JP2003268389A - Method for gasification of sulfur-containing carbonaceous material or sulfur-containing hydrocarbon - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for gasification a raw material comprising a sulfur-containing carbonaceous material, a sulfur-containing hydrocarbon or a waste material thereof to convert efficiently it into a useful gas for recycling without using a complicated desulfurization step. <P>SOLUTION: The method for gasification comprises treating the raw material containing one or more of sulfur-containing carbonaceous materials, or sulfur- containing hydrocarbons in a high-temperature metal bath containing 50% or more copper and less than 50% iron to effect decomposition and gasification and to fix sulfur in the metal bath, thus forming a carbon monoxide/hydrogen mixture gas, a hydrogen rich gas, or a carbon monoxide rich gas which contains no sulfur compound. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses a sulfur-containing hydrocarbon material such as petroleum, heavy oil, coal and coke containing sulfur, and a sulfur-containing hydrocarbon material such as tires, tire scraps and wastes in a metal bath. Carbon dioxide (CO), hydrogen gas (H) used for various chemical raw materials or fuels
₂ ) Alternatively, the present invention relates to a gasification treatment method for producing a useful sulfur-free gas such as a mixed gas (CO + H ₂ ). The present invention also relates to a gasification treatment method for recovering and effectively utilizing sulfur in the material.

[0002]

2. Description of the Related Art Carbon monoxide gas (CO) and hydrogen gas (H) used as fuels and chemical raw materials as energy sources.
Useful gases such as ₂ ) are produced by gasifying carbonaceous materials such as coal, coke and pitch. Typical production methods are (1) incomplete combustion of carbonaceous material for gasification, (2) decomposition of carbonaceous material in a metal bath such as an iron bath, and (3) carbon in an incinerator. A method of burning a carbonaceous material, (4) a method of melting a carbonaceous material in a shaft furnace, and the like are known.

However, in these conventional gasification treatment methods, since the carbonaceous material as a raw material contains sulfur, the produced gas contains a sulfur compound as H ₂ S or COS, and as a fuel. If the produced gas is used, it causes air pollution due to sulfur compounds during combustion, which causes environmental problems.

The problems of the conventional method in the gasification process using a raw material containing sulfur will be described below.

(1) In the case of gasification by incomplete combustion: Carbonaceous material such as coal and oxygen
A method of injecting water vapor to gasify it has been put into practical use.
In this method, the contained sulfur is also gasified and contained in the produced gas as H ₂ S or COS, which is a sulfur compound, so it is necessary to desulfurize it. In order to separate and remove this from the useful gas, a method in which a chemical is absorbed mainly by a wet method is currently adopted, which requires complicated equipment and extra cost. Moreover, since the gas is cooled for desulfurization, the sensible heat of the high temperature gas is not used and is lost. Further, if the oxygen is operated with a slight excess in order to prevent the generation of soot in the produced gas, the utilization factor of the carbonaceous material is increased but the CO / CO ₂ ratio in the produced gas is reduced. Further, this method has a drawback that the gasification rate is affected by, for example, the type of coal used, so that the productivity varies depending on the type of coal.

(2) Method of decomposing in a metal bath such as an iron bath A method has been proposed in which a carbonaceous material such as coal and oxygen are injected into an iron bath at a temperature of about 1400 ° C. to gasify it (Japanese Patent Laid-Open Publication No. Sho. 57-167390). This method is a method of gasifying carbon dissolved in an iron bath with oxygen, but if sulfur is contained in the carbonaceous material, part of it also reacts with iron and is fixed. In the material, slag (CaS) is formed to fix sulfur. However, when the sulfur is high, the slag desulfurization is not sufficient and the amount of sulfur compounds in the produced gas increases, so the need for gas desulfurization appears. Further, in the slag desulfurization, it is necessary to form a basic slag with a large amount of lime, and it is expensive to dispose of the slag and the lime used cannot be separated and recovered. As a result, it is difficult to effectively use the slag.

As a major operational problem, an increase in the sulfur content of the iron bath lowers the carbon solubility, resulting in a lower gasification rate. When the amount of slag increases, it becomes difficult to inject oxygen from above, which causes a problem in operation.

A method for fixing sulfur in a metal bath for gasification using copper having an affinity for sulfur has been proposed (Japanese Patent Laid-Open No. 05-052384), but this method is used as a metal bath. Manganese is contained as an essential component to dissolve carbon and lower the liquidus temperature. Although this method fixes sulfur as sulfide, it does not disclose recovering sulfide to make sulfur useful and regenerate the metal bath. Furthermore, mixed baths of various metals have been proposed to operate by lowering the liquidus temperature (JP-A-54-47707, JP-A-2000-281326, etc.), but lowering the temperature is gasification. However, there is a problem that the productivity of high CO / CO ₂ gas is reduced and the production of high CO / CO ₂ gas becomes difficult.

