JP2013173878A - Method for converting organic substance into profitable material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a reformed product containing a large amount of light content while containing less amounts of heavy content and carbonaceous content, by efficiently reforming organic substances into low-molecular substances using stably available gas, when converting organic substances into low-molecular substances of gas products, liquid products or the like; and to make efficient use of solid residues generated in the molecular reduction reaction.SOLUTION: A method comprises steps of: adding excess steam to exhaust gas (g) containing carbon monoxide generated in a metallurgical furnace to perform a shift reaction; producing a mixed gas (g) including hydrogen and carbon dioxide generated in the shift reaction and steam not consumed in the shift reaction; bringing this mixed gas (g) into contact with an organic substance to cause a reaction of reforming the organic substance into low-molecular substances; recovering a low-molecular reformed product of the organic substance and a solid-state residue generated by the reaction; and utilizing the solid-state residue as a carbon material.

Description

  The present invention relates to a method for making an organic material that efficiently uses a solid residue generated by a low molecular weight reaction while modifying a low molecular weight material by modifying an organic material such as waste plastic.

In integrated steelworks, coke is used in large quantities as a reducing agent for iron ore, and coke is also used as a coagulant for iron ore sintering machines. On the other hand, a large amount of coke oven gas is generated from the coke oven that produces coke, and a large amount of blast furnace gas is also generated from the blast furnace that reduces iron ore with coke. It is used as a reducing agent.
In recent years, carbon sources other than coal, such as LNG, have come to be used as part of fuels and reducing agents at steelworks due to social demands for reducing carbon dioxide emissions and soaring coking coal. . However, in order to further reduce carbon dioxide emissions, it is required to reduce the dependence on fossil fuels such as LNG.

By the way, the present situation is that most of waste plastic, oil-containing sludge, waste oil, biomass and the like are incinerated. However, the incineration process has a high environmental load such as CO ₂ generation, and there is a problem of thermal damage of the incinerator, so that establishment of chemical recycling technology is required.
Among the chemical recycling technologies, technologies for converting an organic substance into a gas product or a liquid product have been variously studied mainly on waste plastics. For example, the following proposals have been made.

In Patent Document 1, a coke oven gas (COG) having a hydrogen concentration of 60 vol% or more, preferably 80 vol% or more and a temperature of 600 ° C or more is reacted with an organic material such as waste plastic, thereby hydrogenating the organic material with high efficiency. A method for increasing the heat of COG by decomposition and gasification is disclosed.
Further, Patent Document 2 discloses a method in which petroleum fluid contact catalyst (FCC) is used as a heat medium / catalyst and waste plastic is decomposed at a temperature of 350 to 500 ° C. to be converted into liquid fuel.
Further, in Patent Document 3, when pyrolyzing RDF, wood, etc., the gas generated by pyrolysis is steam reformed, and the gas having a high hydrogen concentration by this steam reforming is circulated to the pyrolysis section to generate hydrogen. A method of performing pyrolysis in a gas atmosphere with a high concentration is disclosed.

JP 2007-224206 A JP 2010-013657 A JP 2001-131560 A

However, the above prior art has the following problems.
First, regarding Patent Document 1, since the hydrogen concentration in COG is 60 vol% or more is limited to the end of the dry distillation in the coal dry distillation process, in the method of Patent Document 1, the gas flow path is opened at the end of the dry distillation. It is necessary to switch and supply COG of 600 ° C. or more containing a large amount of dust to a waste plastic hydrocracking reactor. However, it is difficult to stably operate the flow path switching valve for a long time under such a severe condition, and in this sense, it can be said that the technique is poor in feasibility. Furthermore, for efficient gasification of waste plastic, it is necessary to continuously supply COG containing 60 vol% or more of hydrogen to the hydrocracking reactor. In addition, it is necessary to install a hydrogen concentration meter and a flow path switching valve, which increases the equipment cost.

Moreover, although the method of patent document 2 advances catalytic cracking and aromatization by addition of an FCC catalyst, since it reacts by an inert gas flow, 13 mass% of heavy oil components and coke are produced | generated in total. (Example 1) It cannot be said that it is a satisfactory level as a light fuel production technology.
Further, the gas generated by the method of Patent Document 3 is mainly H ₂ , CO, and CO ₂ , and the combustion heat is about 1800 kcal / Nm ³ that is slightly lower than that of the exhaust gas generated from the metallurgical furnace. The value is limited.
Furthermore, it is difficult to completely suppress the formation of a solid residue when decomposing a high molecular weight organic substance such as waste plastic to convert it into a gas product or a liquid product. However, at present, there are few known methods for effectively utilizing the solid residue.

  Accordingly, the object of the present invention is to efficiently reform organic substances using gases that can be stably supplied when converting organic substances such as waste plastics into gas products or liquid products by reducing the molecular weight. Organic substances that can be reduced in molecular weight, have a heavy or carbonaceous content, and can be modified to contain a large amount of light components, and can effectively use the solid residue generated in the molecular weight reduction reaction It is to provide a method for making a profit.

  As a result of repeated studies to solve the above-mentioned problems, the inventors of the present invention added an excessive water vapor to an exhaust gas containing carbon monoxide generated in a metallurgical furnace to cause a shift reaction, and a gas after the shift reaction. In other words, according to the method of reforming a high molecular weight organic substance and reducing the molecular weight using a mixed gas containing hydrogen and carbon dioxide generated by the shift reaction and the remaining water vapor, a gas that can be supplied stably can be obtained. It can be used to efficiently modify organic substances to lower the molecular weight, resulting in a modified product containing less heavy and carbon, and containing a large amount of lighter components, and solids generated by the lowering reaction. It has been found that the residue can be effectively used as a carbon material in a manufacturing or processing process performed at a steel mill or the like. In addition, when organic substances are reformed in the presence of an iron-based catalyst, the solid residue produced by the low molecular weight reaction is converted into carbon containing an iron source in a production or treatment process performed at a steel mill or the like. We found that it can be used effectively as a material.

The present invention has been made on the basis of such findings and has the following gist.
[1] Addition of excess water vapor to the exhaust gas (g ₀ ) containing carbon monoxide generated in the metallurgical furnace to cause the shift reaction to consume the hydrogen and carbon dioxide generated by the shift reaction and the shift reaction A mixed gas (g) containing water vapor that has not been produced is brought into contact with the organic substance to cause a reaction to modify the organic substance to reduce the molecular weight, and the reaction is caused by the reaction. A method for producing a material for an organic material, comprising recovering a low molecular weight modified product of the organic material and a solid residue, and using the solid residue as a carbon material.

[2] Addition of excess water vapor to the exhaust gas (g ₀ ) containing carbon monoxide generated in the metallurgical furnace to cause the shift reaction, and hydrogen and carbon dioxide generated by the shift reaction are consumed for the shift reaction. A mixed gas (g) containing water vapor that has not been produced is brought into contact with an organic substance in the presence of an iron-based catalyst, thereby causing a reaction that modifies the organic substance to lower its molecular weight. And recovering a low molecular weight modified product and a solid residue of the organic substance generated by the reaction, and using the solid residue as a carbon material containing an iron source. Method.
[3] A method for making an organic material into use in the method of [2] above, wherein the iron-based catalyst is converter dust.

