTION According to the present invention, the surface of an inorganic base material and / or a metal base material is processed with a coating agent containing silver to modify hydrocarbons. A catalyst for use is provided.

The base material used in the present invention is a base material for producing a catalyst for reforming hydrocarbons by applying a coating agent and heating and curing. In order to maximize the polymerization preventing effect of the reforming catalyst, a material having a large surface area, durability and low cost is preferable. Among such base materials, the inorganic base materials include fine particle aluminosilicate minerals and / or silicate minerals, fine particle metal oxides, fine particle metal hydroxides, and fibrous metal oxides. Examples include a porous molded article obtained by firing at least one selected from the following.

Examples of the aluminosilicate minerals and silicate minerals include zeolite, kaolinite, sepiolite, feldspar, vermiculite, high alumina clay, sillimanite and the like. Further, as the metal oxide, silica gel, alumina, zircon, magnesite, iron oxide, manganese oxide, etc., as the metal hydroxide, aluminum hydroxide, iron hydroxide, etc., as the fibrous metal oxide, , Silica fibers, alumina fibers, silica-alumina fibers, etc., and a porous molded product obtained by firing these at 800 ° C. to 1,800 ° C. and molding them into granules or plates is used as a substrate. The metal base material is preferably a non-eluting material, preferably a foam metal and / or a metal having at least its surface treated to be porous or rough, such as aluminum, iron, stainless steel, copper, and other alloys. What was processed as mentioned above is mentioned. here,
Examples of the foam metal include aluminum foam. Examples of the porous treatment include treatment of aluminum, iron, stainless steel, etc. in a porous state in the manufacturing process, or fusion treatment of a fibrous metal. The rough surface treatment is performed by blast treatment or etching treatment with acid / alkali.

The base material may have any shape such as granular shape, plate shape or the like. In the case of granular shape, the average particle diameter is 1 to 50 mm, preferably 3 to 30 mm. 1
If it is less than 50 mm, it tends to be damaged and it becomes difficult to store it. On the other hand, if it exceeds 50 mm, the surface area becomes relatively small, which is not preferable. In the case of a plate, one side is 2 to 300 m
m is preferred. If it is less than 2 mm, it easily breaks, while 30
If it exceeds 0 mm, it is not preferable because it is difficult to handle and easily cracks. The reforming catalyst of the present invention can be obtained by applying a coating agent to such a base material and curing by heating.

In the present invention, the coating agent contains silver. Such a coating agent contains a composition obtained by mixing the following (a) to (d) as a main component. Is preferred. (A) (a) General formula R ¹ Si (OR ² ) ₃ (wherein R ¹
Is an organic group having 1 to 8 carbon atoms and R ² is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms) (hereinafter referred to as “(a)”). Yes, and (b) Si (OR ² ) ₄ (wherein R
² is the same as the above) and a general formula Zr (OR ') ₄ (in the formula, R's are the same or different and each represents a hydrocarbon residue having 2 to 5 carbon atoms).
At least one selected from the zirconium compound represented by (hereinafter sometimes referred to as “(b)”) (b) a silver salt or colloidal silver in an amount of 0.2 to
10% by weight, at least one inorganic compound selected from the group consisting of zeolite, silica gel, aluminosilicate minerals, and alumino-silica gel, ion-exchanged, adsorbed, or fixed (c) alcohol (d) water

This composition is excellent in adhesion, oil resistance, durability and hardness of a fine-grained inorganic compound having a large specific surface area obtained by adsorbing or ion-exchanging silver in an ion state on the surface of a base material. It is also fixed by an ultrafine particle gel film formed by hydrolysis of an organoalkoxysilane, a tetraalkoxysilane, or a zirconium compound.

The coating composition will be described in detail below for each constituent substance. (A) (a) Organoalkoxysilane represented by the general formula R ¹ Si (OR ² ) ₃ ; The organoalkoxysilane used in the present invention undergoes hydrolysis reaction and polycondensation reaction in the presence of water. It has a high molecular weight, and when it becomes a coating film, it is cured by heating or standing at room temperature, and it functions as a binder in the coating agent of the present invention.

R ^{1 in} such an organoalkoxysilane
Is an organic group having 1 to 8 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group, an n-propyl group, and an i-propyl group, and a γ-chloropropyl group, a vinyl group, 3,3 , 3-trifluoropropyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group, phenyl group, 3,4-
Examples thereof include epoxycyclohexylethyl group and γ-aminopropyl group. In addition, R in the organoalkoxysilane
² is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, Examples include t-butyl group and acetyl group.

