WO2000034208A1

WO2000034208A1 - Reforming material for fluid material

Info

Publication number: WO2000034208A1
Application number: PCT/JP1998/005599
Authority: WO
Inventors: Shuichi Sugita; Takeo Hayashi
Original assignee: Shuichi Sugita; Takeo Hayashi
Priority date: 1998-12-10
Filing date: 1998-12-10
Publication date: 2000-06-15

Abstract

The invention concerns a reforming material comprising a core of ceramic material and a ceramic coating having a vitrified outer layer. It is speculated that with the vibration corresponding to a vibrational spectrum, the substrate portion of a reforming material liberates vibrational energy and transfers it to a fluid material. Then, the vibrational energy is transferred to a target molecule by excitation transfer, in particular, resonance transfer, thereby exciting the target molecule. Thereafter, hydrated electrons are liberated by the transition from the excited state to ground state of the molecule, and by the decomposition of the molecule.

Description

DESCRIPTION

REFORMING MATERIAL FOR FLUID MATERIAL TECHNICAL FIELD

The present invention relates to a reforming material for fluid materials, such as water used for drinking water, agricultural water and industrial water, and fossil fuel used for gasoline and light oil, among others. BACKGROUND ART

Living beings have been generated from water and they have ingested water into their bodies in the process of evolution, and hence water is essential to living beings. In the cyclic process in nature, water infiltrates the soil to become the ground water, and it appears the earth ' s surface with age, as spring water . During this cyclic process, water is closely related to the earth that is a huge mineral. The quality of water that takes up a primary factor in the presence environment of living beings is aggravated as human economic activity is developed. Particularly, tap water for drinking has high oxidation-reduction potential, and its water quality exhibits high oxidizing power. Meanwhile, crude oil that is a fossil fuel yielded from the earth soil is a complicated mixture of various hydrocarbons, and petroleum is the general term of crude oil and a variety of petroleum products obtained by refining crude oil. In cases where petroleum products, such as gasoline, fuel oil and light oil, are utilized as a fuel for internal combustion engine, various medicaments are added to improve their fuel consumption, alternatively, catalysts are used to clean exhaust gas. This type of technique is to activate fossil fuel by bringing a spherulite-shaped activator whose effective ingredient LS an oxide of rare earth elements, into contact with a petroleum product, e.g., gasoline, fuel oil, or light oil.

To solve the above problem, the object of the invention is to provide a reforming material for fluid material which excites the electrons of molecules, such as water molecules or the hydrocarbon molecules of fossil fuel, in a fluid material as a reforming object, to obtain electrons liberated by the transition from the excited state to ground state and by the decomposition of the molecules. Owing to the electrons, water is reformed so as to have water quality of high reducing power and fossil fuel is reformed so as to have oil quality (gasoline) which contains a large amount of aromatic components having a high octane number or contains a large amount of saturated compounds having a high cetane number. DISCLOSURE OF THE INVENTION

A reforming material for fluid materials according to the present invention is a fired product comprising a core portion as a structural member, a substrate portion covering the periphery of the core portion, and a surface portion covering the surface of the substrate portion. The core portion is composed of grains that are formed by using a ceramic powder as a raw material. The substrate portion is composed of a specific mineral. The surface portion is a vitrified layer . The specifIC mineral of the substrate portion has physical properties so that its vibrational spectrum corresponds to the absorption spectrum of a target molecule contained in a fluid material as a reforming object.

Preferably, the ceramic powder of the core portion is selected from among Sι0₂, A1₂0₃, Tι0₂ and Zr0₂, or a combination of these. The substrate portion is constituted, by weight, 80 to 95 percent of a major material and 5 to 20 percent of a supplementary material. In preparing the substrate portion of a major material, an effective mineral is dehydrated by firing it at a temperature m the order of about 400°C to about 850°C, recrystallized, and ground to in the order of about 200 mesh to about 450 mesh. Its supplementary material is one of SrO, Tι0₂, CoO, FeO and Fe₂0^, or a combination of these.