[4] In any one of the above methods [1] to [3], the exhaust gas (g ₀ ) separates at least a part of nitrogen from the exhaust gas containing carbon monoxide and nitrogen generated in the metallurgical furnace. A method for converting an organic substance into a material, characterized in that the exhaust gas has an increased carbon monoxide concentration.
[5] A method for producing an organic material, wherein the mixed gas (g) has a water vapor concentration of 5 to 70 vol% in any of the methods [1] to [4].
[6] In the method of [5] above, the mixed gas (g) is characterized in that the water vapor concentration is 20 to 70 vol%, the hydrogen concentration is 10 to 40 vol%, and the carbon dioxide concentration is 10 to 40 vol%. How to make a material profitable.
[7] The method according to any one of [1] to [6] above, wherein the organic substance to be modified is at least one selected from waste plastic, oil-containing sludge, waste oil, and biomass. How to make organic materials.

[8] In the method according to any one of the above [1] to [7], the solid residue is used as a carbon material in a production or treatment process performed at a steel mill, .
[9] In the method of [8] above, the production or treatment process performed at the steel mill is one or more of a sintered ore production process, a coke production process, a converter decarburization process, and a blast furnace process. A method for converting an organic material into a material.
[10] The organic material according to any one of the above [1] to [9], wherein the low molecular weight reformed product of the recovered organic material is used as a fuel and / or a reducing agent in an ironworks. How to make a profit.
[11] A method for producing an organic material that is characterized in that, in the method of [10], the recovered low molecular weight modified product of the organic material is blown into a blast furnace.

According to the present invention, when a high molecular weight organic substance such as waste plastic is reduced in molecular weight and converted into a gas product or a liquid product, the organic substance is efficiently modified using a gas that can be stably supplied. As a result, it is possible to obtain a high-calorie modified product containing a large amount of light components by reducing the molecular weight, and a small amount of solid residue generated as a carbon material or as a carbon material containing an iron source, It can be effectively used in manufacturing or processing processes performed at steelworks or the like. For this reason, it is possible to chemically recycle high molecular weight organic substances such as waste plastics without emission.
Also, with regard to the implementation equipment, there is no need for special measuring instruments or flow path switching valves, and the organic substance can be reformed even at a relatively low reaction temperature. it can. In addition, since CO ₂ produced by the shift reaction changes to CO during the reforming of the organic material, it is possible to carry out chemical recycling of the organic material without increasing the amount of CO ₂ generated. It becomes.

In the shift reaction performed by adding water vapor to the converter gas, a graph showing the relationship between the amount of water vapor added and the composition of the gas after the shift reaction (calculated equilibrium composition at a temperature of 430 ° C.) In an Example, the graph which shows the relationship between the water vapor | steam density | concentration of shift reaction product gas, and the gasification rate and liquefaction rate in the modification | reformation (low molecular weight) of polyethylene In an Example, the graph which shows the relationship between the water vapor | steam density | concentration of a shift reaction product gas, and LHV of the gas product obtained by the modification | reformation (low molecular weight reduction) of polyethylene. In an Example, the graph which shows the relationship between the water vapor | steam density | concentration of shift reaction product gas, and the polyethylene decomposition rate in the modification | reformation (low molecular weight) of polyethylene In an Example, the graph which shows the relationship between the carbon dioxide gas concentration of shift reaction product gas, and the hydrogen concentration of the gas product obtained by the modification | reformation (low molecular weight reduction) of polyethylene In an Example, the graph which shows the relationship between the hydrogen concentration of shift reaction product gas, and the carbon dioxide gas concentration of the gas product obtained by the modification | reformation (low molecular weight reduction) of polyethylene Explanatory drawing which shows typically the equipment used in the Example (Invention Example 11)

In the method of the present invention, an excess water vapor is added to an exhaust gas (g ₀ ) containing carbon monoxide generated in a metallurgical furnace (hereinafter sometimes referred to as “metallurgical furnace generated exhaust gas”) to cause a shift reaction. A mixed gas (g) containing hydrogen and carbon dioxide gas generated in the shift reaction and water vapor not consumed in the shift reaction, and this mixed gas (g) (hereinafter sometimes referred to as “shift reaction product gas”). Is brought into contact with an organic substance to cause a reaction to modify the organic substance to reduce the molecular weight, and the low molecular weight modified product of the organic substance and a solid residue (small amount) generated by this reaction are recovered. The solid residue is used as a carbon material in a manufacturing or processing process performed at a steel mill or the like. Alternatively, the molecular weight reduction reaction of the organic substance is performed in the presence of an iron-based catalyst, and the low molecular weight modified product of the organic substance and a solid residue (small amount) generated by this reaction are recovered. As a carbon material containing a source, it is used as a material in a manufacturing or processing process performed at a steel mill or the like.
Note that adding excess steam to the exhaust gas (g ₀ ) means adding steam so that excess steam that is not consumed in the shift reaction remains in the mixed gas (g).

In such a method of the present invention, the reduction of the molecular weight of the organic substance is efficiently promoted even at a relatively low reaction temperature, the hydrogen consumption is small, and the generation of heavy components and carbonaceous matter is hardly observed.
Generally, high molecular weight organic substances such as waste plastic are known to start thermal decomposition when heated at a temperature of 300 to 400 ° C. or higher, but at this time, they become lighter and heavier. Coexistence of hydrogen during thermal decomposition is effective in suppressing heavy formation and reducing the molecular weight because hydrogen addition reaction and hydrocracking reaction to hydrocarbon species proceed. However, the high temperature is required for hydrocracking, and the hydrogen consumption is a problem.

On the other hand, steam reforming and carbon dioxide reforming can be regarded as oxidation of hydrocarbons by oxygen in H ₂ O and CO ₂ molecules, achieving low molecular weight and suppressing carbonaceous production with a small amount of hydrogen addition. it can. Furthermore, steam reforming and carbon dioxide reforming are characterized in that the reaction temperature decreases as the carbon chain of the organic molecule to be modified becomes longer. In the method of the present invention, the low molecular weight of an organic substance is efficiently promoted even at a relatively low reaction temperature, the amount of hydrogen consumption is small, and the generation of heavy components and carbonaceous matter is hardly recognized. It is considered that the four reactions of hydrogenation, hydrocracking, steam reforming, and carbon dioxide reforming proceed simultaneously by reforming (reducing molecular weight) the organic substance using (g).
Incidentally, as the hydrogenation reaction, not only hydrogenation reaction to hydrocarbon species, that is gaseous products that also proceed hydrogenation reaction to CO and CO ₂ to produce a light hydrocarbon such as methane It is suggested from the analysis results. In the description of the present invention, for the sake of simplicity, the hydrogenation reaction to CO or CO ₂ is simply described as hydrogenation (or hydrogenation reaction) without being distinguished from the hydrogenation reaction to hydrocarbon species.