Specific examples of these organoalkoxysilanes include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i. -Propyltrimethoxysilane, i-propyltriethoxysilane,
γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ- Mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane, 3,4-
Epoxycyclohexylethyltrimethoxysilane,
3,4-epoxy cyclohexyl ethyl triethoxysilane etc. can be mentioned.

Of these organoalkoxysilanes, methyltrimethoxysilane is particularly preferred. Also,
These organoalkoxysilanes may be used either individually or in combination of two or more. In addition, such an organoalkoxysilane is a partial condensate, and further a complete condensate, as well as producing a corresponding silanol (hydrolyzate) by liberating an alcohol by hydrolysis in an acidic aqueous medium, and causing polycondensation. This produces an organopolysiloxane compound. Therefore, (a) in the present invention includes not only the organoalkoxysilane but also its hydrolyzate, partial condensate, and complete condensate.

(B) a tetraalkoxysilane represented by Si (OR ² ) ₄ (wherein R ² is the same as above) and a zirconium compound represented by the general formula Zr (OR ') ₄ (wherein R ² ′ Are the same or different and have 2 to 2 carbon atoms
5 represents a hydrocarbon residue of 5); Si (OR ² ) ₄ (in the formula,
Examples of the tetraalkoxysilane represented by R ² are the same as the above), for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-
i-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-te
Examples thereof include rt-butoxysilane. These tetraalkoxysilanes may be used alone or in combination of two or more. The tetraalkoxysilane liberates an alcohol by hydrolysis in an acidic aqueous medium to produce a hydrolyzate, and polycondensation occurs to produce a partial condensate and further a silicon dioxide that is a complete condensate. To do. Therefore, the tetraalkoxysilane, which is one component of (b) in the present invention, also includes a hydrolyzate, a partial condensate, and a complete condensate.

Zirconium compound Z used in the present invention
r (OR ′) ₄ is hydrolyzed in the presence of a small amount of water (humidity in the air or humidity of the base material), and the hydrolyzate is polycondensed to form a partial condensate, which is further polymerized to obtain a coating. When it becomes a film, it is cured by heating, and in the coating composition of the present invention, it functions as a binder in combination with the tetraalkoxysilane together with the organoalkoxysilane constituting (a). is there. R's of the zirconium compound are the same or different and are a hydrocarbon residue having 2 to 5 carbon atoms, and are ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert- For example, a butyl group.

Specific examples of zirconium compounds include, for example, zirconium tetraethoxide, zirconium tetra-n-propoxide, zirconium tetra-i-propoxide, zirconium tetra-n-butoxide, zirconium tetra-sec-butoxide and zirconium tetra-. Examples thereof include tert-butoxide. These zirconium compounds may be used alone or in combination of two or more. Of these compounds, zirconium tetra-n-butoxide is preferred.

The zirconium compound is rapidly hydrolyzed to liberate an alcohol to generate a corresponding zirconium hydroxide, and the hydroxyl substituent is polycondensed by the formation of the hydroxide to give the zirconium hydroxide. A partial polycondensation product of silane is produced, and further polycondensation produces a zirconia component which is a complete condensation product. Therefore, the zirconium compound in the present invention, in addition to the zirconium compound represented by the general formula, a hydrolyzate thereof or a partial condensate of the hydrolyzate,
Further, it also includes a complete condensate. Etc. Such hydrolyzate or partial condensate may be those produced from the zirconium compound in the coating composition,
Further, it may be preliminarily compounded when the coating composition is prepared.

The zirconium compound is used together with the above-mentioned tetraalkoxysilane, and the zirconium compound / tetraalkoxysilane (weight ratio) is 1 /
0.5-5 is preferable. If it is less than 1/5, the ratio of the zirconium compound is relatively small, and the hydrolysis does not proceed in a short time so that the film-forming property is poor. On the other hand, if it exceeds 1 / 0.5, the ratio of the zirconium compound is too large and the composition is obtained. The storage stability of the product is deteriorated, and the hydrolysis is too fast to deteriorate the film-forming property.