With this construction, the surface portion of the reforming material is brought into contact with a fluid material as a reforming object, and, due to the vibration corresponding to the vibrational spectrum of the substrate portion, the substrate portion liberates vibrational energy and transfers it to the fluid material. Since the vibrational spectrum of the substrate portion matches the absorption spectrum of a target molecule in the fluid material, the vibrational energy is transferred to the target molecule by excitation transfer, in particular, resonance transfer, thereby exciting the target molecule . Thereafter, hydrated electrons are liberated by the transition from the excited state to ground state of the molecule, and by the decomposition of the molecule . In the presence of the hydrated electrons, the molecules and atoms in the fluid material repeat chemical bonding and dissociation until a chemical equilibrium point s reached, to reform the fluid material .

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a schematic view of a reforming material according to one preferred embodiment of the invention. Fig. 2 is a diagram for explaining a service condition in a test of the reforming material.

Fig. 3 is a schematic view illustrating a case of use of a reforming material according to another preferred embodiment of the invention.0000000 Fig. 4 is a schematic view illustrating a case of use of a reforming material according to still another preferred embodiment of the invention.

BEST MODE FOR CARRYING OUT THE INVENTION

Preferred embodiments of the invention will be described by referring to the drawings. Firstly, the principle of a reforming material for fluid material according to the invention will be described. A polyatomic molecule has a variety of internal energies in rotational, vibrational and electronic states. The atoms constituting a molecule cause a peculiar vibration (normal vibration) depending on its bonding state and, when illuminated with light of the same frequency as the vibration, vibrational resonance occurs to absorb the light. The molecules that have absorbed energies will excite and thereafter transit from the excited state to ground state, or decompose, thereby liberating electrons . As described, a molecule has the internal energies due to vibration at the same time it absorbs the vibrational energy equivalent to the internal energies. Its wavelength region extends from the infrared region to visible ultraviolet region, and the infrared region is especially strong. INDUSTRIAL APPLICABILITY

First Preferred Embodiment

Description will now be given of the case where a reforming material of the invention is applied to water. In water, water exists as a polyatomic cation H₃0⁺ (hereinafter referred to as oxonium) , in which a proton attaches to a monoatomic oxygen anion 0₂ ^~.

In water, every proton rapidly migrates from one oxygen to another oxygen, and each H₃0⁺ has a life time of 10¹²S. A polyatomic cation H₃0⁺ is hydrated to become (H₃0⁺) (H₂0)n, however, an oxonium ion H₃0⁺ dissociates into H₂0 and H⁺ by charge-transfer reaction. A hydrated electron liberated by this dissociation is a strong reducing agent with a reducing potential of about -2.7 V, which reduces a water molecule H₂0 to H₂ ⁺+20H^~.

It is well known that a variety of minerals have vibrational spectrums resulting from their respective components. When the vibrational spectrum of a mineral is identical with the vibrational spectrum of water, resonance occurs in these vibrations. Some hydrophilic rock has a vibrational spectrum resulting from the internal vibration of its crystal, which corresponds to the absorption spectrum of a water molecule. Therefore, when water comes into contact with such a hydrophilic rock, the vibrational energy due to the internal vibration of the rock is transferred to water molecules and oxoniums by excitation transfer, in particular, resonance transfer, thereby exciting the water molecules . Thereafter, hydrated electrons are liberated by the transition from the excited state to ground state of the water molecules, and the decomposition of the water molecules. This results in water having a strong reducing power, owing to the hydrated electrons.

Referring to Fig. 1, a reforming material 1 is a fired product comprising a spherical core portion 2, a substrate portion 3 and a surface portion 4. The core potion 2 is part that serves as a structural member of the reforming material 1, and prepared by granulating a ceramic powder . The ceramic powder can be selected from among Sι0₂, A1₂0₃, Tι0₂ and Zr0₂. The core portion 2 is composed of grains that are formed by using one of the above ingredients or a mixture of these. The substrate portion 3 is composed of specific minerals, which can be roughly divided into two ingredients.