For example, the exhaust gas generated from a metallurgical furnace such as a converter usually contains about 25 to 80 vol% of CO. Therefore, when water vapor is added thereto, H ₂ and CO ₂ are generated by the following shift reaction (1).
CO + H ₂ O → H ₂ + CO ₂ (1)
In the method of the present invention, since excess water vapor is added to the exhaust gas (g ₀ ), the mixed gas (g) after the shift reaction includes H ₂ , CO ₂ generated by the shift reaction, and H ₂ O of excess addition. Will be included. In the reforming of organic substances (lower molecular weight) by this shift reaction product gas (g), four reactions of hydrogenation, hydrocracking, steam reforming, and carbon dioxide reforming by each gas component proceed simultaneously. it is conceivable that.

In the present invention, the concentration of water vapor, hydrogen, and carbon dioxide in the gas is controlled by appropriately controlling the excess ratio of water vapor added excessively to the exhaust gas (g ₀ ) and the reaction rate of the shift reaction. A mixed gas (g) for material modification can be obtained. However, the general composition of the metallurgical furnace generated exhaust gas stored in the gas holder (for example, a general gas holder used in a steelworks) is CO: 50 to 70 vol%, CO2: 10 to ₂₀ vol%, N _{2: 10~20vol%,} H _2: because of the order 0~5vol% (including other saturated steam) generally is not necessary to carry out until the reaction rate control of the shift reaction, only by adjusting the excess percentage of water vapor Thus, each concentration of water vapor, hydrogen and carbon dioxide in the mixed gas (g) can be controlled to a desired level.
The reaction rate of the shift reaction can be controlled by adjusting the residence time in the shift reactor. For example, in order to shorten the residence time, a method in which the shift reactor length is reduced or the catalyst charge amount is reduced is generally used. In this case, the shift reactor length and the catalyst charge amount are almost until equilibrium. What is necessary is just to set it as about 1 / 2-1 / 4 in the case of advancing reaction.

As an example, converter gas of 100 kmol / h (= 2240 Nm ³ / h) having a composition of CO: 65 vol%, CO ₂ : 15 vol%, N ₂ : 18 vol%, H ₂ : 1 vol%, H ₂ O: 1 vol% In the case of performing the shift reaction by changing the amount of water vapor added from 60 kmol / h (= 1340 Nm ³ / h) to 540 kmol / h (= 1100 Nm ³ / h), the amount of water vapor added and the composition of the gas after the shift reaction ( The calculated equilibrium composition at a temperature of 430 ° C. is shown in FIG. According to this, it can be seen that the concentration of water vapor, hydrogen, and carbon dioxide in the mixed gas (g) can be controlled only by adjusting the amount of water vapor added, and a preferable gas composition as described later can be obtained. In addition, it is well known that the shift reaction usually proceeds to almost equilibrium.

Hereinafter, details and preferred conditions of the method of the present invention will be described.
In the present invention, the reason why the metallurgical furnace generated exhaust gas is used as the exhaust gas (g ₀ ) for the shift reaction is that the metallurgical furnace generated exhaust gas contains carbon monoxide at a relatively high concentration and the concentration of unnecessary nitrogen is low. . As the metallurgical furnace-generated exhaust gas (g ₀ ) containing carbon monoxide, any one can be used. The most representative is the converter gas generated from the converter where the decarburization process of the steel manufacturing process is performed, but other than that, for example, it is generated from a hot metal pretreatment furnace, a smelting reduction furnace, a shaft furnace, etc. Exhaust gas to be used can be exemplified, and one kind or a mixture of two or more kinds thereof can be used.
The secondary combustion rate (CO ₂ / (CO + CO ₂ ) × 100), which is the rate at which carbon monoxide produced in the metallurgical process is further oxidized to produce carbon dioxide, is generally only about 10 to 50%. Also, in the exhaust gas (g ₀₎ are also included hydrogen and nitrogen, H ₂ concentration varies depending on the metallurgical process, it is about 0~20vol%. Nitrogen is supplied for in-furnace agitation and flue safety, and the concentration in the exhaust gas (g ₀ ) is usually about 10 to 30 vol%.

From the above points, the composition of general metallurgical furnace-generated exhaust gas (g ₀ ) is generally in the following range.
CO: 80-25 vol% (equivalent to 10-50% secondary combustion rate)
CO _2: 10~25vol% (corresponding to the secondary combustion rate 10-50%)
N _2: 10~30vol%
H2: 0 to ₂₀ vol%
Although carbon monoxide is required for the shift reaction, there is no particular problem with the composition of the exhaust gas (g ₀ ) as long as the gas composition is in the above range. Here, nitrogen does not contribute at all to the chemical reactions (shift reaction, hydrogenation, hydrocracking, steam reforming, carbon dioxide reforming) that occur in the present invention, while diluting the gas product produced. , Lower combustion heat (hereinafter referred to as “LHV”). In particular, when the nitrogen concentration exceeds 50 vol%, the LHV of the gas product is significantly reduced and the shift reaction rate tends to be reduced. Therefore, the nitrogen concentration is preferably within the above composition range.

As mentioned earlier, gas holder (e.g., typical gas holder used in steelworks) General composition of metallurgical furnace generation exhaust gas to be stored in the, CO: 50~70vol%, CO 2 : 10 ˜20 vol%, N ₂ : 10 to ₂₀ vol%, H ₂ : 0 to 5 vol% (including saturated steam in addition), and this composition is high in the composition of the above general metallurgical furnace generated exhaust gas. It corresponds to the CO concentration composition. Since the gas stored in the gas holder is used as fuel gas at each factory in the steelworks, it is necessary to prevent a decrease in combustion efficiency at the use destination. Therefore, setting the lower limit value of the CO concentration in the gas as a storage condition in the gas holder is the reason why the composition has a high CO concentration.
In the present invention, the composition of the exhaust gas generated in the general metallurgical furnace as described above is used even if the exhaust gas has a relatively high CO concentration as stored in a general gas holder used in a steelworks. However, it can be used as exhaust gas (g ₀ ).

By the way, some of the metallurgical furnace-generated exhaust gas (g ₀ ) contains carbon monoxide but has a relatively high nitrogen concentration. Such a metallurgical furnace-generated exhaust gas (g ₀ ) contains at least nitrogen contained therein. A part may be separated (removed) to increase the carbon monoxide concentration, and then an excess of water vapor may be added to cause the shift reaction.
As typical exhaust gas that is preferably subjected to nitrogen separation, blast furnace gas can be mentioned, but in addition to this, exhaust gas generated from an electric furnace or a shaft furnace operating under a condition where the nitrogen concentration becomes high can be mentioned. it can. In addition, the nitrogen gas is separated from an exhaust gas containing a relatively high concentration of carbon monoxide such as a converter gas, and the shift reaction can be performed after further increasing the carbon monoxide concentration.

There is no particular restriction on the method for separating nitrogen from exhaust gas, and any method such as adsorption separation method or distillation separation method can be applied. However, since the boiling point difference between nitrogen and carbon monoxide is small, the adsorption separation method is Particularly preferred. For example, since activated carbon supporting Cu ⁺ , which is known as a CO adsorbent, also adsorbs CO ₂ , blast furnace gas (general composition: N ₂ : 50 vol%, CO ₂ ) is obtained by PSA method using Cu ⁺ supported activated carbon as an adsorbent. : _25vol%, CO 2: approximate composition as desorbed gas from 25 vol%) is _{N 2: 15vol%, CO:} 45vol%, CO 2: it is possible to obtain a 40 vol% of the gas, which separates the nitrogen in the blast furnace gas Thus, the carbon monoxide is concentrated.