(3) Combustion in an incinerator This is a waste treatment method, in which the waste is combusted with air. In this method, in the case of sulfur-containing waste, it is necessary to desulfurize exhaust gas and also to treat dioxin. And carbon and hydrogen contained are also burned, and part of the exhaust heat is used for boilers and power generation,
Currently, it is not used as fuel gas.

(4) In the case of a melting furnace and a gasification melting furnace Recently, as an application of blast furnace technology for iron making, equipment for mixing coke with waste and gasifying and melting in a shaft furnace has been put into practical use. Also, a method of melting waste with a low shaft similar to an electric furnace has been put into practical use. In this method, the sulfur in the waste forms slag and is fixed to it, but it is difficult to use the slag containing sulfur, and the generated gas can be used only as a low-grade fuel.

[0011]

In order to recover a useful gas by gasifying a sulfur-containing carbonaceous material or a sulfur-containing hydrocarbon material, it is necessary to efficiently gasify so as not to cause environmental problems. In particular, the amount of waste related to the above-mentioned sulfur-containing material is generated in large amount with the development of industry, and it is the current situation that appropriate treatment and recovery / reuse are required due to environmental problems.

In view of the above situation, the present invention efficiently converts raw materials such as sulfur-containing carbonaceous materials and sulfur-containing hydrocarbon materials and waste materials related to these materials into useful gases without using a complicated desulfurization process. It is an object of the present invention to provide a method for gasifying and recycling.

[0013]

As a method for gasifying a raw material such as a sulfur-containing carbonaceous material or a sulfur-containing hydrocarbon-based material, and waste materials related to these materials, the present inventor uses a metal bath. The research was conducted focusing on the gasification treatment method used.

As a result, by using a mixed metal bath containing 50% or more of copper and less than 50% of iron and operating in a high temperature molten metal bath of 1450 ° C. or more, sulfur in the raw material is converted into a copper sulfide mat (Cu ₂ The present invention has been completed by finding that the raw material can be collected as S), the raw material can be decomposed into a useful gas containing no sulfur, and the sulfur can be recovered from the mat and the copper can be regenerated.

The gist of the present invention is as follows.

(1) A raw material containing one or two of a sulfur-containing carbonaceous material and a sulfur-containing hydrocarbon-based material, copper
A mixed gas of hydrogen and carbon monoxide containing no sulfur by fixing sulfur in the metal bath by treating it with a high temperature metal bath containing 0% or more and less than 50% iron, and decomposing and gasifying it. A gasification treatment method characterized by producing a rich gas or a carbon monoxide rich gas.

(2) While introducing a raw material containing one or two of a sulfur-containing carbonaceous material and a sulfur-containing hydrocarbon-based material into a high temperature metal bath, an oxidizing agent is blown into the raw material to add sulfur-free carbon monoxide. The gasification treatment method according to (1) above, wherein a mixed gas of hydrogen is generated.

(3) A raw material containing one or two of a sulfur-containing carbonaceous material and a sulfur-containing hydrocarbon-based material is charged into a high temperature metal bath to generate a hydrogen-rich gas containing no sulfur, and then an oxidizer is added. Is injected to generate a carbon monoxide rich gas. The gasification treatment method according to (1) above.

(4) The above-mentioned (1) to (1), wherein two or more container-type reaction furnaces are used to perform gasification operation and to perform discharge and collection of mats alternately by stopping the gasification operation.
The gasification treatment method according to any one of (3).

(5) Any of the above (1) to (4), characterized in that the mat in which the sulfur in the raw material is fixed as a sulfide is recovered, oxidized to remove and recover the sulfur, and the metal is regenerated. The gasification treatment method according to.

(6) When the amount of matte produced by the reaction between sulfur in the raw materials charged during the operation and copper in the metal bath increases, the matte is removed and the matte is oxidized with air or oxygen. The gasification treatment method according to any one of (1) to (5) above, which comprises a step of removing and recovering sulfur to regenerate copper, and returning copper to a metal bath for use.

(7) Using a continuous furnace, a raw material containing one or two of a sulfur-containing carbon-based material and a sulfur-containing hydrocarbon-based material is charged into a high temperature metal bath flow in the first half of the furnace to decompose the same. The generated hydrogen-rich gas is recovered, after which the oxidizer is injected into the metal bath flow in the latter half of the furnace, and the carbon dissolved in the metal bath flow is gasified in the first half to recover the carbon monoxide-rich gas, The formed mat is removed from the metal bath flow in the final part of the furnace, and the metal bath flow whose carbon temperature has dropped and whose temperature has risen is circulated by stirring with an electromagnetic pump or the like (1) above The gasification treatment method according to.