(B) Silver salt or colloidal silver selected from the group consisting of zeolite, aluminosilicate mineral, silica gel, and alumino-silica gel having 0.2 to 10% by weight in terms of silver, ion-exchanged, adsorbed or fixed. The silver-supporting inorganic compound as the component (b), which imparts a polymerization-preventing function and a hydrocarbon fine-molecularizing function to the reforming catalyst of the present invention, is an essential component. Is. The silver in the component (b) is supported in the state of an ionic state on the carrier of the inorganic compound, and it is considered that the polymerization inhibitory action and the fine molecularization action are due to its catalytic function, and the catalyst has a surface area of Since it is extremely large, it has a great effect of preventing polymerization and fine-molecularization even in a small amount, and it lasts for a long time.

To support such silver, a silver salt or colloidal silver is used. Specific examples of the silver salt include silver nitrate, silver sulfate, and silver chloride. However, the present invention is not limited to these. These are used as a mixed aqueous solution by dissolving one kind or two or more kinds in water. The silver salt also functions as an acidic catalyst during the hydrolysis of the organoalkoxysilane constituting the component (a). These metal salt mixed aqueous solutions can be adsorbed or ion-exchanged on the inorganic compound carrier. The colloidal silver has an average particle size of 3 to 100 mμ, preferably 5 to 20 mμ, and more preferably around 5 mμ, and it can be fixed on the surface of the inorganic compound having a large surface area.

The content of silver in the component (b) used in the reforming catalyst of the present invention is preferably 0.2 to 10% by weight, preferably 1 to 8% by weight in terms of silver. This silver is 0.2
If it is less than 10% by weight, the polymerization inhibitory ability and the ability to make fine molecules, which are the objects of the present invention, are too small. It may elute, which is not preferable. As the silver-supporting inorganic compound of component (b), at least one selected from the group of inorganic compounds consisting of zeolite, silica gel, aluminosilicate minerals, and alumino-silica gel is used. The component (b) of the present invention can be obtained by contacting these carriers with an aqueous solution of a silver salt for ion exchange or adsorption, or by contacting with colloidal silver and fixing them.

The carrier inorganic compound will be described in detail below for each component. (Zeolite) The zeolite in the present invention is a natural or synthetic zeolite and has the general formula x M _{2 / p} O · Al ₂ O ₃ · y.
SiO ₂ · z H ₂ O (In the formula, M represents an ion-exchangeable metal ion, which is usually a monovalent to divalent metal, and p
Is the valence, x is the coefficient of the metal oxide, y is the coefficient of silica, and z is the number of crystal water, respectively, and many types with different composition ratios, pore diameters, specific surface areas, etc. is there.

For example, natural zeolites include anarsine, chabazite, clinoptilolite, erionite, faujasite, mordenite, and the like, while synthetic zeolites include A-type zeolite, X-type zeolite, Y-type. Zeolite, T-zeolite and the like can be mentioned. The shape of the zeolite is preferably in the form of particles, and the particle diameter is preferably 10 μm or less. A preferred zeolite has a particle size of 3 μm or less, a specific surface area of 150 m ² / g or more, and a SiO ₂ / Al ₂ O ₃ molar ratio of 14 or less. In the present invention, a zeolite having a large specific surface area and an excellent adsorption ability is preferable, and the above-mentioned synthetic zeolite is preferable.

(Silica gel) Silica gel has the general formula Si
A compound represented by O ₂ · nH ₂ O, which is glass-like transparent or translucent particles and has a fine structure with a rough show. For example, 1 g has a large specific surface area of 450 m ² or more. . In the present invention, silica gel has an average particle size of 10 in order to form a thin film having excellent wear resistance.
μm or less is preferable.

(Aluminosilicate Minerals) Kaolinite, halosite, muscovite, montmorillonite, vermiculite, which is a salt of aluminosilicate ion in which a part of condensed silicic acid is replaced by aluminum and various metal ions, is used to remove zeolite. Feldspar and other natural minerals, which have a large surface area and ion exchange capacity. The particle size of the aluminosilicate mineral is usually 0.1 to 10 μm, preferably 0.5 to 3 μm.
m.

(Alumino-silica gel) General formula Al ₂ O
_There is also an amorphous gel represented by ₃ · mSiO ₂ · nH ₂ O + Al (OH) ₃ which has a large surface area and has both the functions of silica and alumina and is mixed and molded with activated carbon. Excellent adsorption performance. The particle size is 0.5 to 10 μm, preferably 0.5 to 3
μm.