The shift reaction in the method of the present invention may be carried out by a known method and is not particularly limited. Generally, water vapor is added to the metallurgical furnace-generated exhaust gas (g ₀ ) in advance, and this is introduced into a fixed bed reactor filled with a catalyst to perform a shift reaction. Alternatively, the water vapor to be added in advance may be partially used, the catalyst may be packed in multiple stages in the reactor, and the remaining water vapor may be added between the catalyst layer and the catalyst layer.
If water vapor, hydrogen, and carbon dioxide are added to the metallurgical furnace-generated exhaust gas (g ₀ ) without performing the shift reaction as in the present invention, the mixture for organic substance modification obtained by the shift reaction in the present invention is used. Although a gas having a composition equivalent to that of the gas (g) can be obtained, in such a method, in addition to water vapor, expensive hydrogen gas and carbon dioxide gas must be added, resulting in an increase in cost.

In the present invention, the mixed gas (g) for reforming the organic substance obtained by the shift reaction contains water vapor, hydrogen and carbon dioxide gas, and there is no particular limitation on the concentration thereof. Therefore, the water vapor concentration is preferably 5 to 70 vol%. In other words, when the water vapor concentration is low, the decomposition rate of organic substances such as waste plastics is low. However, by setting the water vapor concentration to 5 vol% or more, a certain level of organic material decomposition rate can be secured, and the rate of production of gas products. (Gasification rate)-The production rate (liquefaction rate) of the liquid product can be kept at a constant level, and the production amount of heavy components, which are solid residues, can be reduced. On the other hand, when the water vapor concentration is high, CO ₂ tends to remain in the reforming reaction product gas of the organic substance (gas generated by low molecular weight reforming of the organic substance; the same applies hereinafter), and also a gas product / liquid production However, if the water vapor concentration is 70 vol% or less, the residual CO _{2 in} the reforming reaction product gas can be suppressed, and the LHV of the gas product / liquid product can be reduced. The decrease can also be suppressed.
Further, from the viewpoint of securing the decomposition rate of the organic substance and reducing the solid residue, both the hydrogen concentration and the carbon dioxide gas concentration of the mixed gas (g) are preferably 5 vol% or more.

Moreover, for the following reasons, the more preferable composition of the mixed gas (g) for organic substance reforming is: water vapor concentration: 20 to 70 vol%, hydrogen concentration: 10 to 40 vol%, carbon dioxide concentration: 10 to 40 vol%. It is. In addition, it does not prevent that other gas components (for example, nitrogen etc.) are contained in this mixed gas (g). By setting the water vapor concentration to 20 vol% or more, the decomposition rate of the organic substance can be sufficiently increased, and the LHV of the gas product can be increased. The reason for setting the water vapor concentration to 70 vol% or less is as described above. By setting the hydrogen concentration to 10 vol% or more (more preferably 12 vol% or more), it is possible to suppress CO ₂ from remaining in the gas product even when a reforming reaction of an organic substance is performed at a relatively low temperature. be able to. By setting the carbon dioxide gas concentration to 10 vol% or more (more preferably 13 vol% or more), H ₂ that is a low-calorie gas component is less likely to remain in the gas product as compared to hydrocarbons and CO. Further, by setting the hydrogen concentration and the carbon dioxide gas concentration to 40 vol% or less, the decomposition rate of organic substances such as waste plastic can be set to a preferable level, and solid residue can be reduced. Moreover, from the above viewpoints, a more preferable gas composition of the mixed gas (g) is a water vapor concentration: 25 to 65 vol%, a hydrogen concentration: 15 to 35 vol%, and a carbon dioxide concentration: 15 to 35 vol%. In addition, it does not prevent that other gas components (for example, nitrogen etc.) are contained in this mixed gas (g).

  Further, as one of the features of the present invention, the ratio of the gas product generation amount and the liquid product generation amount in the reforming of the organic substance can be controlled by the water vapor concentration of the mixed gas (g) for the organic substance reforming. Is mentioned. That is, when the water vapor concentration of the mixed gas (g) is 50 vol% or more, a gas product is mainly generated (that is, when the gas product production amount> the liquid product production amount), and when the water vapor concentration is 40 vol% or less, liquid production is generated. The product is mainly produced (i.e., gas product yield <liquid product yield). In addition, since the influence of hydrogen concentration and carbon dioxide concentration is not as remarkable as the influence of water vapor concentration, it may be within the preferable range of the present invention.

Next, conditions for modifying (lowering the molecular weight) of an organic substance with the mixed gas (g) obtained by the shift reaction will be described.
In the present invention, there is no particular limitation on the organic material to be reduced in molecular weight by modification, but high molecular weight organic material is suitable, for example, waste plastic, oil-containing sludge, waste oil, biomass, etc. One or more of these can be targeted.

Although there is no special restriction | limiting in the kind of waste plastics made into object, For example, the object plastics etc. which are an industrial waste type | system | group and a container packaging recycling law can be mentioned. More specifically, polyolefins such as PE and PP, thermoplastic polyesters such as PA and PET, elastomers such as PS, thermosetting resins, synthetic rubbers, foamed polystyrene and the like can be mentioned. In addition, inorganic substances such as fillers are added to many plastics. However, in the present invention, such inorganic substances are not involved in the reaction, so that they are reformed (low molecular weight) reactors (organic substances) as solid residues. Is discharged from a reactor for reducing the molecular weight by modifying the same. In addition, the waste plastic is preliminarily cut to an appropriate size as required, and then charged into the reforming reactor.
Further, if the waste plastic contains a chlorine-containing resin such as polyvinyl chloride, chlorine is generated in the reforming reactor, and this chlorine may be contained in a gas product or a liquid product. Therefore, when there is a possibility that the waste plastic contains chlorine-containing resin, a chlorine absorbent such as CaO is introduced into the reforming reactor and contained in a gas product or liquid product that generates chlorine. It is preferable not to do so.

  Oil-containing sludge is a sludge-like mixture generated in an oil-containing waste liquid treatment step, and generally contains about 30 to 70% by mass of water. Examples of the oil in the sludge include, but are not limited to, various mineral oils, natural and / or synthetic oils and fats, and various fatty acid esters. In addition, in order to improve handling property, such as when supplying oil-impregnated sludge to the reforming reactor, moisture in the sludge may be reduced to about 30 to 50% by mass by a method such as centrifugation.

Examples of the waste oil include, but are not limited to, various used mineral oils, natural and / or synthetic fats and oils, and various fatty acid esters. Moreover, the mixture of these 2 or more types of waste oil may be sufficient. In addition, in the case of waste oil generated in the steel mill rolling process, it generally contains a large amount of water (usually more than about 80% by mass), but this water is also reduced in advance by a method such as specific gravity separation. It is advantageous in terms of handleability.
When the organic substance contains water, water vapor is generated in the reforming reactor. Therefore, the excess ratio of water vapor added in the shift reaction is determined in consideration of the amount.