(A) As a major ingredient, a mineral is present in the range of about 90 to 95 percent by weight. Its maximum vibrational spectrum exists in the infrared wavelength region. The mineral has physical properties to cause stretching vibration or deformation vibration corresponding to the maximum vibrational spectrum. The maximum vibrational spectrum is equivalent to that which serves as a large absorption band in the infrared wavelength region, within the absorption spectrum of a water molecule. The vibrational energy of the above-mentioned mineral is weak for the following reasons: l) Minerals are often composed of a polygonal crystal, not a single crystal. Since the vibrational vectors of constituent molecules face to various directions, the vibratmal energies are balanced out, and hence the vibrational energy effect that is exerted externally of the crystal becomes lessened; and li ) Interlayer water and crystal water as a residue in the growth process of minerals, always remain in the solid interior and crystal of the minerals. The interlayer water and crystal water prevent a vibrational spectrum from being propagated outwardly, and hence the vibrational energy becomes extremely weak.

In order to solve the above problems to take out vibrational energy at high efficient, a mineral is heated to dehydrate an interlayer water. Specifically, the mineral is heated to in the order of about 400°C to about 1000°C within an hour or two by raising the temperature at intervals of 100 to 150°C in a stepwise fashion. This heating causes a structural change, OH dehydration and recrystallization, in addition to the interlayer water dehydration. In general, the entire structural collapse, atom rearrangement and recrystallization will occur in the range of 750°C to 1000°C. It is well known that the recrystallization mainly depends on the chemical constituent of a mineral.

In this preferred embodiment, an extracted mineral is fired in the order of about 400°C to about 850°C to conduct dehydration and recrystallization. The resulting crystal is ground to in the order of about 200 mesh to about 450 mesh, which is then used as a major ingredient of a substrate portion 3. Grinding is normally carried out after firing, however, these may be performed in the inverse order.

(B) A secondary ingredient serves as a supplement of major ingredient (A), and it has the following functions: l) To eliminate the difference in expansion coefficient between the core portion 2 and a major ingredient; and n) To promote the effect of a mineral as major ingredient (A) . As a secondary ingredient, there can be used those which are generally employed as a glaze in ceramic industry. For example, there are SrO, Tι0₂, CoO, FeO and Fe₂0₃.

Major ingredient (A) and secondary ingredient (B) are normally present in amounts within the range of 90 to 95 percent by weight and

5 to 10 percent by weight, respectively. In other cases, the ingredients

(A) and (B) may be present in the range of 80 to 95 percent by weight and 5 to 20 percent by weight, respectively.

The surface portion 4 is formed by firing with the substrate portion 3 disposed the periphery of the core portion 2. The surface portion 4 corresponds to the surface of the substrate portion 3, and it has a vitrified layer to prevent damage and wear to the reforming material 1 from contact with other materials. This vitrifaction enables the vibrational spectrum of the underlying substrate portion 3 to be sufficiently supplied outwardly.

To obtain the reforming material 1, it is necessary to vitrify only the surface of the substrate portion 3 and not to vitrify its interior . Therefore, firing temperature and connection time are limited. Description will now be given of the measurement and actual proof of a reforming material 1 as described.

As a raw water 6, a tap water is used which is adjusted to have a temperature of 25°C, a pH of 6.75, and an ORP (oxidation-reduction potential) of 528 mV.

As shown in Fig. 2, a plurality of reforming materials 1 are stacked in a beaker 5, into which the raw water 6 is poured to immerse the reforming materials 1.

Table 1 Elapsed t me (h) ORP ( V)

0 528

21.5 208

32.5 183

56.5 158 69.5 157

As can be seen from Table 1, the ORP reduces with time.

Utilization of the invention will be described hereafter. Tap water contains a trace quantity of natural organic matter that serves as a precursor of tolyhalomethane . This precursor reacts with chlorine to produce tolyhalomethane. As typical representatives of this precursor, there are natural corrosives, such as humic acid and flubo acid, which are called chromatic ty constituent in water. A fumic acid particle is composed of a protein and triple water layers surrounding the protein. By enhancing the reducing power sequentially from the water of the outermost layer, the water layer in the surface of the protein is thinned. This facilitates contact with microorganisms, leading to microbial decomposition.