(8) The gasification method according to any one of (1) to (7) above, wherein the oxidizing agent is one or more of oxygen, water vapor and carbon dioxide.

(9) Contains 50% or more of copper and 50% of iron
The metal bath containing less than M is a metal having a solubility of carbon
The gasification treatment method according to any one of (1) to (8) above, which is a metal bath containing one or more of n, Cr, Ni, and Mo.

(10) The gasification treatment method according to any one of (1) to (9) above, wherein the temperature of the metal bath is 1450 ° C. or higher.

(11) The raw material is a sulfur-containing carbonaceous material such as coal, coke, petroleum coke, petroleum distillation residue, heavy oil, heavy oil residue, asphalt pitch, slurry oil, extraction residue, or the waste thereof, or The gasification treatment method according to any one of (1) to (10) above, which is various sulfur-containing hydrocarbon materials such as tires and tire scraps and wastes thereof.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The operation method using the metal bath gasification technique of the present invention is constituted by the following metal bath basic techniques.

A mixed metal bath of 50% or more copper and the balance iron is used. Other metals having high carbon solubility may be mixed with iron.

Operate in a high temperature molten metal bath at 1450 ° C. or higher.

Without using external heating or other fuel other than the high temperature metal bath, sulfur-containing carbon and hydrogen-based materials are decomposed to recover concentrated hydrogen containing no sulfur, or waste is decomposed to be harmless. In addition, sulfur is recovered from the mats and the like recovered as sulfides for effective use, and metallic copper is regenerated.

The use of the metal bath of the present invention significantly expands the range of use of the raw material to be treated, and the basic technique of such a metal bath that has a small influence of the raw material on gasification productivity is as follows. It was invented based on the idea.

A) Viscosity of the metal bath is remarkably lowered by increasing the proportion of copper of 50% or more and iron of less than 50%, and increasing the ratio of copper to iron and the temperature of the bath higher than ever, Dispersion of the oxidizer blown into the bath and stirring of the bath are very good. Since the viscosity of copper at high temperature is less than half that of iron containing carbon, an extremely large stirring effect can be obtained. As a result, the blowout of the oxidant is eliminated, the reaction between the oxidant and the dissolved carbon rapidly progresses, and the gasification efficiency increases. Since the reaction efficiency is improved and the temperature is high, the CO / CO ₂ ratio is increased and the injection pressure of the gas that is the oxidant can be lowered.

B) Sulfur of the carbonaceous material charged by containing copper is immediately fixed to copper, and the sulfur percentage of the iron bath can be suppressed to an extremely low level. Therefore, since the carbon solubility due to sulfur in the iron bath does not decrease, the gasification rate can be maintained high. A high copper content of 50% or more enhances the fixation of sulfur and enables the production of fuel gas containing no sulfur. Also,
Since the sulfur storage capacity of the bath increases, long-term operation is possible even with the use of a carbon material having a high sulfur content, and productivity is not reduced. Even if the ratio of iron decreases, increasing the capacity of the reactor can maintain operating efficiency and gasification productivity.

C) A large proportion of copper also suppresses the oxidation of iron due to the addition of an oxidant, eliminating the risk of damage to the refractory due to the formation of iron oxide, and the formation of oxides. It also prevents wear of the oxidant blowing lance. Therefore, although the content of copper in the metal bath is set to 50% or more in the present invention, it is preferably 55% or more. It should be noted that if the carbon content of the iron bath is maintained at about 1% or more, it can be said that iron oxide is not formed regardless of the bath mixing conditions.

D) Decomposition of carbonaceous materials and hydrocarbon-based materials for obtaining hydrogen and decomposition of wastes require that the metal bath be heated to a high temperature and charged, but the carbon in the bath should be removed without external heating. The temperature of the bath can be raised by burning with an oxidant. At this time, a high copper ratio enables rapid heating in a shorter time.

E) By using a high temperature bath even when the ratio of iron is lowered, the dissolution rate of carbon and the reaction rate of gasification are increased and the productivity of gasification is rather improved.

F) In order to obtain a carbon monoxide rich gas that does not contain sulfur after decomposing carbonaceous materials, hydrocarbon materials and wastes in a high temperature bath at 1450 ° C. or higher, it is necessary to generate carbon monoxide rich gas before adding an oxidizing agent such as oxygen. It is necessary to remove the mat that has been removed. Since mats are rich in copper and have good separability from the iron phase of high charcoal, the carbon in iron is increased to remove the mat, and an oxidizing agent is blown into it to burn the carbon, resulting in high temperatures. Since there is sufficient carbon, the operation will be performed under preferable conditions. That is, carbon monoxide gas cannot be generated unless carbon is dissolved in the metal bath. To this end, 5 iron that can dissolve carbon in the metal bath is used.
It should be less than 0%. In addition, M having carbon solubility
Even if one or more of n, Cr, Ni, and Mo are replaced with iron in a total amount of 20% or less, the same effect is obtained.