When the component (b) is used as the component (a), the proportion of the component (b) in the coating composition used for the reforming catalyst of the present invention is 100 parts by weight of the organoalkoxysilane. Usually, it is 5 to 100 parts by weight, preferably 10 to 70 parts by weight. When (b) is used as the component (a), the component (b) is 5 to 100 parts by weight of (b) in terms of tetraalkoxysilane.
100 parts by weight is preferred. (B) When the amount of the silver-carrying inorganic compound used is less than the predetermined amount for each of the above substances, there is almost no effect of preventing polymerization or fine molecularization, while when it exceeds the predetermined amount, the composition becomes too thick, Elution may occur, which is not preferable.

(C) Alcohols; Alcohols are concentration adjusting agents for the component (a), and further, the organoalkoxysilane, tetraalkoxysilane or zirconium compound constituting the component (a) is hydrolyzed by water. In order to prevent excessive gelation at the time of addition, water is also azeotropically distilled off while controlling the condensation reaction of the hydrolyzate.

As this alcohol, ethylene glycol which is a monohydric alcohol or a dihydric alcohol or a derivative thereof can be used. Among these, a monohydric alcohol is preferably a lower aliphatic alcohol having 1 to 5 carbon atoms,
Specific examples include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, sec-butyl alcohol, t-butyl alcohol, and the like, and ethylene glycol or a derivative thereof is ethylene glycol, ethylene glycol monobutyl ether, Examples thereof include ethylene glycol monoethyl ether acetate.

These alcohols are preferably i-
Propyl alcohol, sec-butyl alcohol, and ethylene glycol monoethyl ether acetate. These alcohols may be used alone or in combination of two or more. The proportion of alcohol in the coating composition used in the hydrocarbon reforming catalyst of the present invention is
When (a) is used as component (a), it is usually 15 to 400 parts by weight, preferably 40 to 200 parts by weight, based on 100 parts by weight of component (a), and component (a). When (b) is used as above, it is preferably 80 to 800 parts by weight based on 100 parts by weight of the component (a) in terms of (b).

(C) If the amount of alcohol used is less than the predetermined amount for each of the above substances, the composition may separate into two layers or gelation may occur, while if it exceeds the predetermined amount, the other relatively In some cases, the amount of the component will decrease, the adhesion of the film of the obtained material will be weakened, or the thin film will be too thin to produce the intended product.

(D) Water: Water is an essential component for the hydrolysis of the organoalkoxysilane or tetraalkoxysilane, which is the component (a), and the zirconium compound, and also a viscosity modifier, a drying speed modifier, and (a). ) ~
It serves as a dispersion medium for the component (b) and further for the filler (e) used as necessary.

As this water, general tap water, distilled water, or ion-exchanged water can be used. In particular, distilled water or ion-exchanged water is preferable when making the composition highly pure. The water includes, for example, water produced by hydrolysis of the organoalkoxysilane, the tetraalkoxysilane, and the zirconium compound constituting the component (a). The proportion of water in the coating composition used for the reforming catalyst of the present invention is
When (a) is used as the component (a), it is usually (i)
Is 100 to 100 parts by weight, preferably 15 to 400 parts by weight, preferably 40 to 250 parts by weight, and when (b) is used,
It is 0 to 25 parts by weight, preferably 0 to 15 parts by weight, relative to 100 parts by weight of (b). (D) If the amount of water used is less than the predetermined amount for each of the above substances, (a)
It is difficult for the components to hydrolyze sufficiently. On the other hand, when the amount exceeds the predetermined amount, the stability of the composition used in the present invention deteriorates.

The coating composition for producing a coating film containing silver of the present invention is obtained by mixing the above-mentioned components (a) to (d), and its pH is 2 to 6.5. Preferably, it may contain an acid for pH adjustment. further,
If necessary, a filler (e) can also be added.
(E) The filler has the effect of developing the cosmetic properties of the resulting coating film, the effect of preventing polymerization by increasing the surface area of the coating film, the improvement of fine molecularization of hydrocarbons, the corrosion resistance, the durability and the coating strength. It is used for expressing various characteristics such as improvement.

Examples of the filler (e) include water-insoluble general pigments such as inorganic pigments or particulate or fibrous metal oxides, carbides and nitrides other than pigments.
Or two or more kinds, specifically, silica gel, synthetic zeolite, activated carbon, silicon dioxide, titanium oxide, aluminum oxide, chromium oxide, manganese oxide, iron oxide, zirconium oxide, cobalt oxide, kaolin, synthetic mullite, Examples include zircon (zirconium silicate), silicon carbide, potassium titanate,
It is not limited to these.