Therefore, when tap water containing humic acid in its flowing state is brought into contact with the reforming material 1, the reducing power of the water itself is increased to reduce the thickness of the layer of water molecules surrounding the humic acid. This facilitates to eliminate the precursor of tolyhalomethane.

In addition, against general bacteria, an intermediate product that is present until water molecules are formed by oxygen molecules can be produced by the reducing power, and the toxicity of the intermediate product exerts bactericidal action. Examples of the intermediate product are superoxide (0₂ ^") , peroxide (0₂ ^2") and hydroxy radical (OH^') . Furthermore, C0₂ dissolved in water will react with H₂ m a treated water which occurs by the action of the reforming material 1 as previously described, and H liberated by the decomposition of oxonium, thereby the C0₂ is converted into CO. The CO has a strong reducing power to form a metal carbonyl compound, and a carbonyl as a ligand is substituted by another ligand to form a mixed complex, for example, Fe(C0)₃or (NH₃)₃, thus permitting descaling for water supply pipe (iron pipe) , or the like. Second Preferred Embodiment

Description will be given of the case where a reforming material according to the invention is applied to fossil fuels. The reforming material has the same structure as that which is described by referring to Fig. 1, but differs in the constituent of a substrate portion 3.

The substrate portion 3 of a reforming material 1 according to a second preferred embodiment has a vibrational spectrum equivalent to an absorption spectrum (energy) needed in reforming of petroleum, namely, the absorption spectrum inherent in hydrocarbon. The vibrational energy of the internal vibration corresponding to this vibrational spectrum is transferred to the hydrocarbon molecules of petroleum by excitation transfer, in particular, resonance transfer, thereby exciting the molecules. Thereafter, by the solvate electrons that are liberated by the transition from the excited state to ground state, and the decomposition of the molecules, chemical bonding and dissociation are repeated until a chemical equilibrium point is reached, thereby reforming the petroleum.

Referring to Fig. 3, in a fuel tank 7, partitions 9 define a passage 8 which provides communication of petroleum products as a fossil fuel, for example, gasoline, kerosene, and heavy oil. A wall 7a of the fuel tank 7 and the partitions 9 define a casing 10 for filling the reforming materials 1. Part of the casing 10 which corresponds to the lower part of the inner side of the partitions 9 is made of a mesh member, and the downstream of the passage 8 is in communication with an internal-combustion, e.g., an engine.

The fuel introduced into the fuel tank 7 from its inlet is brought into contact with the reforming materials 1 within the casing 10 and supplied to the internal-combustion through the passage 8. At this time, since the vibrational spectrum of the substrate portion 3 of the reforming material 1 corresponds to the absorption spectrum inherent in hydrocarbon, the vibrational energy of the internal vibration that developed in the substrate portion 3 of the reforming material 1 is transferred to the hydrocarbon molecules of the petroleum by means of excited transfer, particularly, resonance transfer, to excite the molecules. Thereafter, by the solvate electrons that are liberated by the transition from the excited state to ground state, and the decomposition of the molecules, chemical bonding and dissociation are repeated until a chemical equilibrium point is reached, thereby reforming the petroleum.

Referring to Fig. 4, the casing 10 may be disposed externally of the fuel tank 7, so that fuel circulates between the casing 10 and the fuel tank 7 by a fuel circulatory system 13 having a motor 11 and a pump 12. The following Tables 2 and 3 show the results of experiments in which a fossil fuel is brought into contact with the reforming materials 1.

Table 2 Changes n constituents (gasoline) No-treatment lQ-min. contact 1-hr. contact

Density (15°C) 0.7159 0.7236 0.7541

Constituents Aromatic series 19.7% 21.6% 30.6% Olefin 22.3% 21.7% 17.8% Saturated hydrocarbon 58.0% 56.7% 51.6% Table 3

Changes in constituents (light oil) No-treatment 10-min contact 1-hr contact

Aniline point (15°C) 70.9 71.1 71.1 Constituents

Aromatic series 24.1% 24.1% 23.3%

Olefin 0.6% 0.8% 0.7%

Saturated hydrocarbon 75.3% 75.1% 76.0%

The results of the following test on exhausted gas are given in

Tables 3 to 5.