G) Conventionally, it has been said that there is a problem with refractory materials in order to operate at high temperature in such a reactor, but recently, very good refractory materials have been developed, and 145
It can be said that there is no problem with refractories at high temperatures of about 0 ° C. In particular, as described above, the production of iron oxide slag is suppressed due to the metal bath mainly containing copper, which is an advantageous method for refractories.

The following various operations can be performed using such a metal bath as a medium.

Sulfur-containing carbonaceous material, sulfur-containing hydrocarbon-based material, and one or two kinds of waste containing these materials
Perform continuous gasification operation by continuously feeding more than one raw material and oxidizer. However, if mats increase during long-term operation, the operation is interrupted, the mats are removed, sulfur is recovered, and copper is regenerated. In this sense, it can be said to be an intermittent operation.

The metal bath is heated to a high temperature and the above-mentioned raw materials of hydrogen-containing and carbon are charged and decomposed to obtain a hydrogen-rich gas. Carbon dissolves in iron in a metal bath. When the carbon in the metal bath approaches saturation, an oxidant is blown into the bath to gasify the dissolved carbon and produce a concentrated CO gas. As the mats increase, the mats are treated intermittently.

It is preferable that a carbonaceous material and an oxidizing agent are charged into a high-temperature metal bath, the temperature of the bath is raised by heat generated by gasification, and then waste is charged to decompose the same. Depending on the content of waste, the produced gas is recovered as fuel. When the temperature of the bath falls to some extent, the carbonaceous material is burned again to raise the temperature of the bath. Remove mats and slag intermittently.

The above is the intermittent operation using the container type reactor, but the following three operations can be continuously performed by using the following continuous operation furnace.

Continuous operation method In a gutter-shaped or donut-shaped circular furnace, one or more raw materials of a sulfur-containing carbonaceous material or a sulfur-containing hydrocarbon material, and waste containing these materials in a metal bath flowing from one side At the same time, the top blowing lances are installed at several places in the flow path to inject the oxidizer to gasify the raw materials. The product gas is collected by the cover on the furnace. A matte or slag is gradually formed on the metal bath, which is separated from the metal bath by a weir at the end of the furnace. The metal bath is circulated by a stirring device such as an electromagnetic pump and returned to the beginning of the furnace. When the concentrated hydrogen is separately recovered, the furnace may be divided into the first half and the second half, only the raw materials may be charged in the first half, and the oxidizer may be injected in the latter half to gasify the carbon. The gas is separated and collected with the upper cover separate. The gasification rate is controlled by the feed rate of the raw materials and the flow rate of the metal bath.

As described above, the present invention is an excellent process capable of treating various materials and performing various operations in a very simple facility to obtain various useful gases and detoxify wastes. is there.

The present invention will be described below with reference to the drawings.

FIG. 1 is a diagram showing an example of an apparatus for carrying out an intermittent operation of the gasification process of the present invention. In FIG. 1, reference numeral 1 is a reactor or a reaction furnace that holds a metal bath 6, and a generated gas discharge pipe 2 for discharging generated or generated gas is connected to the upper part. The reaction furnace 1 is tilted by the tilting device 5 so that the metal bath 6 inside is tilted to the furnace opening 3
Can be discharged from. Further, a discharge hole 4 which can also discharge the metal bath 6 is attached to the bottom of the furnace. The reaction furnace 1 is constructed by lining a refractory material in a steel container, and an oxygen top-blown or bottom-blown converter used in steel refining in the steel industry can be appropriately modified and used.

At the start of operation, 145
A metal bath 6 having a temperature of 0 ° C. or higher is prepared. The bath is mainly a copper-iron mixed bath in which the proportion of copper is higher than that of iron, but other metals having high carbon solubility (Mn, Cr, Ni, Mo, one or two).
It is also possible to mix more than one kind). Numeral 7 is a mat or slag layer, but it is not a mat at the start of operation, but is a mat mainly composed of Cu ₂ S which is produced by the reaction of sulfur from raw materials introduced with copper over time, or waste. Examples include slag generated by processing. It is discharged from the furnace once it has accumulated to some extent.