In order to increase the surface area of the coating film, colloidal silica, alumina, titania, ultrafine particles of silica, alumina, titania, etc. can be used. In addition, if necessary, chelating agent, surfactant,
Conventionally known additives such as a silane coupling agent, a titanium coupling agent, and an alkali metal salt can be used. The solid content concentration of the coating composition is usually 10 to 10.
60% by weight, preferably 15-45% by weight, 10
If it is less than 60% by weight, the thickness of the obtained coating film is too thin to reduce the effect of preventing polymerization or fine molecule, or the coating film strength is too low. On the other hand, if it exceeds 60% by weight, gelation tends to occur. It is not preferable because the viscosity increases too much or the adhesiveness deteriorates.

In order to prepare a coating composition, firstly, the above-mentioned components (a) to (d) or components (a) to (e) are mixed, and the mixing method in this case is as follows. A method of simultaneously mixing the components (a) to (d) or the components (a) to (e), the mixture of the components (a) and (c) with the component (b), and optionally the component (e). And a method of mixing (d) water at the time of use. In the component (b), silver is not supported in advance on the inorganic compound carrier, but an aqueous solution of a silver salt and the inorganic compound carrier are mixed with the components (a), (c), (d), or further the component (e). You may.

In the present invention, the components (a) to (d) or the components (a) to (e) can be used after being mixed in this manner.
When the above is used, it is advisable to carry out aging for 2 to 72 hours, more preferably 3 to 24 hours after mixing all the components.
When the aging time is less than 1 hour, the hydrolysis and polycondensation reaction of the component (a) do not proceed sufficiently, and the heat of reaction remains,
The cissing phenomenon easily occurs when applied to the substrate, while 7
If it exceeds 2 hours, the polycondensation reaction of the component (a) proceeds too much, the dispersion stability of the composition deteriorates, and the density of the obtained film,
Adhesion and hardness may decrease and the gloss may be lost. The aging temperature is usually preferably 10 to 30 ° C. under normal temperature.

The coating composition used in the present invention is dispersed by a high-speed stirrer, a ball mill, or other dispersers, and filtered to obtain a uniform and stable dispersion liquid. Application of the coating agent,
The coating composition prepared as described above is then coated on the surface of the base material by a coating means such as dipping, kneading, spraying, or brushing to give 100-400.
By heating at 5 ° C. for 5 to 120 minutes, it is easily cured, and a coating film excellent in polymerization prevention of hydrocarbons and fine molecularization can be obtained. The ratio of the coating agent to the substrate is 0.2.
-20% by weight (converted to a dry coating film) is preferable, and more preferably 0.5-5% by weight.

The content of silver in the reforming catalyst of the present invention thus obtained is preferably 0.03 to 1.
It is 5% by weight, more preferably 0.05 to 1.0% by weight. If it is less than 0.03% by weight, the effects of preventing the polymerization of hydrocarbons and fine molecularization are small, while if it exceeds 1.5% by weight, silver is eluted and the adhesion is lowered, which is not preferable. The reforming catalyst thus obtained may have any shape such as a granular shape or a plate shape. When the particles are granular, the particle size is preferably 1 mm to 50 mm. Particle size is 1
If it is less than mm, it tends to be damaged and it is difficult to store it. On the other hand, if the particle size exceeds 50 mm, the surface area becomes small and it becomes difficult to handle, which is not preferable.

The granular material is preferably used by putting it in a metal mesh container as shown in FIG. In FIG. 1, (A) is a top view of a spherical or hemispherical wire mesh container, (B) is a perspective view of the hemispherical wire mesh container, (C) is a side view of the hemispherical wire mesh container, and (D) is a cylinder. FIG. 3E is a perspective view of a box-shaped wire mesh container, and FIG. However, the particles may be put in the container as they are without being put in the container. Further, FIG. 2 shows a perspective view of a square (A), a circle (B), and a rectangle (C) as a plate-like object, but the present invention is not limited to these, and any shape is possible. . Its thickness is
It is preferably 3 to 50 mm. Further, FIG. 2D shows a perspective view of a catalyst using foamed aluminum as a base material.

