JPS59122592A - Thermal decomposition of carbonaceous substance - Google Patents

Abstract

PURPOSE:To suppress a ratio of conversion into mathane gas and to raise a ratio of conversion into gasoline and gas oil, by hydrogenating a carbonaceous substance in the presence of both a Cr-containing compound and a metal(compound) of Fe, Co or Ni under specific conditions. CONSTITUTION:A carbonaceous substance such as anthracite, bituminous coal, etc. is hydrogenated in the presence of both a Cr-containing compound and one or more substances selected from three metals(compounds) of Fe, Co and Ni at 35-250kg/cm<2> partial pressure of hydrogen at 500-950 deg.C under rapid heating, so that the carbonaceous substance is gasified or liquefied.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for pyrolyzing carbonaceous materials in the presence of hydrogen to directly produce gas and liquefied oil; The present invention relates to a novel method for increasing the conversion to gasoline and light oils.

Recently, primary carbonaceous materials such as coal and tar sands, which are the most abundant fossil fuel resources and are widely distributed around the world, have been proposed as a means to cope with the future depletion of oil resources. It is now being reevaluated as an alternative energy source and chemical raw material resource to petroleum. However, 5 coal is an extremely complex liquid polymer compound, and in addition to its main components carbon and hydrogen, it also contains significant amounts of heteroatoms such as oxygen, nitrogen, and sulfur, as well as ash, so it can be burned as is. In addition to producing large amounts of air pollutants, it also has a lower calorific value than 1 petroleum, and poses problems in transportation and storage.

As a means to solve these essential problems associated with coal, coal is liquefied, heteroatoms and ash are removed, and clean fuel oil and fuel gas are produced.

Many other methods of obtaining high value-added chemical raw materials have been proposed. Representative methods among these methods include, for example, a method of extracting coal with a solvent, a method of liquefying coal in the presence of hydrogen or a hydrogen donor, and a method of liquefying and gasifying coal in the presence of hydrogen. , a method of liquefying or gasifying coal in an inert gas, etc.

However, although these methods can directly obtain all of the components that are energy sources, they have not been able to proactively and efficiently obtain gasoline fractions as transportation fuels and chemical raw materials.

Conventionally, as a method for directly obtaining a gasoline fraction, for example, finely pulverized coal is injected into a high-temperature, high-pressure hydrogen stream in a short period of several tens of milliseconds to a few minutes.
Methods of high-speed hydrogenation and thermal decomposition of coal are known. In this method, for example, pulverized coal is heated to a pressure of 50 to 2so K.
g/cdt (gauge pressure), is injected into a hydrogen stream at a temperature of 600 to 1200°C, and hydrogenated and pyrolyzed, producing gaseous products such as methane, ethane, carbon dioxide, -
Contains carbon oxide, water vapor, hydrogen sulfide, ammonia, etc. as liquid products, gasoline fraction, heavy oil (aromatic compounds with carbon atoms of 10 or more and high boiling point tar), and ash called char as a solid component. Solid products etc. are obtained.

However, in this method, when the reaction temperature is low, the total conversion rate of coal to liquid or gas (the number of carbon atoms in the total product divided by the number of carbon atoms in the feed coal, multiplied by 100) is low. Furthermore, the main products are aromatic compounds with 10 or more carbon atoms and heavy oils such as tar. Also, if the reaction temperature is high.

Although the total conversion rate is high, the decomposition of the liquid product is promoted and methane becomes the main product, resulting in a decrease in the conversion rate of the gasoline fraction, which is no more than 3 to 8 inches.

On the other hand, carbonaceous materials such as coal contain Fe and Co.

By adding compounds such as Ni and then pyrolysis, the amount of liquid product as a gasoline fraction precursor is increased, and the gasoline fraction is produced by hydrogenation pyrolysis with prolonged condensation. A method of increasing the conversion rate to this fraction and the conversion rate to lightened oil is known. Note that the light oil referred to here is a 2- to 5-ring condensed aromatic compound.

However, although these compounds such as Fe, Co, and Ni have the effect of increasing the conversion rate from carbonaceous substances to Ganlin fraction and light oil, they also significantly increase the conversion rate to methane gas, which has low added value. This has the undesirable drawback of significantly increasing hydrogen consumption and causing large economic losses.