In the gasification operation, the raw material is fed into the upper lance 8
And by injecting the oxidizer into the metal bath from one or two of the bottom tuyeres 8'and from the top lance 9 and one or two of the bottom tuyeres 9 '. Is continuously performed. When the oxidant is oxygen, when jetting from the tuyere 9'on the bottom of the furnace, the tuyere is made into a double pipe 10 so that the reaction heat at the injection destination does not damage the pipe, and the hydrocarbon gas 12 is supplied from the outside.
It is desirable to blow it in to cool it. Reference numeral 11 is an oxidizer holder. Reference numeral 13 is a raw material (including waste) storage tank, and it is preferable to provide various facilities depending on the form of the raw material. Raw materials are supplied from reservoir 13 to supply path 14 and supply path 15
It is preferable to carry it by means of the upper charging lance 8 and the tuyere 8'on the bottom of the furnace to continuously charge the furnace.

In the case of hydrogen recovery or waste treatment, the raw materials are put into the heated metal bath from the upper feeding lance 8 and hydrogen or an inert gas is blown from the tuyere 16 at the bottom of the furnace to stir the bath. Decomposes or dissolves raw materials. At this time, the oxidizer is not injected. High-concentration hydrogen gas is generated by decomposition or dissolution, and is recovered from the generated gas discharge pipe 2. After a certain amount of treatment, the temperature of the bath will drop as the carbon in the bath approaches saturation.Therefore, end the input of raw materials and inject the oxidizer to gasify the carbon dissolved in iron in the metal bath. Lower the carbon and raise the bath temperature. In the case of waste, depending on the form, it is necessary to make the input pipe in the upper part larger and to facilitate transportation. Further, in the above example, the intermittent operation of one reactor was explained, but if two or more reactors are installed for gasification operation, continuous gasification operation is possible while switching the furnaces. Therefore, efficient gasification treatment can be carried out.

Next, the continuous operation method of gasification treatment of the present invention will be described with reference to FIG.

FIG. 2 is a diagram showing an example of an apparatus for carrying out continuous operation of gasification treatment of the present invention. As shown in FIG.
A donut-shaped circular furnace 17 is used as a reaction container. The cross section of the circular furnace is lined with refractory as a rectangle or a rectangle with a slightly rounded bottom and is designed to allow the metal bath to have some depth.

A separation weir 18 that divides the furnace into two is provided, the operation starts from one side 19 of the weir, and the metal bath 20 flows as shown by the arrow. At the end of the operation 21 opposite the weir 18,
The metal bath is transported to the operation start side by the electromagnetic pump 22. The operating speed is determined by the flow velocity of the metal bath 20, which is the pump 2
Controlled at a transport rate of 2. The mat or slag 23 formed on the metal stream 20 is stopped by the stopper 24 and removed from the outlet 25. Stopper 24 for metal bath
It is circulated by a flow pump through the bottom to the reservoir 26 between the weir 18.

Although not shown in the figure, a cover capable of sealing the furnace is installed above the metal flow. The cover is bisected by a furnace divider 27, the front half 28 is sealed by a cover 29 and the rear half 30 is sealed by a cover 31. The division of the furnace is necessary when collecting concentrated hydrogen separately, and the division ratio is designed according to the amount of hydrogen generated.

The sulfur-containing carbonaceous material to be gasified, the sulfur-containing hydrocarbon material, and one or more raw materials of the waste containing them are fed from the raw material charging hopper 32 through a supply pipe, It is charged into the metal stream from the charging port 33 such as a charging lance. The figure shows two charging ports, but any number may be installed depending on the operation. The oxidizer is blown into the metal stream from the oxidizer holder 34 by a jet lance 35. One or more oxidant injection lances are installed through the cover. Although the figure shows that the lance is installed only in the latter half of the furnace, it may also be installed in the first half depending on the operation method. Oxidizer is oxygen and water vapor 2
For types, use separate lances or use double pipe lances.

The generated gas is stored in the gas holder 37 through the gas discharge port 36 in the first half portion 28. The gas in the latter half portion 30 is collected by the cover and stored in the gas holder 39 through the discharge port 38. The gas is sucked by the blowers 40 and 41 as needed. The equipment shown in the figure is an example where hydrogen gas is collected separately, but in the case where all raw materials are gasified, an oxidizer injection lance is also installed in the first half of the furnace, and the generated gas is put together in a gas holder. Can be sent.

The discharged mat is treated separately and the copper bath regenerated after recovering SO ₂ is returned to the reservoir 26 so that the total amount of metal flow does not change.

The furnace is provided with a measuring device 42 for temperature measurement, carbon analysis of a metal bath, etc., and a gas analyzer 43 at appropriate positions, which are used for controlling the operation.

The raw materials used are coal, coke, petroleum coke, petroleum distillation residue, heavy oil, heavy oil residue, asphalt pitch, slurry oil, extraction residue, other hydrocarbon-containing substances, various wastes, Tires, waste, industrial waste, and so on.