The hydrocarbon reforming catalyst of the present invention has a polymerization inhibiting effect when added to hydrocarbons in an amount of 0.3 to 10% by weight, and prevents deterioration of oils and fats and petroleum products used at high temperatures. You can For example, in the case of edible oil, no increase in viscosity, discoloration, odor, etc. was observed even when deep-fried, the oil did not change, and the state of the new oil was 3 to 5 times that of the conventional one. It will continue for a long time. It was also found that when the catalyst for reforming hydrocarbons was added to fresh oil, the viscosity of the oil further decreased. That is, the hydrocarbon reforming catalyst of the present invention can maintain the state of fresh oil and simultaneously further reduce the viscosity.

The reforming catalyst of the present invention is a non-eluting solid catalyst having excellent heat resistance and can be continuously used for a long time. Due to this catalytic effect, deterioration of fats and oils and petroleum products is largely prevented. Since the oils and fats and lubricating oils used under high temperature can be used by a method such as replenishment, the amount of waste disposal can be greatly reduced. In addition, hydrocarbons such as burning gasoline, kerosene, heavy oil, jet fuel, and crude oil usually have agglomerated molecules, but the addition of the reforming catalyst of the present invention makes the agglomerated molecules finer. As a result, atomization is improved and combustion efficiency is improved. Furthermore, the catalyst of the present invention has, as an additional effect, the ability to decompose and destroy bacteria and odorous components. That is, it oxidizes and destroys the surface of bacteria cells to sterilize them, and oxidatively decomposes odorous components. In addition, the clean dispersibility of engine oil for automobiles and ships can be greatly improved.

Specific examples of the method of using the reforming catalyst of the present invention are as follows. That is, the hydrocarbons
In the case of fuel oil such as gasoline and light oil, the catalyst of the present invention may be charged through the fuel oil supply port and contacted for preferably 10 minutes or longer, more preferably 2 hours or longer. Further, in the case of a high-viscosity lubricating oil such as engine oil, it is preferably contacted for 4 hours or more. In the case of these fuel oils and lubricating oils, the contact treatment may be carried out at the operating temperature, that is, room temperature. Furthermore, in the case of edible oil, it may be used in a dipping state at all times during storage of the edible oil as well as at high temperature when frying frying or tempura.

[0047]

The catalyst for reforming hydrocarbons of the present invention has a large surface area carrier to which a coating film containing silver is adhered, and the catalytic function is hydrocarbons which are liquid by catalytic reaction. Is excited, the radicals generated by the oxidation reaction are eliminated, the formation of RR (dimer) described later is blocked, and the aggregated molecules are further made into fine molecules. This will be described in detail below. The oxidative polymerization reaction of hydrocarbons is considered to proceed as follows. RH + O ₂ → R ・ + OOH ROOH → RO ・ + ・ OH R ・ + O ₂ → ROO ・ (chain reaction) ROO ・ + RH → ROOH + R ・ R ・ + R ・ → RRROO ・ + R ・ → ROOR (however, RH is carbonized Hydrogen molecule, ROOH represents hydroperoxide.)

The conventional antioxidant reacts with the free radical ROO · of the above formula to inhibit the progress of the chain, but the reforming catalyst of the present invention uses the R · in the above formulas.
It is considered that the reaction between ROH and ROO * prevents the formation of RR (dimer). This is because when the catalyst of the present invention containing silver is contacted with hydrocarbons and excited, R., ROO.
It eliminates radicals and prevents polymerization. That is, the catalyst of the present invention does not inhibit the production of oxides and peroxides, but inhibits the production of polymers and prevents the increase in kinematic viscosity of hydrocarbons. And, this is particularly effective under conditions where thermal polymerization rapidly progresses, such as edible oil and engine oil. In addition, hydrocarbons such as gasoline, kerosene, heavy oil, jet fuel, and crude oil usually have agglomerated molecules, but they are excited by the addition of the reforming catalyst of the present invention, and the agglomerated molecules become fine molecules. Therefore, atomization is improved, combustion efficiency is improved, and the amount of hydrocarbons in the exhaust gas can be extremely reduced.

Further, the coating composition used in the present invention has a large specific surface area of zeolite, silica gel, aluminosilicate minerals, alumino-silica gel, etc. as a carrier in order to maximize the function of silver or silver ions. A hydrolyzable silane compound (organoalkoxysilane), or a tetraalkoxysilane and a zirconium compound was used as a binder so that the coating film itself had a large surface area as if ultrafine particles were spread. Furthermore, since it is applied to the porous base material, the catalytic function can be exhibited very effectively.