(i) A pipe in which reforming materials 1 were put was fit in halfway a pipe that supplies fuel to an engine.

(ii) An absorption pipe was inserted into an exhaust flue to collect gas, and the gas was measured.

(iii) Soot and smoke (carbon soot) was measured at the time of idle running and the time the engine was warmed as first and second measurements, respectively.

Table 4 Idling 2000 revolutions No-treatment Treated No-treatment Treated

Light oil CO (ppm) 230-245 165-175 410-454 289-316 C0₂ (ppm) 1.91-2.18 2.29-2.42 2.39-2.48 2.38-2.46 NOv (ppm) 74-107 57-80 56-68 42-46 Table 5

3000 revolutions No-treatment Treated

Light oil

CO (ppm) 129- 181 83-84

C0₂ ( ppm) 1 . 97 -2 . 05 1 . 89- 1 . 93 NOy ( ppm) 117 -127 100- 107

Table 6

First Second

Before fitting 35% 24% After 1-month 20% 7%

After 2-month 7 9-

From the results of these experiments, the following matters are expected to occur.

(a) Saturated hydrocarbon content decreases and aromatic series content increases (i.e., the dehydrogenation of naphthene and dehydrogenation of paraffin) . (b) Olefin content decreases and aromatic series content increases (i.e., the cyclization of olefin).

(c) As shown m the results of the experiment on light oil, no problem of ignition arises although octane value increases and no anti-cetane value substance occurs. This is due to the hydrocracking of paraffin and isomerization of paraffin. (d) Water is produced by the oxidation of the separated H₂ gas, alternatively, excess H₂ assists the hydrogenation of olefin, to improve the volatility of gasoline and to aide the cetane value of light oil, at the time of idling. (e) An improvement in fuel consumption is due to an increase in octane value. Generally, aromatic hydrocarbon has the greatest octane value, with isoparaffins, naphthenes, and n-paraffms following in that order.

These matters will thus have the effects of improving fuel consumption and of cleaning exhausted gas at the same time.

Based upon the Woodward-Hoffmann rules, it might be summarized as follows:

(l) In thermal cyclization, the electron of HOMO (Highest Occupied Molecular Orbital) determines stereoselective reactivity. Hence, for symmetric HOMO, namely, when the number of carbon atoms is 4n+2, reaction proceeds m disrotation fashion. On the other hand, when the number of carbon atoms is 4n, reaction proceeds in conrotation fashion because HOMO is anti-symmetrical .

(n) In optical cyclization, the electron excited by LUMO (Lowest Unoccupied Molecular Orbital) determines stereoselective reactivity. When the number of carbon atoms is 4n+2, reaction proceeds in conrotation fashion because LUMO is anti-symmetrical . On the other hand, when the number of carbon atoms is 4n, reaction proceeds disrotation fashion because LUMO is symmetrical. Resonance between the reforming material 1 and vibrational energy corresponds to item (11). It is assumed that repetitive contact with the reforming material 1 allows both ends of polyene to join each other in the same phase, alternatively, several olefms form an olefin and the mutual bond of polyenes causes cyclization. In the meanwhile, molecular vibration is also closely related to chemical reaction. At the instant when the energy obtained by molecular collision is converted into molecular vibration energy, chemical reaction is induced. Neither translation motion nor rotational motion takes part m cutting of bonds. However, as vibrational energy is enhanced, amplitude becomes large and bond strength is significantly reduced. When a bond is formed by chemical reaction, the bond energy generated by the chemical reaction is often stored as vibrational energy, and then released by vibration-rotation interaction, or the like.

