JPS60186586A - Pyrolysis of carbonaceous substance - Google Patents

Abstract

PURPOSE:A carbonaceous substance is pyrolyzed by rapidly heating up to a specific temperature in a hydrogen atmosphere containing methane to increase the yield of light fractions including gasoline with reduced gas formation and decreased hydrogen consumption. CONSTITUTION:In the gasification or liquefaction of carbonaceous substances, the pyrolysis is carried out in a hydrogen atmosphere containing 10-60v% of methane at a pressure of 20-150kg/cm<2>G, preferably in the presence of at least one selected from compounds of a metal of group VI or VIII in the periodic table by heating rapidly up to 600-850 deg.C. More preferably, rapid heating is first effected at 600-800 deg.C, then pyrolysis is conducted at 650-850 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a method for directly producing gas and liquefied oil by thermally decomposing carbonaceous materials in the presence of hydrogen. The present invention relates to a novel method for suppressing the amount of gas produced, reducing the amount of hydrogen consumed, and increasing the yield of liquefied oil including gasoline fraction and light oil by performing cracking.

Recently, archaic 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 used as a means to prepare for the future depletion of oil resources. is now being reevaluated as an alternative energy source and chemical raw material resource to petroleum. but,
Coal is an extremely complex polymer compound, and in addition to its main constituents carbon and hydrogen, it also contains considerable amounts of heteroatoms such as oxygen, nitrogen, and sulfur, as well as ash. In addition to emitting air pollutants, it also has a lower calorific value than petroleum, and poses problems in transportation and storage.

As a means to solve these essential problems associated with coal, we liquefy coal, remove heteroatoms and ash, and produce clean fuel oil, fuel gas, and other high value-added chemical raw materials. methods have been proposed.

Typical of 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 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 to directly obtain gasoline fractions, for example, finely pulverized coal is injected into a high-temperature, high-pressure hydrogen stream, which converts the coal into high-speed water in a short period of several tens of milliseconds to several minutes. Methods of thermal decomposition are known. In this method, for example, pulverized coal is heated at a pressure of 50 to 250.
kP10tn2 (gauge pressure), temperature 600-1200C
The process is carried out by ejecting hydrogen into a stream of hydrogen and pyrolyzing it, producing methane, ethane, carbon dioxide, and gaseous products.
- Carbon oxide, water vapor, hydrogen sulfide, ammonia, etc. are also used as liquid products such as gasoline fraction, heavy oil (carbon number 1
0 or more aromatic compounds and high boiling point tars) are crushed,
A solid product containing ash called char as a solid component is obtained.

However, in this method, when the reaction polarity is low,
The total conversion rate from coal to liquid or gas (the number of carbon atoms in all products divided by the number of carbon atoms in the feed coal, multiplied by 100) will be lower (7, or even 10 or more carbon atoms). The main products are aromatic compounds and heavy oils such as tar.

In addition, if the reaction temperature is high, although the total conversion rate will be high, the decomposition of the liquid product will be accelerated and methane will become the main product, and the yield of liquid products such as gasoline fraction and light oil fraction will decrease. Moreover, there is a problem in that the amount of hydrogen 'M consumed increases significantly, which is extremely disadvantageous industrially.

In the present invention, Nagisa et al. solved these problems and converted carbonaceous materials such as coal into gasoline fractions and light oils as transportation fuels and chemical raw materials in high yields.J! ;
As a result of intensive studies to suppress the production of carbonaceous substances and reduce the amount of carbonaceous substances consumed, we found that by rapidly heating and decomposing all carbonaceous substances in an atmosphere of hydrogen gas containing methane, It has been found that it is possible to reduce methanoic acid generated from carbonaceous Naru'P1, thereby reducing hydrogen consumption and increasing the conversion rate to 11 in the broken liquid. Based on this knowledge, Schiff was able to complete the present invention.The light oil mentioned here is mainly composed of 2-5 condensed aromatic compounds.

In other words, the present invention mainly suppresses the production of methane,
The main objective is to reduce hydrogen consumption, and as a result, it is a new decomposition method that can directly produce liquid compounds, including light oil, from carbonaceous materials in high yield. When gasifying or liquefying a substance, a pressure of 20 to 150 liters containing 10 to 60'8 #t% of methane is used.
Kr), 10ttL2G (gauge pressure) in a hydrogen gas atmosphere, the present invention provides a method for thermally decomposing a carbonaceous material, which is characterized by rapid heating to a temperature of 600 to 850C for decomposition.

The reaction mechanism of methane is unknown, but active species such as methyl radicals and carbenes generated by thermal decomposition of supplied methane stabilize active intermediates generated by thermal decomposition of carbonaceous materials, and convert into gases such as methane. This is thought to suppress further decomposition of .