As a result of intensive studies to solve this problem, the present inventors have found that by adding a Cr-containing compound to a carbonaceous material together with a metal or a compound of Fe, Co, or Ni, it is possible to convert it into a gasoline fraction and light oil. It has been discovered that the conversion rate to methane gas can be effectively suppressed while further increasing the conversion rate, and based on this knowledge, the present invention has been completed.

In other words, the present invention increases the decomposition of carbonaceous materials and promotes their conversion to liquid products while suppressing their conversion to methane gas, thereby producing gasoline fractions and light oils (mainly naphthalene, etc.) in extremely high yields. A new decomposition method that can directly produce gasification or liquefaction of carbonaceous materials.
, in the coexistence of a Cr-containing compound and at least one substance selected from three metals, Fe, Co, and Ni, or their compounds, at a pressure of 35 to 250 Kg/ca (gauge pressure). A method for thermally decomposing a carbonaceous material, characterized in that the carbonaceous material is decomposed by rapidly heating it to a temperature of 500 to 950°C in a gas atmosphere, and in the presence of the catalyst,
After rapidly heating the carbonaceous material to 500 to 900 °C to decompose it in a substantial hydrogen gas atmosphere at the above pressure,
Furthermore, it is higher than the heating temperature of the previous stage, 60Q ~ 950℃
This is a method of pyrolyzing carbonaceous materials, which is characterized by decomposing them at a temperature in the range of .

The Cr-containing compounds used in the method of the present invention include:
Cr2O5, Cr0a Cr (NOa)a, K2'
There are various other types of Cr2O7 (), but when these compounds are used in combination with at least one metal or a compound thereof from among the three metal elements FeICo and Ni, which will be described later. , Fe + Co +
In addition to the characteristic effects of Ni-containing compounds, the rate of rapid thermal decomposition of carbonaceous materials, especially to gasoline fractions and light oils mainly containing naphthalene, is increased, while the rate of conversion to methane gas is increased. can be kept extremely low. This selective increase in the conversion rate to gasoline fraction and naphthalene-based light oil and the decrease in the conversion rate to methane gas are not observed in other metal compounds and are characteristic of chromium-containing compounds. This is a great effect.

There are no particular restrictions on the metals or compounds of Fe, Co, and Ni used in combination with the above-mentioned chromium-containing compound in the method of the present invention, and any metal or compound may be used. , the conversion rate to gasoline fractions and light oils is extremely high, but these effects are further enhanced when used in combination with Cr-containing compounds. This is particularly advantageous because the effect of the Cr-containing compound appears more markedly than in the case of the Cr-containing compound. What is also unique is that these compounds had the major drawback of significantly increasing the conversion rate to methane gas, but by combining it with a Cr-containing compound, it became possible for the first time to keep this conversion rate low. That's what happened.

From the above, chromium-containing compounds, Fe, and C.

The combination of Ni and metals or compounds is particularly effective for the purpose of the method of the present invention, which is to increase the conversion rate to gasoline fractions and light oils while suppressing the production of methane gas. In this case, Fe, Co and N
The metal or compound of i may be one type, or two or more types may be mixed. Moreover, metal compounds other than these may be added to these compounds.

However, in order to efficiently increase the conversion to gas and liquid products, it is necessary to mix the carbonaceous material and the metal compound in advance and send the mixture to the reactor. It is desirable to sink in.

For example, mixing of carbonaceous substances and these additives can be carried out mechanically by finely pulverizing them in a mortar, ball mill, type powder mixer, stirring mixer, etc. The additive may be dissolved or suspended in alcohol or other organic solvent, the carbonaceous material may be added thereto, and then the solvent may be removed.

Furthermore, hydroxides or oxides produced by adding Cr or halides of Fe, Co, or Ni, or alkali hydroxides such as potassium or sodium hydroxide are in a very fine powder state and have poor dispersibility in carbonaceous materials. Very good. Among these, a method in which hydroxides and oxides are generated in the coexistence of carbonaceous substances and then filtrated and washed has excellent dispersibility and adhesion of additives to carbonaceous substances in the resulting mixture. It is one of the desirable methods because it shows extremely high reaction activity.

Cr-containing compounds and Fe used in the method of the present invention
, Co, and Ni metals or compounds are added as follows:
Although they can be appropriately selected depending on the type of raw material carbonaceous material to be used, it is generally desirable that the amount is in the range of 0.0001-0.2 parts by weight per 1 part by weight of the carbonaceous material on an anhydrous and ash-free basis. If either amount is less than 0.000 parts by weight, the conversion rate to gasoline fraction and light oil will not be particularly high and it will not meet the purpose of the present invention, and if it exceeds 0.2 parts by weight, The increase in conversion rate becomes extremely small with respect to the increase in additives.