[0050]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples unless it exceeds the scope of the claims. In the examples, parts and% are based on weight unless otherwise specified.

Reference Example (Preparation of reforming catalyst) In order to investigate the performance of preventing the polymerization of fats and oils, clean dispersibility, non-elution property, etc., a reforming catalyst was prepared as follows.
First, eight kinds of coating compositions A to H shown in Table 1 were prepared. The composition A was prepared by adding (a) methyltrimethoxysilane (400 parts), (c) isopropanol (229 parts) and (b) silver-supporting synthetic zeolite (120 parts) to a mixing tank, and lightly agitating the resulting mixture with a 200-mesh filter. Was added, 250 parts of (c) ion-exchanged water and 1 part of acetic acid were added, and the mixture was stirred at 2,000 rpm for 15 minutes.
Composition A was prepared by aging this mixed solution for 3 hours. Hereinafter, Compositions B to C and E to H were similarly prepared. The composition D was prepared by adding (c) isopropanol 3 to 160 parts of (a) tetraethoxysilane and 140 parts of (a) tetrabutoxyzirconium in a mixing tank.
90 parts, (b) 100 parts of silver-supporting kaolin, (b) 100 parts of silver-supporting silica gel, and 110 parts of black pigment were added and lightly stirred, and then mixed by a ball mill for about 6 hours.

[0052]

[Table 1]

Next, the coating composition shown in Table 1 was applied to the base material shown in Table 2 to prepare a 1P to 9P reforming catalyst. In addition, the base material is obtained by firing the samples in the table at 1,100 to 1,600 ° C. except for aluminum foam. The curing conditions after coating are Compositions A to H.
All were heated at 280 ° C. for 30 minutes. Also,
The shape of the particles of the base material is shown in FIG.

[0054]

[Table 2]

Example 1 In order to examine the effect of preventing the polymerization of fats and oils by the reforming catalyst of the present invention, the fats and oils were heated to promote thermal polymerization, and the kinematic viscosity thereof was measured. The iodine value and peroxide value were also measured. The measuring method was carried out by the standard oil and fat analysis test method edited by Japan Oil Chemists' Society. The results are shown in Table 3. The iodine value is
It is a numerical value proportional to the total number of double bonds possessed by unsaturated fatty acids, and this shows the change during the progress of polymerization. Also, it can be seen that the peroxide value hardly changes even if a catalyst is used, and increases in some cases.

[0056]

[Table 3]

Example 2 In order to investigate the state of prevention of formation of a polymer by the reforming catalyst of the present invention, the constituent fatty acids of soybean oil were analyzed and measured with time by gas chromatography. The results are shown in Table 4.

[0058]

[Table 4]

Example 3 In order to examine the change in viscosity and the cleansing dispersibility of a lubricating oil after oxidation, an internal combustion engine lubricating oil oxidation stability test according to JIS K2514 was conducted using the catalyst of the present invention. Table 5 shows the test results after 24 hours and 36 hours.

[0060]

[Table 5]

Example 4 In order to examine the silver elution property of the reforming catalyst of the present invention, the reforming catalyst was put in a predetermined amount of 1 liter of cooking oil and engine oil, and immersed at 180 ° C. for 3 hours to elute. A sex test was conducted. The analysis was performed by the atomic absorption spectrophotometric method. The results are shown in Table 6.

[0062]

[Table 6]

Example 5 (Deterioration Prevention Test of Oils and Fats) The rapeseed oil with or without 50 g / liter of the reforming catalyst 2P prepared above was subjected to a standard oil and fat analysis test method of 200%.
The peroxide value, saponification value and kinematic viscosity were measured after 4 hours at ℃. The results are shown in Table 7.

[0064]

[Table 7]

(Elution test into edible oil) 15 g of the reforming catalyst 4P prepared above was added to 1 liter of edible oil at 180 g.
The sample was immersed at 30 ° C. for 30 minutes and a dissolution test was conducted. The results are shown in Table 8
Shown in.