According to the present invention, the amount of methane contained in the hydrogen gas is 10 to 60 grams. If the volume ratio is less than 10% by volume, the object of the present invention cannot be achieved. If it exceeds 60% by volume, soot may be generated due to thermal decomposition, which is not preferable. In order to achieve the object of the present invention, the volume is preferably 15 to 40, more preferably 20 to 35.

Note that this methane produced from carbonaceous material by the method of the present invention can be recycled and used. In fact, the hydrogen gas containing methane does not have to be pulverized hydrogen gas at all, and may contain a small amount of carbon oxide, carbon dioxide, water vapor, nitrogen, etc.

If the pressure of hydrogen gas containing methane is less than 20 kP/αM2G, the overall rate of conversion of carbonaceous material to gas or liquid will decrease1~, which is not favorable because the yield of liquid product will eventually decrease. . In addition, if the pressure is high, the equipment cost will increase and it will be economically disadvantageous, so a pressure of 150 kflom"G or less is appropriate. A preferable range that produces the effects of the present invention and does not become economically disadvantageous is 35 to 120 kP. /(s2G, and the more preferable range is 50 to 100 ky/Sono2G
The carbonaceous material is rapidly heated in a hydrogen gas atmosphere containing methane and thermally decomposed at 600 to 850C, but this thermal decomposition temperature depends on the raw material, such as the type, viscosity, and particle size of the carbonaceous material. It can be appropriately selected within the above range depending on the characteristics, heating time, etc., but if it is less than 6,000, the decomposition of the raw carbonaceous material and the supplied methane will be slow, and the overall width increase rate will decrease.

On the other hand, if the temperature exceeds 850C, decomposition of liquid products such as gasoline fractions and light oils will occur, resulting in a decrease in yield and undesirable production of soot from methane.

There are no particular restrictions on the heating time, but it is usually 2 to 6 hours.
0 seconds is appropriate, and if the decomposition temperature is high, a short time is desirable.

The heating rate of the carbonaceous material is desirably 100 C/sec or more, particularly preferably 1000 C/sec or more, in order to efficiently generate a liquid product and suppress gas generation. On the other hand, the present inventors As a result of repeated studies to obtain gasoline fractions and light oils at higher yields, it was discovered that thermal decomposition could be accelerated by adding metal compounds from Group ■ or Group ■ of the periodic table to carbonaceous materials. The carbonaceous materials are effectively converted into liquid products, which are subsequently converted into gasoline fractions and light oil by water-cooled cracking, and the supplied methane suppresses the conversion of carbonaceous materials to methane, reducing the consumption of hydrogen. It was found that the amount was reduced.

That is, the pressure containing methane i10-60 by volume is 20
A carbonaceous material is heated to a temperature of 600 to 850 C in a hydrogen gas atmosphere of ~150 kPl and 2 G in the presence of at least one metal compound selected from Group 1 of the Periodic Table.
By rapidly heating and decomposing it, methane production is suppressed, the amount of hydrogen consumed is reduced, and gasoline fractions and light oil can be economically obtained in high yields.

The metal elements of group Ⅰ of the periodic table used in the method of the present invention include Mo, W, etc., and the metal elements of group Ⅰ of the periodic table include
Fe, C0% Nis Ru, Rhs Pd.

Examples include pt. As compounds of these metal elements, salts such as oxides, hydroxides, sulfides, sulfates, nitric acid groups, halides, acid ammonium salts, or inorganic metal compounds are used.

In the method of the present invention, the above metal compounds may be used alone or in combination of two or more.

Further, metal compounds other than those mentioned above may be added or used in combination.

As an addition method, the carbonaceous material and the metal compound can be introduced separately into the cracking reactor, but in order to efficiently increase the conversion rate to gas and liquid products, it is necessary to add the carbonaceous material and the metal compound in advance. It is desirable to mix the metal compounds and pump the mixture into the reactor. The amount of the additive can be appropriately selected depending on the raw material carbonaceous material used, but it is generally 0.0001 to 0.2 parts by weight per 1 part by weight of the carbonaceous material on an anhydrous and ashless basis. The scope of the section is heavy. If it is less than 0.0001 parts by weight, it is not suitable for the present purpose, and even if it exceeds 0.2 parts by weight, the effect will not change. Also, 2a! When using a mixture of the above additives,
Preferably, the amount of at least 1 stick of additive is in the range of 0.000'05 to 0.1 parts by weight per 1 part by weight of carbonaceous material. As a result of studying the idea of converting it into light oil, we found that it is desirable to further decompose the liquid raw material produced by rapid heating of carbonaceous material at a temperature higher than its thermal decomposition temperature.