Consequently, when resonance occurs between the frequency of the reforming material of the invention and the inherent frequency m various petroleum products, the petroleum constituents receive the energy liberated by the resonance, resulting in its excited state which causes chemical reaction. In a molecule in its excited state, one of the electrons presented in a bonding molecular orbital moves to an antibonding molecular orbital, and therefore, the chemical bond structure is distinctly different from that of a molecule in its ground state .

The excited molecules are stimulated by mutual collision to induce chemical reaction, thereby chemical bonding and dissociation are repeated until a chemical equilibrium point is reached. Accordingly, in order that the vibrational spectrum of the reforming material is absorbed by molecules to cause chemical reaction, a fossil fuel is required to directly collide with the reforming material under a proper pressure. The fossil fuel absorbs the vibrational spectrum of the reforming material at the instant of collision, resulting in its excited state .

The reforming material is preferable to emit one or two kinds of vibrational spectrums for gasoline, depending on its absorption spectrum, and emit three or four kinds of vibrational spectrums for light oil, depending on its absorption spectrum. Third Preferred Embodiment

In the foregoing first and second preferred embodiments, the core potion 2 of the reforming material 1 is composed of a ceramic power of Sι0₂, Alιθ₃, Tι0₂, or Zr0₂, alternatively, a combination of these. The core portion 2 can also be prepared in the following method.

A background matter is firstly provided to permit a clearer understanding of a third preferred embodiment.

In general, the burned ash of municipal refuse to be generated in incineration equipment contains heavy metal and a variety of toxic substances, thus making it difficult to directly recycle the burned ash. Therefore, it is mostly disposed in dumping sites in the present circumstances. In the recent years, however, it has been difficult to find a new dumping site from the viewpoint of environmental protection. Hence, there have been demands to recycle burned ash as a utilizable resource. For example, burned ash is utilized as the raw material for interblock to pave sidewalks.

The third preferred embodiment is directed to convert burned ash into a utilizable resource by employing the burned ash as the raw material for a core portion 2 of a reforming material 1. The burned ash of municipal refuse and a mineral clay for raw material in ceramic industry are mixed at a ratio of one to five, to prepare a mixture. This mixture is then formed into a suitable shape, melted, and then fired at an appropriate temperature in the range of 1200 to 1300°C, to obtain a core portion 2 of a reforming material 1. Examples of the mineral clay are quartz powder and alumina powder for use in ceramic industry.

Thereafter, a glaze that serves as a substrate portion 3, is applied to the core portion 2, and fired at a proper temperature around 1300°C, thereby obtaining a reforming material 1. This glaze is prepared by adding a mineral powder having a specific vibrational spectrum as stated earlier, to a glaze for use in ceramic industry. Examples of the glaze are SrO, Tι0₂, CoO, FeO and Fe₂0₃. The mineral content is between 90 and 95 percent by weight and the glaze content is between 5 and 10 percent by weight. In some instances, the former is between 80 and 95 percent by weight and the latter is between 5 and 20 percent by weight.

Claims

1. A reforming material for fluid material which is a fired product comprising a core portion, a substrate portion and a surface portion, characterized in that: the core portion serving as a structural member, is composed of granules formed by using a ceramic powder as a raw material; the substrate portion covering the periphery of the core portion is formed by using a specific mineral as a raw material, the vibrational spectrum of the specific mineral having physical property that corresponds to the absorption spectrum of a target molecule in the fluid material; and the surface portion covering the surface of the substrate portion is composed of a vitrified layer.

2. The reforming material of claim 1 wherein, the ceramic powder of the core portion is one of Sι0₂, A1₂0₃, Tι0₂ and Zr0 , alternatively, a combination of these; the substrate portion consists of 80 to 90 percent by weight of a major raw material and 5 to 20 percent by weight of a supplementary raw material; to obtain the major raw material, an effective mineral is dehydrated by firing at a temperature in the order of about 400 °C to about 850°C, recrystallized, and ground to in the order of about 200 to about 450 mesh; and the supplementary raw material is one of SrO, Tι0₂, CoO, FeO and Fe₂0₃, alternatively, a combination of these.