[0061]

[Examples] Various operations will be described below with reference to Examples.

(Example 1) An example of gasifying a sulfur-containing carbonaceous material will be described.

An example of gasification operation using 8% sulfur petroleum coke as the sulfur-containing carbonaceous material will be shown. In the conventional method, the sulfur content such as H ₂ S in the produced gas becomes so high that the desulfurization of the gas is required, but in the present invention, the gasification treatment can be easily performed without performing the desulfurization treatment. A metal bath containing 55% copper and 45% iron, which was heated to 1500 ° C or higher, was prepared in a converter-type gasifier, and the ratio of carbon to oxygen was 1 in terms of chemical equivalent ratio.
Blow in the amount of petroleum coke and oxygen calculated to be. As the petroleum coke, a large lump was crushed before being blown and the particle size was adjusted to about 2 mm or less. Oxygen was jetted from the top of the furnace with a lance directly above the metal bath at a speed of about 100 m / sec. Lance is placed so as not to soak in the bath,
A stream of oxygen gas penetrated deeply into the bath to agitate the bath. Petroleum coke was sprayed with carbon dioxide as a carrier from the tuyere at the bottom of the furnace to enhance the dissolution. The amount of carbon dioxide gas required for blowing is small, and CO gas is generated by its decomposition, and it also has the role of cooling the bath.

At the stage of preparing the metal bath, petroleum coke and oxygen equivalent to gasify it into CO were injected into the metal bath in which the carbon content in the portion corresponding to the iron bath was less than 3% to inject the carbon content. Continued to operate so that the temperature did not change significantly. The temperature of the metal bath and the carbon content of the metal bath were measured or sampled at regular time intervals and analyzed and understood. Since a relatively small furnace was used in this operation test, there was little change in the temperature of the metal bath due to the balance between gasification heat generation and heat loss. Is expected to increase, it is necessary to adjust the temperature of the metal bath by blowing in steam. This can increase the proportion of hydrogen in the produced gas.

The analytical value of the obtained product gas is CO: 7
_{2.3%, H 2: 24.6%} , CO 2: 2.8%, N 2:
It was 0.3%. The amounts of H ₂ S and COS were 50 ppm or less, which was good enough to eliminate the need for gas desulfurization.

While continuing continuous operation in a steady state, depending on the amount of the metal bath, in this test, after about 1 hour, the sulfur of the petroleum coke charged was combined with copper to form Cu.
The amount of so-called slag, which is called a matte containing ₂ S as a main component, increases, and about half of the copper becomes a matte, which accounts for 25% of the total.
Has started to occupy as much capacity. Since gas desulfurization decreases when the amount becomes too large, the operation was stopped, a mat having a specific gravity lower than that of the metal was floated on the surface, and the furnace was tilted from the metal bath of the main body to discharge only the mat. The mat at this temperature had sufficient fluidity that it could easily be transferred to another ladle. When air is blown into the mat transferred to the ladle to oxidize sulfur in the mat to generate SO ₂ gas, copper is regenerated and returned to the reaction furnace for use. In this example, SO ₂ gas was discarded, but in industrialization, sulfuric acid can be produced from this and all sulfur can be used.

After the mat is removed and the copper is regenerated, the gasification operation is restarted. In this example, the operation was carried out intermittently, but in industrialization, if two or more reaction furnaces are provided, it is possible to carry out continuous gasification operation while switching the furnaces.

(Example 2) An example of an operation in which hydrogen recovery and gasification are combined will be described. In the operation of Example 1, both the carbon and hydrogen components of petroleum coke were gasified, but the petroleum coke contained hydrogen in a mass of about 3%, and it was considerably separated if recovered. The gas with high hydrogen concentration is recovered and can be used for various purposes.

The components of the metal bath used are the same as in Example 1. When removing the mat from the reaction furnace, the temperature of the metal bath dropped somewhat, so oxygen was blown in to raise the temperature of the metal bath to about 1550 ° C. In this work, the carbon content of petroleum coke is dissolved in iron in the metal bath to increase the carbon percentage, so it is possible to lower the carbon percentage of the metal bath in advance in order to allow a certain amount of carbon dissolution margin. This is one of the purposes. Except for the mat, when entering the hydrogen recovery operation as it is,
This is because hydrogen may react with sulfur to generate H ₂ S gas and reduce the concentration of hydrogen gas. In this way
When only petroleum coke is added to the high temperature metal bath,
Hydrogen-containing components of petroleum coke are thermally decomposed to generate hydrogen. If this was continued, the temperature of the metal bath decreased due to the heat of decomposition, and the decomposition ability decreased, so the hydrogen recovery operation was stopped when the temperature reached about 1450 ° C. The time for the hydrogen recovery operation depends on the hydrogen content of the carbonaceous material, the temperature of the metal bath, and the carbon content of the iron bath. When the hydrogen gas recovery was completed, the carbon content of the petroleum coke was dissolved in the iron bath, and the carbon content of the iron bath had risen to near saturation. Therefore, gasification work was performed again. This operation is the same as in Example 1. This work can be carried out by incorporating it into the gasification work at various timings according to the required amount of hydrogen recovery.