  Examples of biomass include, but are not limited to, sewage sludge, paper, construction waste, thinned wood, and other processed biomass such as waste solid fuel (RDF). Since biomass usually contains a large amount of water, it is preferable to dry it beforehand in view of energy efficiency. In addition, in the case of biomass containing relatively high concentrations of alkali metals such as sodium and potassium, alkali metals may be deposited in the reforming reactor. It is preferable to keep it. In addition, large biomass such as construction waste is cut in advance and charged into the reforming reactor.

  The reaction temperature during organic substance modification is preferably as follows according to the type of organic substance. In the case of waste plastic or biomass, a reaction temperature of about 400 to 900 ° C. is appropriate. When the reaction temperature is less than 400 ° C, the decomposition rate of waste plastics and biomass is low. On the other hand, when the reaction temperature exceeds 900 ° C, the production of carbonaceous matter increases. In the case of oil-containing sludge or waste oil, the reaction temperature is suitably about 300 to 800 ° C. When the reaction temperature is less than 300 ° C., the decomposition rate of oil-containing sludge and waste oil becomes low. On the other hand, even if the reaction temperature exceeds 800 ° C., there is no effect on the reforming (lower molecular weight) characteristics of the oil-containing sludge or waste oil, but it is not economical because the temperature is higher than necessary.

Moreover, when the mixture which consists of waste plastics and / or biomass and oil-containing sludge and / or waste oil is made into object, about 400-800 degreeC is suitable for reaction temperature from the point mentioned above. In addition, the influence of reaction temperature with respect to the ratio of a gaseous product production amount and a liquid product production amount is hardly seen. In addition, since the influence of pressure is hardly observed, it is economical to operate the reforming reactor at normal pressure or at a slight pressure of about several kg / cm ² .
The type of reforming reactor is not particularly limited, but organic substances such as waste plastic can move smoothly in the reactor, and can be efficiently contacted with the mixed gas (g) for organic substance reforming. A horizontal moving bed type reactor such as a rotary kiln is preferable because the residue can be continuously discharged.

  In the present invention, since a catalyst is not particularly required for reforming the organic substance, the solid residue generated when the catalyst is not used is used as a carbon material in a production or treatment process performed at a steel mill or the like. In the present invention, a Ni-based reforming catalyst, a Ni-based hydrogenation catalyst, a Pt / zeolite-based petroleum refining catalyst, etc. each have steam reforming activity, carbon dioxide reforming activity, hydrogenation activity, and hydrocracking activity. The reforming reaction can also be carried out using a seed or two or more kinds of catalysts, and the solid residue generated in that case is used as a carbon material in a manufacturing or processing process carried out at an ironworks after separation from the catalyst. Is done. The method for separating the catalyst is not particularly limited, but any method such as separation by visual observation can be adopted in addition to a separation method using a specific gravity difference such as centrifugal separation or cyclone.

  On the other hand, when an organic material reforming reaction is performed using an iron-based catalyst, the generated solid residue is used as a carbon material containing an iron source (an iron source derived from an iron-based catalyst). As the iron-based catalyst, converter dust generated in the converter, a high-temperature shift catalyst such as Fe-Cr, and iron-based catalysts supported on various carriers such as alumina and zeolite are preferable. In particular, converter dust is a fine iron particle that not only exhibits high activity in organic material reforming reactions, but also is a byproduct of hot metal pretreatment processes such as converter dephosphorization and converter decarburization processes, and is inexpensive. Therefore, it is particularly preferable because it can be disposable. On the other hand, a catalyst having dehydrogenation activity such as an ethylbenzene dehydrogenation catalyst (for example, Fe-K system) is not preferable because it increases carbonaceous matter generated in the reforming reaction.

When packing the catalyst, contact between the organic material such as waste plastic and the catalyst is good, so a vertical reforming reactor is used instead of a horizontal moving bed reforming reactor such as a rotary kiln. It may be adopted. In this case, the mixed gas (g) obtained by the shift reaction is supplied from the lower part and / or the side part rather than the upper part of the reforming reactor. Is preferable.
As a vertical reforming reactor, a general fixed bed reactor used in the chemical industry can be used, but in particular, when a method of supplying a mixed gas (g) from the lower part of the reforming reactor is employed. In addition, a blast furnace, a shaft furnace, or a converter, which is an iron manufacturing facility, can be used as a reforming reactor. When a blast furnace or shaft furnace is used as a reforming reactor, an organic substance and a catalyst are supplied continuously from the top of the furnace, and a mixed gas (g) is continuously supplied from the bottom of the furnace to counter-current contact, and gas is supplied from the top of the furnace. It is preferable that the product is a moving bed type in which the liquid product, the solid residue, and the catalyst are continuously extracted from the lower part of the furnace because the reaction efficiency becomes high. When a converter is used as a reforming reactor, an organic substance and a catalyst are introduced into the furnace, then a mixed gas (g) is continuously supplied from the lower part of the furnace, and a gas product is continuously supplied from the upper part of the furnace. The liquid product, the solid residue, and the catalyst can be extracted in a batch reaction mode similar to blowing, in which the furnace is tilted after the reaction for a certain time. In either case, the solid residue and the catalyst are separated from the liquid product, and when the catalyst is an iron-based catalyst, it is usually used as a carbon material containing an iron source in a production or treatment process performed at a steel mill or the like. Used. Further, when the catalyst is a non-ferrous catalyst, the solid residue and the catalyst are separated, and the solid residue is used as a carbon material in a production or treatment process performed in an ironworks or the like.

  In particular, when converter dust is used as a catalyst, it is also preferable to use a horizontal moving bed reactor such as a rotary kiln because the converter dust is inexpensive and can be made disposable. In this case, an organic substance and a catalyst are continuously supplied from the front of the furnace, and a mixed gas (g) is continuously supplied from the rear of the furnace to be brought into countercurrent contact, and a gas and a liquid product are supplied from the front of the furnace and a solid is supplied from the rear of the furnace. It is preferable to use a moving bed type in which the solid residue and the catalyst are continuously extracted, since the reaction efficiency becomes high. The solid residue and the catalyst can be used in a production or treatment process performed at a steel mill or the like as a carbon material containing an iron source without any separation step.

The reformed product of the organic substance obtained by the method of the present invention can be separated into a gas product and a liquid product, respectively, by cooling the reforming reaction product gas and then performing gas-liquid separation. In addition, the liquid product can be separated into a naphtha-equivalent fraction, a kerosene-equivalent fraction, a light oil-equivalent fraction, and the like by distillation separation as necessary. The cooling method, the gas-liquid separation method, and the distillation separation method of the reforming reaction product gas can be performed by known methods, and there is no particular limitation.
Combustible components of the gas product consists hydrocarbons of carbon monoxide and C1 -C4, the LHV of about 6~10Mcal / Nm ^3. Thus, although it is LHV comparable to natural gas, since carbon monoxide concentration is high, it is characterized by higher combustibility than natural gas. Since it has a high carbon monoxide concentration and high combustibility, it can be used as an alternative fuel for coke oven gas, which is the main fuel of integrated steelworks. Moreover, since it is a mixed gas consisting of CO and light hydrocarbons, it can be blown into the blast furnace as an alternative to natural gas.