That is, the pressure containing 10 to 60 parts of methane is 20
~Is Oky/m"G (7) In a hydrogen gas atmosphere, in the presence of at least one metal compound selected from Group Ⅰ or Group Ⅰ of the Periodic Table, the carbonaceous material is heated to 600~
After decomposition by rapid heating to 800C, further decomposition is performed at a temperature higher than this temperature and in the range of 650 to 850C, suppressing methane production and producing gasoline fractions and suspicious oils with a higher yield. The purpose is to obtain

In this method, the optimum silk combination between the decomposition temperature of the carbonaceous material in the previous stage and the decomposition temperature in the latter stage is determined by
Although it is selected as appropriate depending on the type of carbonaceous material, the temperature difference is generally 10 to 100 C. For example, coal with a low degree of coalification requires a low temperature in the front stage and a large temperature difference with the latter stage. It's in the direction of Iroki.

The weight ratio of the reaction aqueous system to the supplied carbonaceous material (anhydrous and ashless basis) in the present invention varies depending on the type of carbonaceous material, but is preferably 0.05 or more and 265 or less.

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

According to the process of the invention, the amount of methane produced from the decomposition of carbonaceous materials is reduced, and therefore the hydrogen consumption is significantly reduced, which is economically advantageous, as well as liquid products, especially gasoline fractions, Higher yield of light oil.

Next, the present invention will be further explained by examples.
IIK However, the present invention is not limited to these embodiments.

In addition, the conversion rate to each reaction product (good, defined by the following formula).

World Example 1 Australian lignite is 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: Dry under reduced pressure heating at 2011mHg and 75C,
This pulverized coal 31 produced by I-A with a water acid content of 5 ivt% was heated at a temperature of 805 C1 and a pressure of 0 kg/ra"G using an Incoloy 800 model in which a hydrogen mixed gas containing 20 volumes of methane was flowing. The reaction was carried out by uniformly supplying the gas to the reaction tube over a period of 3 minutes.At this time, the residence time of the mixed gas passing through the heating reaction section, that is, the reaction time, was 7 seconds.Of the products that came out of the reaction tube, , the char is separated in a char trap, and the gasoline fraction and oil are -68U
The gas was condensed and separated using an indirect cooler using a refrigerant, and after reducing the pressure, the gas was collected in a sampling container and analyzed. The amount of methane produced was calculated by subtracting the amount of methane supplied from the amount of methane collected. As a result of the analysis of these reaction products, the conversion $ (the same applies hereinafter) from coal to each product on a carbon basis was as follows.

CH420, 2% C,H,,3,8 CO1C0,7,5 Gasoline fraction 6.7 Oil 12,6 Char 49.2 The oil contained 44% light oil.

Comparative Example 1 This was carried out in the same manner as in Example 1, but with different supply gas and temperature. That is, the reaction was carried out at a temperature of 795C in a hydrogen gas atmosphere with a pressure of P/1m2G. In order to keep the reaction time the same, the hydrogen flow rate was varied depending on the reaction temperature (the same process was carried out in Example 2 and later and Comparative Example 2 and later). The results of analysis of the reaction product were as follows.

C11425.8% C2H65.4 "CO+C027.8〃 Ganlin fraction 6.6 I oil 4.81 Char 51.6# Also, the oil contained 66% light oil.

The reaction in Example 1 in a hydrogen gas atmosphere containing methane produced 22% less methane than the reaction in Comparative Example 1 in a hydrogen gas atmosphere; .6 times, and 6.2 times for light oil.''W
The effects of the present invention on suppressing methane production and improving oil yield are clear.

Example 2 The same pulverized coal 20゛7 as used in Example 1 was preliminarily mixed with ferric chloride 1. Add Of to 500 d of distilled water,
Stir for 30 minutes. From this mixture, 20 mm H
Most of the water is removed under reduced pressure heating conditions of GS 75C,
Pulverized coal was coated with ferric chloride.

The water content contained in this added carbon was adjusted to 5% by weight.

Using this added carbon, a reaction was carried out in the same manner as in Example 1, except that the methane content was changed to 24 volumes and the temperature was changed to 745C. As a result of analyzing the reaction product, CH42
1.1%, (:2)1. 6.2%, CO17,
1%, gasoline fraction 10.4%, oil 21.0% (light oil content in the oil was 62%), and char 34.2%.

Comparative Example 2 The same enriched ferric-containing pulverized coal as used in Example 2 was used and reacted at a temperature of 730C in hydrogen gas at a pressure of 0 kg/(ln''G).

Reaction generation? As a result of analyzing 1, CH426, 7%, C,
H, 5.8%, CO + C□, 7.5%, gasoline fraction 10.3%, oil 14.0% (light oil content in oil is 60%), char 65.9%. .

In the reaction in Example 2, compared to the reaction in Comparison Series 2, the amount of methane produced was reduced by 21%, while the amount of oil was reduced by 1.
It increased five times. In fact, in Example 2, the yields of the Kallin fraction and light oil fraction increased by a large amount as compared to Actual Mat Example 1. From the above, the %l effect referred to in the present invention is clear.