In addition, when two or more additives are mixed as a metal or compound of 1' e + Co + Ni and used in combination with a Cr-containing compound, the amount of at least one of the multiple additives is carbon. per part by weight of the substance
-c, o, oooi to 0.1 parts by weight of the desired substance or Fe, Co, NM group or compound group or 100 parts by weight of the compound.
The amount of the r compound is preferably in the range of 1 to 200 parts by weight, particularly preferably in the range of 20 to 80 parts by weight.

The decomposition temperature in the method of the present invention is in the range of 500 to 950°C, which is higher than the normal liquefaction process temperature using a solvent, but lower than the gasification process temperature, and the heat of the carbonaceous material without adding metal compounds. Compared to the decomposition temperature, 20
The maximum yield of Ganlin fraction can be obtained at temperatures as low as ~200°C.

The thermal decomposition temperature can be appropriately selected within the above range depending on the type of raw carbonaceous material, characteristics of the raw material such as viscosity and particle size, and heating time, but if the temperature is less than 500 ° C.
Cracking is slowed down and the total conversion rate and conversion rate to gasoline fraction and light oil decreases, while above 950°C;
The decomposition rate of gasoline fraction and light oil increases significantly, resulting in a decrease in the yield of gasoline fraction and light oil, and a large increase in methane, which is undesirable.

There are no particular restrictions on the heating time, but it is usually 0.02
~60 seconds is appropriate.

On the other hand, the present inventors have discovered that Cr-containing compounds and Fe, Co
+ As a result of a more detailed study on the conversion of a liquid product, which is a precursor of a gasoline fraction, produced by thermal decomposition of a carbonaceous material to which Ni metal or its compound has been added into a gasoline fraction, it was found that the addition of the metal or its compound The carbonaceous material was rapidly heated at SOO ~ 900 °C to decompose it, and the volatile matter was diffused through a solid mass (IJ), and then this was heated to 600 °C at a temperature higher than the heating temperature in the previous stage.
It has been found that a larger amount of gasoline fraction can be obtained by decomposing at a temperature in the range of ~950 t:.

In the above method, the optimal combination of the decomposition temperature of the carbonaceous material in the previous stage and the decomposition temperature in the latter stage is as follows:
Although it is selected appropriately depending on the type of carbonaceous material, the temperature difference is generally 10-100 °C, and coal with a low degree of coalification requires a low temperature in the front stage and a large temperature difference with the latter stage. In addition, the reaction time in the later stage of decomposition is preferably 1 to 6 seconds; if the time is less than 1 second, the conversion to gasoline fraction and light oil will not proceed sufficiently; If the time exceeds 60 seconds, the possibility of decomposition of gasoline fraction and light oil increases.

The heating rate of the carbonaceous material in the method of the present invention is desirably 100°C/sec or more, particularly preferably 1000'C/sec or more, in order to efficiently generate gasoline fraction and light oil during thermal decomposition. . A heating rate of 100 U/sec or more preferentially cleaves the crosslinks of the carbonaceous material structure, which can produce the desired product and its precursor liquid product.

Further, the pressure of the substantial hydrogen gas atmosphere in the present invention is 3
It is necessary that it is 5 to 250 ~/- (gauge pressure), preferably 50 to 200 Ky/crA. The substantial hydrogen gas atmosphere here refers not only to pure hydrogen gas but also to a gas atmosphere in which hydrogen gas is the main component, such as inert gas, thin ice vapor, carbon dioxide gas, - It may be diluted with a total of up to about 30 volumes of gas such as carbon oxide, methane, etc. The pressure of this substantial hydrogen gas atmosphere is a particularly important condition for providing the effect of preventing polycondensation of the active liquid compound produced during direct thermal decomposition of carbonaceous materials, and also for preventing the gasoline fraction of the liquid compound. It is necessary for efficient conversion to

In the latter stage of decomposition, the higher the pressure, the more effective it is, but once the pressure exceeds a certain level, the effect does not increase much, and rather becomes economically disadvantageous due to increased equipment costs.