Since the liquid product consists of C5 to C24 hydrocarbons, it is a mixture of naphtha (C5 to C8), kerosene (C9 to C12), and light oil (C13 to C24). High quality light oil not included. This liquid product may be used separately as naphtha, kerosene, or light oil by distillation separation, but as a mixture, it can be used as a reducing agent instead of heavy oil in blast furnaces and fuels in factories with metallurgical furnaces such as ironworks. Can be used.
Since the content of naphtha (C5 to C8) is high, the naphtha is separated by distillation and used as a raw material for chemical industry, and only the distillation residue (mixture of kerosene and light oil) after separation of naphtha is replaced with heavy oil at the steelworks. It may be used as a reducing agent.

  As described above, in the method of the present invention, the low molecular weight reformed product (gas product, liquid product) produced and recovered by the low molecular weight reaction of the organic substance is subjected to steps such as distillation separation as necessary. Thereafter, they can be effectively used as gaseous fuel, liquid fuel, and the like. In particular, it can be used as fuel and / or reducing agent in steelworks and can be blown into the blast furnace as a heat source and reducing agent. Can be secured. The gas product (gas) is usually blown into the blast furnace through a tuyere, but is not limited thereto. When blowing a gaseous product from a tuyere, it is common to install a blowing lance in the tuyere and to blow from this blowing lance.

  On the other hand, the solid residue generated and recovered by the low molecular weight reaction of the organic substance is produced at a steel mill or the like as a carbon material (including the case of “carbon material containing an iron source”). Alternatively, it can be used effectively in the processing process. Examples of production or treatment processes performed at steelworks include sinter production processes, coke production processes, converter decarburization processes, blast furnace processes, and the like, and are used as carbon materials in one or more of these processes. can do. Moreover, you may utilize as a carbon material in manufacture or a process other than a steelworks. Specifically, use as an alternative carbon source in a carbon material manufacturing process such as activated carbon or graphite electrode can be exemplified.

In the sintered ore production process (sintering machine), powdered coke is used as a coagulating material for iron ore, and a part of the powdered coke can be replaced with the solid residue. When the solid residue contains an iron source, the iron source condenses with the iron ore to form a massive ore.
In the coke production process (coke oven), the solid residue can be used as a partial substitute material for raw coal. Since coke ovens use waste plastic as a partial substitute for coking coal, it can be used as a substitute for this waste plastic.

In the converter decarburization process (converter), the solid residue can be used as an alternative material for converter carburized material such as earth graphite. In particular, the solid residue containing the converter dust after the organic substance reforming reaction using the converter dust as a catalyst is a carbon material using the dust generated from the converter as an iron source. This is preferable because it does not affect the operation.
Regarding the use of the solid residue in the blast furnace process, the fact that the block ore and coke produced by using the solid residue in the sinter ore production process is used as the blast furnace raw material itself, This corresponds to the use of a solid residue. In addition, the molded solid residue can be used as a blast furnace raw material (carbon material) as it is, especially after an organic substance reforming reaction using an iron-based catalyst (especially converter dust). What formed the solid residue can be used as a blast furnace raw material consisting of iron source (iron source derived from iron-based catalyst) + carbon material.

In addition, from the point mentioned above, if the mixed gas of the composition equivalent to the mixed gas (g) obtained by this invention is used, an organic substance can be decomposed | disassembled efficiently and a molecular weight can be reduced. In particular, water vapor concentration: 20-70 vol%, hydrogen concentration: 10-40 vol%, carbon dioxide concentration: 10-40 vol%, more preferably water vapor concentration: 25-65 vol%, hydrogen concentration: 15-35 vol%, carbon dioxide concentration: By using a mixed gas of 15 to 35 vol%, the decomposition rate of the organic substance can be sufficiently increased, and the LHV of the gas product can be increased. In addition, it does not prevent that other gas components (for example, nitrogen etc.) are contained in this mixed gas.
The reason for limiting the gas composition is the same as the reason for limitation in the method of the present invention described above. In order to obtain a mixed gas having such a composition other than the method of the present invention, for example, one or more of water vapor, hydrogen, and carbon dioxide gas is added to the base gas.
The conditions for modifying (decreasing the molecular weight) of the organic substance by the mixed gas are the same as the conditions for modifying (decreasing the molecular weight) in the method of the present invention described above.

Therefore, the gist of the method is as follows [i] to [viii], and the examples of the present invention described later are also examples of the methods [i] to [viii] below.
[I] Reducing the molecular weight of the organic material by modifying the organic material by bringing a mixed gas having a water vapor concentration of 20 to 70 vol%, a hydrogen concentration of 10 to 40 vol%, and a carbon dioxide gas concentration of 10 to 40 vol% into contact with the organic material. The organic substance produced by the reaction is recovered, the low molecular weight modified product of the organic substance and the solid residue are collected, and the solid residue is used as a carbon material. Method.
[Ii] By bringing a mixed gas having a water vapor concentration of 20 to 70 vol%, a hydrogen concentration of 10 to 40 vol%, and a carbon dioxide gas concentration of 10 to 40 vol% into contact with the organic material in the presence of an iron-based catalyst, Reducing the molecular weight by reforming, recovering the low molecular weight modified product and solid residue of the organic substance generated by the reaction, and using the solid residue as a carbon material containing an iron source A method for making organic materials into a material.
[Iii] In the method [i] or [ii] above, the mixed gas has a water vapor concentration of 25 to 65 vol%, a hydrogen concentration of 15 to 35 vol%, and a carbon dioxide concentration of 15 to 35 vol%. How to make organic materials.

[Iv] The method according to any one of [i] to [iii] above, wherein the organic substance to be modified is at least one selected from waste plastic, oil-containing sludge, waste oil, and biomass. A method for making the organic substance described in the above.
[V] In the method according to any one of [i] to [iv] above, the solid residue is used as a carbon material in a production or treatment process performed at a steel mill, .
[Vi] In the method of [v] above, the production or treatment process performed at the steel mill is one or more of a sintered ore production process, a coke production process, a converter decarburization process, and a blast furnace process. A method for converting an organic material into a material.
[Vii] The organic material according to any one of the above [i] to [vi], wherein the recovered low molecular weight reformed organic material is used as a fuel and / or a reducing agent in a steel mill. How to make a profit.
[Viii] In the method of [vii] above, a method for converting an organic substance into a profitable material is characterized in that the low molecular weight modified product of the recovered organic substance is blown into a blast furnace.

・ Invention Example 1
A branch pipe is provided in the gas discharge pipe of the gas holder for temporarily storing the converter gas, and a part of the converter gas can be extracted through the branch pipe. Downstream of this branch pipe is a flow control valve, steam mixer, preheater (for converter gas and steam mixed gas), shift reactor (cylindrical vertical type), reforming reactor (externally heated rotary kiln), A gas cooler for cooling the reforming reaction product gas equipped with a liquid product collector was arranged in this order. On the inlet side of the reforming reactor, a screw conveyor type waste plastic quantitative charging device was installed. A sampling port and a flow meter were installed in the outlet piping of the shift reactor and the outlet piping of the gas after cooling of the gas cooler.

