JPS6024043B2 - Method for producing isotropic carbon - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for producing isomerly carbon.

More specifically, isotropic carbon is produced by heating coal-based heavy oil or petroleum-based vehicle oil in the presence of a catalyst. It is generally known that carbide of non-melting substances becomes isotropic carbon, and carbide of melting substances becomes anisotropic carbon.

That is, if a molten state does not exist at the stage of 400 to 600 qo in the carbonization process, it becomes isotropic carbon, and if a molten state exists, it becomes anisotropic carbon. An example of the former is charcoal,
Examples of the latter include activated carbon and glassy carbon, and examples of the latter include petroleum-based heavy oil and coal-based vehicle oil. The present invention provides a method for producing isotropic carbon from a meltable substance.

In other words, the present invention proposes that when a meltable substance that produces anisotropic carbon by ordinary heating carbonization is heated in the presence of a specific catalyst, it can be heated to 10,000 ton of force without causing a molten state at a temperature of 400 to 600 qC. The present invention has been completed based on the discovery that it is possible to generate the following. That is, the present invention uses as a catalyst one or more of a metal selected from the group consisting of nickel, cobalt, molybdenum, tungsten, chromium, and vanadium, an oxide of the metal, or a double oxide of the metal; Isotropic carbon is produced by heating coal-based heavy oil or petroleum-based heavy oil in the presence of .

The present invention will be explained in detail below.

In the present invention, a catalyst is added to raw material heavy oil and heated under an inert gas atmosphere at normal pressure or pressurization.

The raw electrolyte oil becomes a pitch-like substance that melts when heated in a temperature range of 350 to 450 q0, and becomes a solid substance that does not melt when heated at about 600°C. By further heating this collective substance to 25,000 C or higher and graphitizing it, the isomertile carbon of the present invention can be obtained. At this time, the catalyst can also be removed in advance from the solid material before the graphitization treatment. Of course, even if the catalyst contained in the solid substance is removed and graphitized, or if it is graphitized without removal, no change is observed in isomerality. That is, in the present invention, an isotropic carbon precursor is formed by coexisting the raw material heavy oil and the catalyst of the present invention in a temperature range of about 60,000 °C or less, which is the initial stage of heating carbonization, and isotropic carbon precursor is formed from 600 °C to 600 °C. 25 more
It is believed that isotropic carbon is produced by heating to a temperature of 00qo or higher. In the present invention, the heating method is not particularly limited, but it is preferable to gradually raise the temperature to a temperature range where pitch-like substances are generated.
For example, it is preferable to carry out the heating at a rate of 0.01 to 100/min. Further, it is preferable to heat the mixture while worshiping it until a pitch-like substance is generated. Of course, the present invention can be achieved even without performing Nada Azusa. After the temperature range where pitch-like substances are generated, the temperature may be increased at the temperature increase rate, or
Furthermore, the temperature increase rate may be further increased, and is not particularly limited. Examples of the coal-based heavy oil used in the present invention include coal tar, coal solvent extracted oil, and the like.

Petroleum-based heavy oils include naphtha tar, fluid catalytic cracking tar, crude oil thermal cracking residue, crude oil atmospheric distillation residue, and crude oil vacuum distillation residue. The oxides or double oxides of nickel, cobalt, molybdenum, tungsten, chromium and vanadium used in the present invention include:

For example, nickel oxide (Ni○), cobalt oxide (Coo)
, Co304), molybdenum oxide (Moo3), nickel molybdenum double oxide (NjO.Moo3), cobalt molybdenum double oxide (Coo.Moo3), and the like. In the present invention, a metal selected from the group consisting of nickel, cobalt, molybdenum, tungsten, chromium, and vanadium, an oxide of the metal, or a double oxide of the metal can be supported on a carrier.

Examples of the carrier include alumina, silica alumina, silica, and diatomaceous earth. The amount of the catalyst used in the present invention is 0.1 to 3% by weight based on the organic matter.
, preferably from 1 to 1% by weight.