Carbonaceous material supplied in the method of the present invention (anhydrous/ashless standard)
Although the weight ratio of reaction hydrogen to the carbonaceous material varies depending on the type of the carbonaceous material and the composition of the required reaction product, generally the theoretically necessary weight ratio of hydrogen is 0.03 to 0.08. However, by improving the acid expansion of liquid products from carbonaceous materials and the diffusion of hydrogen into the pores of carbonaceous material powder, the conversion rate from carbonaceous materials to gasoline fractions and light oil is greatly reduced.
To prevent coking: It is desirable to supply hydrogen in excess. However, excess hydrogen is separated from products from carbonaceous materials and returned to the reactor for recycling, so as the amount of excess hydrogen increases, the energy and equipment required for separation, circulation, and heating also increase, making it economical. be at a disadvantage. Therefore, the actual weight ratio of supplied hydrogen to supplied carbonaceous material is preferably 0.1 or more and 2.5 or less, and more preferably 0.12 or more and 2.0 or less.

Carbonaceous substances used as raw materials in the method of the present invention include, for example, anthracite coal, bituminous coal, subbituminous coal, and charcoal, lignite,
Examples include coal such as peat and grass charcoal, oil shale, tar sands, organic waste, plants such as wood, and crude oil.

According to the process of the present invention, the cracking of carbonaceous materials is increased and the conversion to gaseous and liquid products is promoted, resulting in very high yields of gasoline fractions and light oils.

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples.

In addition, the conversion rate to each reaction product is defined by the following formula.

Example 1 Australian lignite was crushed to produce 100 mesh (J
The coal was passed through a sieve of IS standard) to produce pulverized coal. The elemental analysis values of this coal were as shown in Table 1 on an anhydrous basis.

Table 1 10 fP of this pulverized coal was added to 500 tnl of distilled water in which 2.9 t of chromium nitrate (anhydrous standard) had been dissolved in advance and stirred for 30 minutes. To this mixed solution was added 50 mm of ammonia water containing 1.01 ammonia as NH3, and the mixture was further stirred all day and night. The precipitated mixture of chromium oxide and coal was separated from this liquid by suction filtration and thoroughly washed with water until no ammonium ions were detected in the filtrate.

Next, this mixture was added to 500 ml of distilled water in which 5 t of ferrous sulfate S (anhydrous basis) had been dissolved in advance, and stirred day and night.

Finally, the mixture created here is 201Ht, 75
The mixture was dried under reduced pressure and heating conditions at 0.degree. C., and the moisture content was adjusted to 5 parts by weight based on 100 parts by weight of the mixture.

This added carbon was heated to a temperature of 730°C and a hydrogen pressure cuff of 0 Ky/
Hydrogen gas was uniformly supplied over 1 minute to a reaction tube made of Incoloy 800 in which hydrogen gas was flowing under the condition of cA (gauge pressure) to cause a reaction. At this time, the residence time of the hydrogen gas passing through the heating reaction section, that is, the reaction time, was 7 seconds, and the weight ratio of the amount of hydrogen supplied for reaction to the supplied coal was i, s. Of the products that came out of the reaction tube, char was separated using a char trap, the reed gasoline fraction and oil were condensed and separated using an indirect cooler using a refrigerant at -68°C, and the gas was depressurized and then transferred to a sampling container. collected and analyzed.

As a result of analyzing these reaction products, the conversion rates from coal to each product on a carbon basis were as shown in Table 2.

Example 2 The same procedure as Example 1 was carried out, except that the additives and reaction temperature were changed. , that is, the pulverized coal 101F used in Example 1
1=51 chromium nitrate (anhydrous standard) and 2.9 g of ferric nitrate (anhydrous standard) were dissolved in 500 - of distilled water.
After stirring for 30 minutes, 100 m of aqueous ammonia containing 1.0 g of ammonia was added as NH3 to the mixture, and the mixture was further stirred all day and night. From this liquid, precipitated chromium oxide and a mixture of iron hydroxide and coal were separated by suction filtration and thoroughly washed with water until no ammonium ions were detected in the filtrate.

The mixture was then dried under reduced pressure and heating conditions of 20 mxHl and 75°C to adjust the moisture content to 51 parts by weight per 100 parts by weight of the mixture. This mixture was dried under the same conditions as in Example 1 except that the temperature was 680°C. The reaction was carried out. The results of analysis of the reaction products are shown in Table 2. In addition, in order to keep the reaction time the same, the hydrogen flow rate was changed depending on the reaction temperature. (The same method was followed for Example 3 and subsequent examples and Comparative Examples.) Example 3 The same procedure as Example 1 was carried out, but the additives and reaction temperature were changed. That is, the pulverized coal 1Of used in Example 1 was preliminarily mixed with chromium nitrate 1. Of (anhydrous basis) and nickel sulfate2. 500 ml of distilled water containing Of (anhydrous standard)
and stirred for 1 hour. From this mixture, 20 u
Hf % Based on 100 parts by weight of the mixture after removing most of the moisture under vacuum heating conditions at 75°C.