The average composition of the converter gas in the gas _{holder, H 2: 12vol%, CO} : 54vol%, CO 2: 17vol%, H 2 O: 1vol%, N 2: was 16 vol%. The converter gas 74 nm ³ / h, a steam pressure 10 kg / cm ² G and 100 Nm ³ / h supplied as steam against a steam mixer, after raising the temperature to 320 ° C. in the preheater, the shift reactor (Fe- (Cr-based high temperature shift catalyst filling). Due to the shift reaction in the shift reactor, gas having a gas composition of H ₂ : 26 vol%, CO: ₂ vol%, CO ₂ : 28 vol%, H ₂ O: 37 vol%, N ₂ : 7 vol% (shift reaction product gas) Obtained. This shift reaction product gas had a flow rate of 172 Nm ³ / h (170 kg / h in mass flow rate) and a reactor outlet gas temperature of 430 ° C.

The externally heated rotary kiln, which is a reforming reactor, is preheated to 500 ° C. in advance, and 880 kg of polyethylene that has been crushed into granules as a model material of waste plastic is introduced into this reforming reactor while introducing a shift reaction product gas. / H, and the temperature was raised to 800 ° C., which is the planned reaction temperature. After reaching 800 ° C., the liquid product collected in the liquid product collector was discharged, and then the reforming reaction of the waste plastic was continued for 1 hour.
The amount and composition of the gas product are determined from the gas analysis results after cooling by the gas cooler, and the liquid product content is determined from the analysis results of the liquid product collected in the liquid product collector. Moreover, LHV was calculated | required about the gaseous product. The results are shown in Table 1.

Since the total amount of shift reaction product gas and polyethylene supplied as raw materials was 1050 kg / h, the production rate relative to the total amount of the feed materials was 36% for gas products and 62% for liquid products. Since it is difficult to directly measure the amount of unreacted polyethylene, the sum of the gas product (380 kg / h) and the liquid product (650 kg / h) relative to the total amount of shift reaction product gas and polyethylene (1050 kg / h) supplied. When the yield is defined as the polyethylene decomposition rate, in Example 1, the polyethylene decomposition rate is 98%, which is a sufficiently high value, and the production of hydrocarbons of C25 or higher is hardly observed. It is clear that the molecular weight was reduced. H ₂ O, CO ₂ and H ₂ are completely consumed by the reforming reaction of the organic substance, and it is considered that four reactions of steam reforming, carbon dioxide reforming, hydrogenation, and hydrocracking proceeded simultaneously. . The LHV of the produced gas product was 8.9 Mcal / Nm ³ and increased to 4.7 times that of the converter gas (1.9 Mcal / Nm ³ ).

  Polyethylene was efficiently reduced in molecular weight, but in addition to the above gas product and liquid product, a solid residue was generated although it was a little 2 mass% (20 kg / h). Since the reforming reaction was carried out without a catalyst, this residue corresponds to a carbon material containing no iron source. An experiment was conducted in which this residue was used in a coke oven. 1 ton of solid residue and 19 ton of coking coal were mixed in advance and charged in one carbonization chamber. Carbonization proceeded in the usual process, and coke could be produced without any problems. Since the coking coal charge amount per coking chamber of the coke oven is 20 tons, the coking coal can be reduced by 5%.

Inventive examples 2 to 10
In the same equipment as Invention Example 1, except that the steam flow rate supplied to the shift reactor was variously changed and the reforming reaction temperature was set at two levels of 800 ° C. and 500 ° C., the same as in Invention Example 1, Experiments were carried out on the shift reaction of the converter gas and the reforming reaction of polyethylene with the shift reaction product gas. The results are shown in Table 2 and FIGS.

FIG. 2 shows the relationship between the water vapor concentration of the shift reaction product gas and the gasification rate and liquefaction rate in the reforming of polyethylene (reaction temperature: 800 ° C.). Here, the gasification rate is a ratio of the production amount (kg / h) of the gas product to the total amount (kg / h) of the supplied shift reaction product gas and polyethylene, and the definition of the gas product is shown in Table 1. From H ₂ to C 4 as shown in FIG. Similarly, the liquefaction rate is a ratio of the production amount (kg / h) of the liquid product to the total amount (kg / h) of the supplied shift reaction product gas and polyethylene, and the definition of the liquid product is shown in Table 1. As shown, it was from C5 to C24. FIG. 3 shows the relationship between the water vapor concentration of the shift reaction product gas and the LHV of the gas product and liquid product obtained by the modification of polyethylene (reaction temperature: 800 ° C.). Here, the LHV of the liquid product was expressed as LHV per volume in the standard state in terms of gas of the liquid product. FIG. 4 shows the relationship between the water vapor concentration of the shift reaction product gas and the polyethylene decomposition rate due to the modification of polyethylene, and in particular, shows that the polyethylene decomposition rate is equivalent at reaction temperatures of 500 ° C. and 800 ° C. It is a thing. FIG. 5 shows the relationship between the carbon dioxide concentration of the shift reaction product gas and the hydrogen concentration of the gas product obtained by the reforming of polyethylene (reaction temperature: 800 ° C.). FIG. 6 shows the relationship between the hydrogen concentration of the shift reaction product gas and the carbon dioxide concentration of the gas product obtained by the reforming of polyethylene (reaction temperature: 500 ° C.).

-Invention Example 11
An outline of the equipment used in this example is shown in FIG. This equipment is provided with a vertical reforming reactor 2 (internal volume: about 3 m ³ ) having a gas dispersion plate 20 at the bottom, and in this reforming reactor 2, the lowermost layer is crushed into granules. Was filled with 880 kg of the polyethylene a, and a metal net b (10 mesh) was placed on the top, and further Ni catalyst c (Ni loading: 10% by mass, support: α-Al ₂ O ₃ ) was placed on the top 800 kg. Filled. The shift reaction product gas generated in the shift reactor 1 is introduced into the bottom of the reforming reactor 2, and is supplied into the reactor through the gas dispersion plate 20, and ascends in the reactor. The reformed product is discharged from the upper part of the reforming reactor 2 and separated into a gas product and a liquid product by the liquid product collector 3. The separated gas product is cooled by the gas cooler 4. The equipment configuration from the gas holder for temporarily storing the converter gas to the shift reactor 1 was the same as that of Invention Example 1.

Except for using the above equipment and setting the planned reaction temperature in the reforming reactor 2 to 750 ° C., the same conditions as in Invention Example 1 (conditions for obtaining the converter gas composition, shift reaction product gas, shift The reaction reaction gas composition, temperature, flow rate, etc.) were used to conduct experiments on the reforming of polyethylene.
The production amount and composition of the gas product and the liquid product were determined in the same manner as in Invention Example 1. The results are shown in Table 3. The reaction results were almost the same as those of Invention Example 1, and it was considered that the reaction temperature in the reforming reactor 2 was 750 ° C., which was 50 ° C. lower than that of Invention Example 1, due to the effect of catalyst addition.