[0066]

[Table 8]

Example 6 In order to investigate the effect of the reforming catalyst of the present invention in a gasoline automobile, an exhaust gas test was conducted before and after the catalyst was put into a fuel tank in an idling state. The test was performed in the order of before and after charging. The catalyst 4P prepared in Reference Example was used as the reforming catalyst, and the test after charging was started about 24 hours after charging. The input amount is 10
It was set to 0 g.

The contents of the test vehicle are as follows. Type: Small / passive cycle number of cylinders: 4 cycle 6 cylinders Total displacement: 1,988 cc Maximum output: 130 / 5,400 (ps / rpm) Regular no-load speed: 700 rpm Fuel type: Smokeless gasoline transmission; Automatic (4 steps forward) Vehicle weight: 1,290 kg Types of exhaust gas countermeasures: Three-way catalyst + O ₂ sensor The exhaust gas analyzer is M manufactured by HORIBA, Ltd.
EXA-9400 / CVS-9100 type was used. The test results are shown in Table 9. It can be seen that when the reforming catalyst of the present invention is added to gasoline, the amount of hydrocarbons in the exhaust gas exhibiting combustibility is extremely reduced.

[0069]

[Table 9]

[0070]

INDUSTRIAL APPLICABILITY The catalyst of the present invention is capable of inhibiting the formation of a polymer of hydrocarbons under conditions in which thermal polymerization rapidly proceeds, such as edible oil and engine oil. It is possible to prevent an increase in kinematic viscosity. For example,
Prevents deterioration of edible oil due to frying, etc., prevents viscosity increase, does not impair heat conduction to the fried food, no matter how many times it is used, there is little oil penetration and a good flavor,
The result is crispy fried food, which can significantly extend the life of cooking oil.

The hydrocarbon reforming catalyst of the present invention is a non-eluting solid catalyst having excellent heat resistance and can be continuously used for a long time. Due to this catalytic effect, fats and oils and petroleum products can be obtained. It is possible to greatly prevent the deterioration of oil and oil and lubricating oil used at high temperatures, and to use it in a method such as replenishment, so that the amount of waste disposal can be greatly reduced. Further, the burning of gasoline, kerosene, heavy oil, jet fuel, crude oil, etc. is improved in atomization due to the finer molecular structure, and the combustion efficiency is improved. Furthermore, the catalyst of the present invention has, as an additional effect, the ability to decompose and destroy bacteria and odorous components. In other words, ionized oxygen destroys bacteria cells to kill them,
It oxidizes and decomposes odorous components. In addition, the clean dispersibility of engine oil for automobiles and ships can be greatly improved.

[Brief description of drawings]

FIG. 1 is a top view, side view, or perspective view of a container containing a granular catalyst of the present invention.

FIG. 2 is a perspective view of a plate-shaped catalyst of the present invention.

FIG. 3 is a schematic view showing the shape of the base material in Table 2.

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Claims (5)

[Claims] 1. A catalyst for reforming hydrocarbons, characterized in that the surface of an inorganic base material and / or a metal base material is processed with a coating agent containing silver. 2. The group of inorganic base materials is a group of fine-particle aluminosilicate minerals and / or silicate minerals, fine-particle metal oxides, fine-particle metal hydroxides, and fibrous metal oxides. The catalyst for reforming hydrocarbons according to claim 1, which is a porous molded product obtained by firing at least one selected from the group consisting of: 3. The catalyst for reforming hydrocarbons according to claim 1, wherein the metal base material is a foam metal and / or a metal having at least its surface treated to be porous or roughened. 4. A silver-containing coating agent comprises: (a) (a) General formula R ¹ Si (OR ² ) ₃ (wherein R ¹
Is an organic group having 1 to 8 carbon atoms, R ² is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms), and (b) Si (OR
² ) ₄ (wherein R ² is the same as above) and a general formula Zr (OR ′) ₄ (in the formula,
R's are the same or different and each represents a hydrocarbon residue having 2 to 5 carbon atoms), and at least one selected from zirconium compounds (b) a silver salt or colloidal silver is 0.2 in terms of silver. ~ 1
0% by weight, ion-exchanged, adsorbed or fixed, at least one inorganic compound selected from the group consisting of zeolite, silica gel, aluminosilicate minerals, and alumino-silica gel (c) alcohol, and (d) water The composition obtained as described above as a main component.
The catalyst for reforming hydrocarbons according to any one of items. 5. The catalyst for reforming hydrocarbons according to any one of claims 1 to 4, which contains 0.03 to 1.5% by weight of silver.