The moisture content was adjusted to 5 parts by weight, and chromium nitrate and nickel sulfate were applied to the pulverized coal.

This mixture was reacted under the same conditions as in Example 1 except that the temperature was 750°C. The analysis results of the reaction products are shown in the second
It was the front door.

Example 4 The same procedure as Example 1 was carried out, but with different additives and reaction temperature. That is, cobalt carbonate was used instead of ferrous sulfate among the additives, and the reaction temperature was changed to 685°C.

The amount of additives, preparation of the mixture, and reaction conditions other than temperature were the same as in Example 1. The results of analyzing the reaction products are shown in the second
It was as shown in the table.

Example 5 The pulverized coal 10f used in Example 1 was treated with chromium nitrate o,
sy (anhydrous basis) was added to 500 d of distilled water and stirred for 1 t+-. From this mixture, 2°+
u+HP, remove most of the moisture under reduced pressure heating conditions at 75°C and adjust the moisture content to 5 parts by weight per 100 parts by weight of the mixture, then place it in a porcelain ball mill with 1.01 parts of metal nickel powder, and place in a container. The inside was sealed with nitrogen and mixed day and night.

This mixture was reacted under the same conditions as in Example 1. The analysis results of the reaction products were as shown in Table 2.

Comparative Examples 1 to 2 The same conditions as in Example 1, but without adding any additives.
The dried coal was reacted at temperatures of 730°C and 670°C, respectively. The results of analysis of each reaction product are shown in Table 2.

Comparative Examples 3 to 5 The pulverized coal 10F used in Example 1 was preliminarily mixed with 0.52% of ferrous sulfate, 0.51% of nickel sulfate, and 0.51% of cobal carbonate).
Distilled water with 0.5 F (each anhydrous standard) dissolved in 50
01nl and stirred for 1 hour. From these mixed liquids, most of the water was removed under reduced pressure and heating conditions of 20 van Hff and 750°C to adjust the water content to 5 parts by weight per 100 parts by weight of the mixture, and ferrous sulfate, nickel sulfate, and cobalt carbonate were added, respectively. was stuck on pulverized coal. Using these added carbons, the temperature was set to 740°C, 745°C, and 6°C, respectively.
The reaction was carried out under the same conditions as in Example 1 except that the temperature was 70°C. The analysis results of each reaction product are shown in Table 2.

Comparative Example 6 The pulverized coal 10IF used in Comparative Examples 1 and 2 was placed in a porcelain ball mill together with metal nickel powders i and ot, and stirred all day and night under a nitrogen atmosphere.

Using this mixture, a reaction was carried out under the same conditions as in Example 1. The analysis results of the reaction products are shown in Table 2.

From the above results, it is clear that the chromium-containing compound according to the present invention and Fe
In the thermal decomposition of coal to which Co or Ni compounds have been added, the conversion rate to Ganlin fraction and oil fraction increases significantly compared to the case of coal without additives, and the conversion rate becomes higher. It is clear that the thermal decomposition reaction is accelerated. In addition, compared to coal with only Fe, Co, or Ni compounds added without Or compounds, the conversion rate to methane is significantly lower, and moreover, the conversion rate to gasoline fraction and light oil fraction is significantly lower. It is clear that the conversion rate of

This remarkable and selective improvement in the conversion of gasoline fractions and light oils when thermally decomposing coal to obtain products is novel and unprecedented.

Alternatively, the method of mixing and adhering hydroxide to coal has a high conversion rate and conversion rate of the added coal to gasoline fraction, light oil, and ethane, and a low conversion rate to methane and a low reaction temperature. It is also clear that this is a particularly desirable method.