Example 3 Finely powdered molybdic acid oxide, which was precipitated using ammonium molybdate and sulfuric acid, was added to the pulverized coal used in Example 1 in a layer using T-1 based on anhydrous and ashless standards. Additive charcoal with a moisture content of 5 times was prepared by adding the charcoal at a ratio of 100% and drying under reduced pressure. Using this added carbon, the procedure was the same as in Example 1, but with a methane content of 25 vol. and a temperature of 74 vol.
The reaction was performed in place of 0C.

As a result of analyzing the reaction product, CH422, 5%, C, H
,4.4%, CO+CO26.6%, Ganlin fraction 7.
1 inch, oil 12.1% (light oil in oil is 44%
%), and the char was 47.5%.

Comparative Example 5 The same pulverized coal as used in Example 6 was used, and the pressure
0 kg/(ltz”G hydrogen gas, r blackness 725C
I reacted with

As a result of analyzing the reaction product, CH429,5CH, C2H
.

Section 4.2, CO+Co, 6.2%, gasoline fraction 6.
9%, oil 5.2% (light oil in oil is 40%)
), the char was 48.0%.

Example 4 The Incoloy aooy reactor is divided into two regions, one of which is the front stage is connected to a coal feeder, and the supplied coal is rapidly thermally decomposed and the residence time of the decomposition products and the reaction gas stream is Try to keep it within 1 second. The second step, which is the latter part, is to ensure that the residence time of the decomposition products and the reaction gas stream is 6 seconds, and a thin tube is used to connect the two regions, and the gas passage time through that tube is 50 milliseconds. I made it so that Also, heating JQ? Air heaters were installed separately in both areas.

The front stage was set at 755C and the rear stage at 80DC, the EjE in the reactor was kept at 73ky, /Gy+2, and hydrogen gas containing 12% and 26% of methane and 26'H was added so that it would open during the retention period. It's distribution style.

In the same manner as in Example 2, added carbon enriched with nickel oxide was supplied to this reactor at a rate of 11 per minute to cause a reaction.

As a result of analyzing the reaction product, CH, 22.9%, C21
1,5,8%, CO+CO27,5%, gasoline fraction 1
5.5%, oil 12.4% (light oil in the oil was 69%), and char 36.1%.

Comparison Example 4 The same as Example 4, but the temperature in the first stage was set to 745C, and the reaction was carried out using hydrogen gas not containing methane.

Analysis of the product revealed that CI (430.8%, C2
1 (65.2%, CO + CO, 7.4%, Ganlin fraction 15.2%, light oil in oil 7.4% (oil) 65%), char 36.7%.

In the reaction in Example 4, compared to the reaction in Comparative Example 4, the amount of methane produced was reduced by 26%, while the oil was
．． It increased six times. Sorry, gasoline distillate is increasing.
The term 93+ dumbness referred to in the present invention is obvious.

procedure? 111 Author: April 20, 1980 Director of the Patent Office Kazuo Wakasugi 1 Indication of the case Patent application No. 13'52 1981 2 Title of the invention Method for thermal decomposition of carbonaceous materials 3 Case of a person who submits an amendment Relationship/Patent Applicant (003) Asahi Kasei Kogyo Co., Ltd. 4 Agent 5th Floor, Toranomon Sangyo Building, 2-29 Toranomon-chome, Minato-ku, Tokyo Column 6 Detailed Description of the Specified Invention Detailed Description of the Specification of the Amendment No. 11 "10~1oOtl'j on page 15 is corrected by [10~200c, preferably 10~50CJ].

Claims (1)

[Claims] +11. When gasifying or liquefying a carbonaceous material, a pressure of 20 to 150 k containing 10 to 60 volumes of methane;
In a hydrogen gas atmosphere of g10m2G, the temperature is 600-85
A method for thermal decomposition of carbonaceous materials, characterized by rapid heating to 0C and disintegration. (21. When gasifying or liquefying carbonaceous substances, a pressure of 20 to 150 k containing methane of 10 to 60 vol.
g/1ytn2G hydrogen gas atmosphere in the presence of at least one metal compound selected from Group ■■ or Group V■ of the periodic table, and is rapidly heated to a temperature of 600 to 850C to cause decomposition. A method of thermal decomposition of carbonaceous materials. (3) When gasifying or liquefying carbonaceous materials, use 10 to 60 volumes of methane! ! Pressure containing t% 20-150
k1. /(yI/L2G) in a hydrogen gas-Ir atmosphere, at least one member selected from Group VI or Vl of the periodic table.
In the presence of a seed metal compound, the carbonaceous material is
A method for thermally decomposing a carbonaceous material, which comprises decomposing it by rapidly heating it to 0C, and then decomposing it at a temperature higher than the heating temperature in the previous stage and in the range of 650 to 850C.