If the catalyst is too small, the effect of the present invention cannot be expected, and if the catalyst is too large, no better effect can be achieved; it is not only wasted, but also more than necessary when removing the catalyst as necessary. This is not desirable as it requires a lot of effort. The reason why isotropic carbon can be obtained by using the catalyst of the present invention is not strictly clear, but it is thought to be as follows.

That is, when coal-based car oil, petroleum-based heavy oil, etc. are heated, chemical reactions such as decomposition, dehydration, dehydrogenation, cyclization, condensation, and polymerization proceed. As a result of heating these reactions relatively slowly, the molten state of the reaction system is maintained up to 40,000 or more. in this case,
Each molecule can move freely within the system, and as a result, a structure in which planes of polycyclic aromatic nuclei, which are the most energetically stable, are stacked is likely to be formed, and this is the main cause of the manifestation of anisotropy. I think that the. However, in the case of the method of the present invention, reactions such as decomposition, dehydration, dehydrogenation, cyclization, condensation, and polymerization proceed rapidly at temperatures below 350 qo, and as a result, no molten state appears at temperatures above 40,000 qo, and each molecule It is thought that the structure becomes isotropic because the movement of the polycyclic aromatic nucleus is restricted and a structure in which the planes of polycyclic aromatic nuclei are stacked is difficult to form.
Furthermore, even if the isotropic solid material obtained in this way is further turned into so-called graphitization at a high temperature of 250,000 or higher, the isomerality is maintained with almost no progress in crystal growth or molecular orientation. The isomerogenic carbon of the invention is obtained. Among the catalysts of the present invention, metals selected from the group consisting of nickel, cobalt, and molybdenum, oxides thereof, or double oxides of these metals are particularly effective in the present invention. The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 100 qo of naphsatal and 3 qo of nickel oxide were placed in a flask equipped with a fly frame and heated at a heating rate of 300/min to 350 qo while removing volatile components from the system, and held at 350 qo for 1 hour.

Next, the obtained pitch-like material was placed in a 200 ml stainless steel container and heated at a heating rate of 3°C/min under a nitrogen atmosphere to 600 ml while removing volatile matter.
It was held at C for 2 hours.

Then, the obtained carbide was graphitized at 2700 qo', and according to X-ray diffraction measurement, Lc=20A,C.

! 6.80A, and carbon with excellent isotropy was obtained. Comparative Example 1 According to X-ray diffraction measurement of carbon obtained by heating and graphitizing in the same manner as in Example 1 except that nickel oxide was not used, Lc = 630A, C.

=6.75A. Example 2 100 hours of crude oil residual oil (alambian light) and 3 hours of cobalt oxide and molybdenum monoxide double oxide (Co/Mo=1/3: weight ratio) were placed in a flask equipped with a hawker and heated at 3°C. The mixture was heated at a heating rate of /min until 380:00 pm while removing volatile matter from the system, and held for 1 minute at a temperature of ooo.

Next, the obtained pitch-like substance was placed in a 200°C stainless steel container and heated at a heating rate of 300°/min to 600°C under a nitrogen atmosphere while removing volatile matter.
It was held at oo for 2 hours.

Then, the obtained carbide was graphitized at 270,000° C. According to X-ray diffraction measurement, Lc=20A,C.

= 6.81A, and it was confirmed that the carbon was isomerial carbon. Comparative Example 2 According to X-ray diffraction measurement of carbon obtained by thermal graphitization in the same manner as in Example 2 except that cobalt oxide/molybdenum oxide double oxide was not used, LC: 360A, C.

=6.74A. Examples 3 to 11 The present invention was carried out by changing the starting crude oil and catalyst.

The results are shown in the table. table Examples 12-14 The present invention was carried out by changing the raw material car oil and catalyst.

table

Claims (1)

[Claims] 1. A method for producing isotropic carbon from coal-based heavy oil or petroleum-based heavy oil, in which a metal selected from the group consisting of nickel, cobalt, molybdenum, tungsten, chromium, and vanadium, an oxide of the metal, or the metal A method characterized by heating coal-based heavy oil or petroleum heavy oil in the presence of one or more types of double oxides.