(Example 3) An example of operation in which waste treatment and gasification are combined will be described. In this example, an artificial waste was prepared by mixing wastes such as plastics, rubber, wood, sulfur-containing heavy oil residue, electric furnace dust, etc., and crushed to a certain size and used. These wastes contain sulfur, dioxins, metals, organic substances and the like, and it is difficult to detoxify them by ordinary methods. Using a metal bath having the same components as in Example 2, the metal bath was heated by the same method, and then the waste was continuously added to dissolve and decompose the waste.

Waste is completely dissolved, dioxins and organic substances are decomposed, metals are dissolved, sulfur is captured by copper,
The inorganic content was made harmless as a whole by slaging. In this operation test, the generated gas was burned in the furnace, but it can be recovered and used as a low-grade fuel gas depending on the content of the waste.
With continuous input of waste, the temperature of the bath gradually decreased, and 1450
When the temperature reached ℃, the charging was stopped, the temperature of the bath was raised again by the normal gasification operation, and the above operation was repeated when the temperature of the bath reached 1550 ° C. As a result, it was confirmed that various wastes can be easily treated. If it is a normal waste treatment, it is good to discharge slag or mat from time to time,
Although a small amount of other metal is dissolved in the metal bath, the function of the bath is not hindered. During operation, the carbon content of the bath is 2-3
% Was maintained, but this decreases with heating of the bath and increases with dissolution of carbon from waste, so analyze the bath appropriately, and if there is a large fluctuation, oxygen injection or other charcoal. This is the result of adjusting the addition of wood.

(Example 4) An example of recovery of concentrated hydrogen by continuous operation will be described. In the test, a gutter type furnace was used. The furnace was tilted slightly to allow the metal bath to flow slowly. 55 heated to 1550 ° C from above gutter
A high temperature metal bath mixed with a ratio of 45% copper and 45% iron is charged, flows downward in the gutter, and is received by a pan from an outlet. Coal dust was injected into the metal bath from the vicinity of the charging side of the gutter with a lance and argon was used as a carrier gas. A high volatile coal containing 1.2% sulfur was used in the test.

A cover for catching the generated gas is installed over the entire gutter, and a cover is provided in the middle part of the gutter so that the gas in the first half and the latter half of the gutter can be separately captured. It is separated. Before the test, the dissolution test of the coal used was carried out to understand the hydrogen gas generation time and amount, and the division ratio of the cover was adjusted beforehand accordingly. In this test, about one-third of the first half was the hydrogen recovery part, and the rest was the CO gas recovery part.

The coal powder charged in the high temperature metal bath is decomposed / dissolved in the first half, hydrogen-rich gas is generated, carbon is dissolved in iron, and sulfur is fixed in copper. Initially, a metal bath having a carbon content of about 2% was charged, but the addition of coal increased the carbon content to about 4%. The temperature of the metal bath is 14
It dropped to 60 ° C. The generated hydrogen gas was collected by the cover of this part and collected in the holder.

The metal bath then flowed to the latter part of the cover where oxygen gas was injected into the metal bath from five lances spaced at some distance. Carbon dissolved in iron was oxidized to generate CO gas. The gas was collected by the top cover and sent to the holder. The carbon content of the metal bath dropped to around 2% and the temperature rose to 1550 ° C. This time it was received in a pan, but in the actual machine you can circulate the metal bath. There was little copper sulfide matte and slag because the sulfur content in the coal was low, but
Separated and analyzed at the outlet of the gutter.

As a result of gas analysis, no sulfur compound was detected in all the gases, and the effect of the bath mixed with copper was recognized. The first half gas is 85% hydrogen and the rest is argon etc., and the latter half gas is 84% CO, 4% CO ₂ , 0.5% H ₂ etc.
An O-rich gas was obtained. The gas could be continuously and separately recovered.

[0077]

According to the present invention, a sulfur-containing carbonaceous material,
Sulfur-containing hydrocarbon materials and wastes containing these materials can be gasified without using a complicated desulfurization process, and the gasification can be efficiently performed. Further, when treating the waste, even if dioxin, PCB, etc. are contained, they can be detoxified and the contained sulfur can be recovered and effectively used. is there. In the conventional method, the sulfur content such as H ₂ S in the produced gas becomes so high that desulfurization of the gas is required, but in the present invention, gasification can be easily performed.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a reactor used in an intermittent operation.