Example A reactor made of Incoloy 800 is divided into two regions, one of which is the front stage is connected to a coal feeder, the supplied coal is rapidly heated and decomposed, and the residence time of the decomposition products and the hydrogen gas stream for reaction is determined. was made to be within 1 second. In the other rear stage, the residence time of the decomposition products and the hydrogen gas stream for reaction is set to 6 seconds5, and the two regions are connected using a thin tube, so that the fractional distillation product and the hydrogen gas for reaction are connected to each other using a thin tube. The passage time with the gas was set to 50 milliseconds. In addition, separate electric heater systems were used for both areas. The front stage was set at 670°C and the rear stage at 800°C, and the reactor internal pressure was set at 70 K9/cr.
/1 (gauge pressure), and the hydrogen gas for reaction was made to flow so that the residence time shown above was achieved.

Pulverized coal containing chromium oxide and iron hydroxide was supplied to this reactor at a rate of 1 ton per minute in the same manner as in Example 2, and a reaction was caused. The weight ratio of reaction hydrogen to coal was 1.6. The reaction product was collected and analyzed in the same manner as in Example 1.

The product analysis results are shown in Table 3 using conversion from coal on a carbon basis.

Example 7 The same procedure as Example 6 was carried out except that the additives and the temperature of the front stage were changed. That is, instead of iron hydroxide, nickel hydroxide was precipitated together with chromium oxide and added to the coal, and the reaction was carried out at a temperature in the front stage of 6so°C and a temperature in the rear stage of 800°C. The analysis results of the reaction products are shown in Table 3.

Example 8 The same procedure as Example 6 was carried out, except that the additives and the pre-stage temperature were changed. That is, the pulverized coal 101 used in Example 1 was pre-coated with cobal nitrate)2. Of (anhydrous standard) was dissolved in distilled water of 500% and stirred for 30 minutes.
．． 4 F sodium hydroxide dissolved in distilled water 100-
was added thereto, and the mixture was further stirred all day and night. A mixture of precipitated cobalt hydroxide and coal was separated from this liquid using a suction P pan, and the mixture was thoroughly washed with water until no sodium hydroxide was detected in the furnace liquid.

Next, this mixture was added to 500 μl of distilled water in which 0.4 t of chromium nitrate (anhydrous standard) had been preliminarily heated and stirred for 2 hours. Finally from this mixture 20 關HS', 75
Most of the water was removed under reduced pressure heating conditions at ℃, and the mixture i
The amount of water was adjusted to 5 parts by weight based on 0 parts by weight. This mixture was reacted under the same conditions as in Example 6 except that the temperature in the first stage was changed to 670°C.

The analysis results of the reaction products are shown in Table 3.

Comparative Example 7 A reaction was carried out under the same conditions as in Example 6 using crushed and dried Australian lignite without adding any additives.

The analysis results of the reaction products are as shown in Table 3.Comparative Example 8-1O The reaction was carried out under the same conditions as in Example 6, except that only the temperature of the front section and the additives were changed. The conditions and reaction product analysis results are shown in Table 3. From Table 3, it can be seen that the use of the additive in the present invention significantly increases the conversion rate from coal to gasoline fraction, light oil and ethane, and increases the conversion rate to methane. It is clear that the conversion rate of is not significantly different.

Furthermore, compared to the addition of only Fe, Co or Ni compounds, when a Cr compound is used in combination, methane is significantly reduced, and the conversion rate to Ganlin fraction and light oil is improved. , the effect of using Cr compounds is obvious.

Furthermore, from Tables 3 and 2, it is clear that after rapid thermal decomposition during the pyrolysis of the present invention, the decomposition products are subsequently hydrocracked at a higher temperature than in the previous stage, resulting in further conversion to gasoline fraction. It is clear that the conversion rate is improved.

Below margin

Claims (1)

[Claims] 1. For gasifying or liquefying carbonaceous materials F), C
Under the coexistence of an r-containing compound and at least one substance selected from three metals, Fe, Co, and Ni, or their compounds, a substantial The carbonaceous material is heated to a temperature of 50°C in a hydrogen gas atmosphere.
Method 2 of thermal decomposition of carbonaceous materials characterized by decomposition by rapid heating to 0 to 950°C In gasifying or liquefying carbonaceous materials, a Cr-containing compound and three metals of Fe, Co and Ni are used. Or in the coexistence with at least one substance selected from the compounds, under a pressure of 35 to 2 s OKg.
/ctA (gauge pressure) in a substantial hydrogen gas atmosphere, the carbonaceous material is rapidly heated to a temperature of 500 to 900°C to decompose it, and then further heated to a temperature higher than the previous heating temperature and 600 to 950°C. A method for thermal decomposition of carbonaceous materials characterized by decomposition at a temperature in the range of