  Similar to Invention Example 1, a solid residue was generated although it was a little 2 mass% (20 kg / h). In the example of the present invention, since the Ni catalyst was filled, the solid residue and the catalyst were primarily separated by centrifugal separation, and only the solid residue was separated visually. Therefore, this recovered residue corresponds to a carbon material that does not contain an iron source. The solid residue recovery rate was 90% (recovery amount: 0.9 tons). Similar to Invention Example 1, an experiment was conducted in which this residue was used in a coke oven. 0.9 tons of solid residue and 19.1 tons of coking coal were mixed in advance and charged into one carbonization chamber. Carbonization proceeded in the usual process, and coke could be produced without any problems. Since the coking coal charge per coking chamber of this coke oven is 20 tons, the coking coal was reduced by 4.5%.

Comparative example 1
In order to examine the reforming reaction efficiency of polyethylene with a gas having a low water vapor and hydrogen concentration, H ₂ : 1 vol%, CO: 61 vol%, CO ₂ : 19 vol%, H ₂ O: 1 vol%, N ₂ : 18 vol% A standard gas of composition was made, and a polyethylene reforming reaction experiment was conducted with this gas. As a result, even at a temperature of 800 ° C., the polyethylene degradation rate was only 16%, the gasification rate was 10%, and the liquefaction rate was only 5%.

Invention Example 12
Blast furnace gas was used as an exhaust gas generated from a metallurgical furnace containing carbon monoxide. The composition of the blast furnace gas after desulfurization / drying treatment was H ₂ : 3 vol%, CO: 23 vol%, CO ₂ : 21 vol%, N ₂ : 53 vol%, so that nitrogen separation was performed by the PSA method described below, Increased concentration of carbon monoxide.
In nitrogen separation by the PSA method, the above blast furnace gas was supplied at 136 Nm ³ / h at normal pressure to an adsorption tower packed with 400 kg of Cu ⁺ supported activated carbon as an adsorbent. Desorption is performed at 7 kPa (absolute pressure), and the composition of the desorption gas (= blast furnace gas enriched with carbon monoxide) is H ₂ <1 vol%, CO: 47 vol%, CO ₂ : 37 vol%, N ₂ : 16 vol%, flow rate Was 58 Nm ³ / h. The carbon monoxide and steam 73 nm ³ / h a pressure 10 kg / cm ² G was supplied to the steam mixer as blast furnace gas 58 nm ³ / h and steam were concentrated and subjected to a shift reaction in the same manner as in Invention Example 1. As a result, a gas (shift reaction product gas) having a gas composition of H ₂ : 19 vol%, CO: ₂ vol%, CO ₂ : 35 vol%, H ₂ O: 37 vol%, and N ₂ : 7 vol% was obtained. This shift reaction product gas had a flow rate of 130 Nm ³ / h (146 kg / h in mass flow rate) and a reactor outlet gas temperature of 430 ° C.

Using the same apparatus as in Invention Example 1, 50 kg / h of the converter dust dehydrated and dried as a catalyst and 880 kg / h of polyethylene crushed in the same manner as in Invention Example 1 were supplied, and the shift reaction product gas (146 kg) was supplied. / H), a reaction for reducing the molecular weight of polyethylene was carried out at a reaction temperature of 600 ° C. As a result of the reaction, the production amount of gas product was 320 kg / h (LHV: 7.5 Mcal / Nm ³ ), the production amount of liquid product was 650 kg / h, and the polyethylene degradation rate was 95%.

The generated solid residue was 110 kg / h, which includes converter dust (50 kg / h) as a catalyst. The iron content in the converter dust is about 50 to 80% by mass as Fe. In calculation, the solid residue of this example corresponds to a carbon material containing 23 to 36% by mass of an iron source in terms of metallic iron, but for simplicity, it is composed of 30% by mass of metallic iron and 70% by mass of carbon. did.
An experiment was conducted in which this residue was used as a converter carburizing material. In this converter, 5 kg / t-steel of earth graphite is used as a carburizing material. In the experiment, a solid residue of 1.4 kg / t-steel (carbon content) is added to 4 kg / t-steel earth graphite. A mixture of 1 kg / t-steel) was used as a carburized material. As a result, there was no change from usual and it was possible to blow without problems.

DESCRIPTION OF SYMBOLS 1 Shift reactor 2 Reforming reactor 3 Liquid product collector 4 Gas cooler 20 Gas dispersion plate a Polyethylene b Net c Ni catalyst

Claims (11)

By adding excess water vapor to the exhaust gas (g ₀ ) containing carbon monoxide generated in the metallurgical furnace to cause the shift reaction, hydrogen and carbon dioxide generated by the shift reaction were not consumed in the shift reaction. A mixed gas (g) containing water vapor is brought into contact with the organic substance to cause a reaction that modifies the organic substance and lowers the molecular weight. A method for producing an organic material, which comprises recovering a low molecular weight modified product and a solid residue, and using the solid residue as a carbon material. By adding excess water vapor to the exhaust gas (g ₀ ) containing carbon monoxide generated in the metallurgical furnace to cause the shift reaction, hydrogen and carbon dioxide generated by the shift reaction were not consumed in the shift reaction. A mixed gas (g) containing water vapor is brought into contact with the organic substance in the presence of an iron-based catalyst to cause a reaction to modify the organic substance to reduce the molecular weight, A method for producing an organic material comprising collecting a low molecular weight modified product and a solid residue of an organic substance generated by the reaction, and using the solid residue as a carbon material containing an iron source.   The method for converting an organic substance into a material according to claim 2, wherein the iron-based catalyst is converter dust. The exhaust gas (g ₀ ) is an exhaust gas whose carbon monoxide concentration is increased by separating at least a part of nitrogen from exhaust gas containing carbon monoxide and nitrogen generated in a metallurgical furnace. A method for converting an organic substance into a material according to any one of?   The method for converting an organic substance into a material according to any one of claims 1 to 4, wherein the mixed gas (g) has a water vapor concentration of 5 to 70 vol%.   The mixed gas (g) has a water vapor concentration of 20 to 70 vol%, a hydrogen concentration of 10 to 40 vol%, and a carbon dioxide gas concentration of 10 to 40 vol%. Method.   The organic material to be reformed is one or more kinds selected from waste plastic, oil-containing sludge, waste oil, and biomass. .   The solid residue is used as a carbon material in a manufacturing or treatment process performed at a steel mill, The organic material utilization method according to any one of claims 1 to 7.   9. The manufacturing or processing process performed at a steel mill is one or more of a sinter ore manufacturing process, a coke manufacturing process, a converter decarburization process, and a blast furnace process. How to make organic materials.   10. The method for converting an organic substance into a profitable material according to any one of claims 1 to 9, wherein the recovered low molecular weight modified product of the organic substance is used as a fuel and / or a reducing agent in an ironworks.   The method for making a material for an organic material according to claim 10, wherein the low molecular weight modified product of the recovered organic material is blown into a blast furnace.

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