FIG. 2 is a diagram showing an example of a reactor used in continuous operation.

[Explanation of symbols]

1 Reactor 2 generated gas exhaust pipe 3 furnace mouth 4 discharge holes 5 Tilt device 6 metal bath 7 Matt slag layer 8 Lance 8'tuyere 9 Lance 9'tuyere 10 double pipe 11 oxidizer holder 12 hydrocarbon gas 13 storage tanks 14 Supply path 15 supply path 16 tuyere 17 circular furnace 18 Separation weir 19 One side of weir 20 metal bath 21 Opposite side of weir 22 Electromagnetic pump 23 Matt or slag 24 stopper 25 outlet 26 Reservoir Separation of 27 furnaces 28 First half 29 cover 30 Second half 31 cover 32 Raw material charging hopper 33 booth 34 Oxidizer holder 35 injection lance 36 Gas outlet 37 gas holder 38 Gas outlet 39 gas holder 40, 41 blower 42 Measuring instrument 43 gas analyzer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yasuhito Shimomura             1-6 Kojimachi, Chiyoda-ku, Tokyo Nittetsu Co., Ltd.             Inside the Technical Information Center F-term (reference) 4G140 EA01 EA04 EA05 EB01 EB13                 4G146 JA01 JB08 JC03

Claims (11)

[Claims] 1. A raw material containing one or two of a sulfur-containing carbonaceous material and a sulfur-containing hydrocarbon-based material is treated with a high temperature metal bath containing 50% or more of copper and less than 50% of iron to decompose the raw material.・ A gas mixture of carbon monoxide and hydrogen that does not contain sulfur by gasifying and fixing sulfur in a metal bath,
A gasification treatment method characterized by producing a hydrogen-rich gas or a carbon monoxide-rich gas. 2. Carbon monoxide and hydrogen containing no sulfur content by blowing an oxidizing agent while introducing a raw material containing one or two kinds of a carbon material containing sulfur and a hydrocarbon material containing sulfur into a high temperature metal bath. The gasification treatment method according to claim 1, wherein the mixed gas of (1) is generated. 3. A high temperature metal bath is charged with a raw material containing one or two of a sulfur-containing carbonaceous material and a sulfur-containing hydrocarbon-based material to generate a hydrogen-rich gas containing no sulfur, and then an oxidizer is added. The gasification treatment method according to claim 1, wherein the carbon monoxide rich gas is generated by injection. 4. The gasification operation using two or more container type reactors, and the matting discharge collection is alternately performed by stopping the gasification operation. The gasification treatment method according to any one of claims. 5. A mat in which sulfur in a raw material is fixed as a sulfide is separated and recovered from a metal bath, oxidized to remove and recover sulfur, and metal is regenerated. The gasification treatment method according to. 6. The mat is removed and oxidized with air or oxygen when the amount of mat produced by the reaction of sulfur in the raw materials charged during operation with copper in the metal bath increases. The gasification treatment method according to any one of claims 1 to 5, comprising a step of removing and recovering sulfur, regenerating copper, and returning the copper to a metal bath for use. 7. A continuous furnace is used to introduce raw materials containing one or two of a sulfur-containing carbon-based material and a sulfur-containing hydrocarbon-based material into a high temperature metal bath flow in the first half of the furnace to cause decomposition. To recover the hydrogen-rich gas, and then to inject the oxidizer into the metal bath flow in the latter half of the furnace to gasify the carbon dissolved in the metal bath flow in the first half to recover the carbon monoxide-rich gas. The matte is removed from the metal bath stream in the final part of the furnace, and the metal bath stream whose carbon temperature has dropped and whose temperature has risen is circulated by a stirring device such as an electromagnetic pump. The gasification treatment method described. 8. The oxidizer is one or more of oxygen, water vapor and carbon dioxide, and is characterized in that.
The gasification treatment method according to any one of 1. 9. A metal bath containing 50% or more of copper and less than 50% of iron is a metal having a solubility of carbon, that is, Mn and C.
The gasification treatment method according to any one of claims 1 to 8, which is a metal bath containing one or more of r, Ni, and Mo. 10. The gasification treatment method according to claim 1, wherein the temperature of the metal bath is 1450 ° C. or higher. 11. A raw material is a sulfur-containing carbonaceous material such as coal, coke, petroleum coke, petroleum distillation residue, heavy oil, heavy oil residue, asphalt pitch, slurry oil and extraction residue, or a waste thereof, or a tire. 11. A gasification treatment method according to any one of claims 1 to 10, which is various sulfur-containing hydrocarbon materials such as tire scraps and wastes thereof.