JP6461345B2 - Coke additive manufacturing method and manufacturing equipment - Google Patents

Description

  Disclosed is a method and apparatus for producing a coke additive capable of improving the strength of coke.

  In general, coke is produced by a coke production process using coking coal. Coking coal used for producing coke is classified into strong viscous coal and slightly viscous coal according to the degree of caking property. Use of high-strength coke is required for stable operation of large blast furnaces. In order to produce high-strength coke, it is advantageous to use strong viscous coal having excellent caking properties, or to use a large amount of strong viscous coal compared to slightly viscous coal. For this reason, up to now, high-grade and expensive strong coking coal has been used in large quantities in the production of coke.

However, due to the rapid increase in demand for caking coal for metallurgical use worldwide and the limited reserves of strong coking coal, it is becoming more difficult to secure strong coking coal, which has led to a surge in the price of strong coking coal. A problem occurred. Therefore, technological development capable of producing high-strength coke is being actively promoted while using low-quality and inexpensive non-caking coal such as subbituminous coal or lignite as raw coal.
For example, a technology for producing a quality improving agent for coke production has been developed by a solvent extraction method in which low-grade raw coal is dissolved in an expensive supercritical solvent under high temperature and high pressure conditions to extract a caking substance.

However, the conventional method has a drawback that construction of a large facility is required and the capital investment cost is excessive, and expensive hydrogen must be continuously supplied. This requires a large amount of equipment, resulting in an increase in manufacturing costs.
Conventionally, the production of oil from coal has been mainly focused on, and mass production of coke additives has not been sufficiently performed.

This invention makes it a subject to provide the manufacturing method and manufacturing apparatus of the additive for cokes optimized for the extraction of the additive for cokes.
Further, the present invention provides a method and apparatus for producing a coke additive capable of easily and effectively producing a coke additive for improving coke strength by a coal liquefaction process optimized for extraction of the coke additive. The issue is to provide.

Furthermore, this invention makes it a subject to provide the manufacturing method and manufacturing apparatus of the additive for cokes which can produce an additive, without construction of large sized facilities, such as a hydrogenation facility.
Moreover, this invention makes it a subject to provide the manufacturing method and manufacturing apparatus of the additive for cokes which can simplify a manufacturing process more.

  Furthermore, this invention makes it a subject to provide the manufacturing method and manufacturing apparatus of the additive for cokes which can manufacture the additive for cokes using low grade coal.

  The method for producing an additive according to an aspect of the present invention includes a coal pretreatment step in which coal is dispersed in a solvent to form a slurry, and a dispersion type iron catalyst is added to a product of the coal pretreatment step to form a coal slurry. A coal liquefaction step in which the coal slurry is liquefied by reacting the coal slurry and cracking gas; and a product of the coal liquefaction step; and COG (Coke Oven Gas) and / or LNG (Liquid Natural) as a cracking gas Gas) to produce a liquefied product, a separation step of separating a coke additive from the liquefied product to produce a liquid oil, and a liquid pre-treatment step for the liquid oil obtained in the separation step And a recirculation step used as the solvent.

  The coal pretreatment process may further include a step of pulverizing the coal and a step of drying the pulverized coal.

The coal may include lignite or subbituminous coal.
In the coal pulverization step, the coal is pulverized to a size of 60 mesh or less.
The coal drying step may be performed so that the moisture content of coal is 20 wt% or less.

The coal pretreatment step may be a step of slurrying the coal dried with respect to the solvent at a weight ratio of 1/1 to 1/4.
The dispersion type iron catalyst may be Fe ₂ O _{3 The} dispersion type iron catalyst may be added in an amount of 0.5 to 3.0 parts by weight with respect to 100 parts by weight of coal.

The coal liquefaction step is performed at a temperature of 250 to 450 ° C. and a pressure of 30 to 120 bar.
In the coal liquefaction step, cracking gas can be heated to 300 to 600 ° C. and supplied.

The separation step includes a separating step of separating a gas component from the liquefied product, a filtration step of separating the liquid substance and the solid substance, and distilling the liquid substance separated in the filtration step. A fractional distillation step for separating the coke additive, and the recycling step may be a step of supplying oil separated from the coke additive to the coal pretreatment step in the fractional distillation step.
The filtration step is performed at a temperature of 120 to 400 ° C.
The fractional distillation step is performed at a temperature of 200 to 350 ° C.

  The manufacturing apparatus according to this aspect liquefies coal slurry that has passed through the mixing drum, a mixing drum that mixes and slurries pretreated coal and a solvent, a catalyst supply unit that supplies a dispersion catalyst to the mixing drum, and the mixing drum. A reactor, a gas supply unit for supplying cracking gas to the reactor, a separation unit for separating the additive from the liquefied product produced from the reactor, and between the separation unit and the mixing drum And a supply line that supplies the oil separated by the separation unit to the mixing drum as a solvent.

  The separation unit separates a gas component from a liquefaction process product, a filter device connected to the separator and separates a liquid material and a solid material, and distills the liquid material separated by the filter device And a distiller connected to the mixing drum via the supply line and supplying the additive and separated oil to the mixing drum.

The manufacturing apparatus may further include a mill for pulverizing the coal for the coal pretreatment and a dryer for drying the pulverized coal.
The catalyst supply unit may have a structure for supplying a dispersed iron catalyst.
The gas supply unit may be a step of supplying COG and / or LNG.

According to such an aspect of the present invention, an optimized additive manufacturing process can be realized.
In addition, the additive manufacturing process can be optimized to produce a coke additive more economically and efficiently.

Furthermore, by simplifying the process, cost can be reduced, and the manufacturing cost of the additive for coke can be reduced.
In addition, since the grounding of the equipment for hydrogen production is unnecessary, the production cost can be reduced.

It is a schematic block diagram which shows the manufacturing apparatus of the additive for cokes by a present Example.

  The terminology used below is merely for the purpose of reference to particular embodiments and is not intended to limit the invention. As used herein, the singular form also includes the plural form unless the text clearly indicates the opposite meaning. As used herein, the meaning of “comprising” embodies particular characteristics, regions, integers, steps, operations, elements and / or components, and other specific properties, regions, integers, steps, operations, elements, It does not exclude the presence or addition of ingredients and / or groups.

  Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains can easily carry out. As will be readily understood by those skilled in the art to which the present invention pertains, the embodiments described below can be modified into various forms without departing from the concept and scope of the present invention. Thus, the present invention can be implemented in various different forms and is not limited to the embodiments described herein.

FIG. 1 is a schematic configuration diagram illustrating a configuration of a coke additive manufacturing apparatus according to the present embodiment.
As shown in FIG. 1, the manufacturing apparatus of the present embodiment includes a mixing drum 10 that mixes a pretreated coal and a solvent to form a slurry, and a catalyst supply unit 20 that supplies a dispersion catalyst to the mixing drum 10. , A reactor 30 for liquefying the coal slurry that has passed through the mixing drum 10, a gas supply unit 32 for supplying cracking gas to the reactor 30, and an additive from the liquefied product generated from the reactor 30 And a supply line 50 connected between the separation unit 40 and the mixing drum 10 and supplying oil separated by the separation unit to the mixing drum 10 as a solvent.

The manufacturing apparatus may further include a grinder 12 that crushes the coal and a dryer 14 that dries the pulverized coal in order to pretreat the coal.
In the present embodiment, the raw material coal for producing the additive may include low-grade non-caking coal such as lignite and subbituminous coal. Low-grade coal such as lignite and sub-bituminous coal has low physical properties such as caking properties, but has abundant reserves and is inexpensive, so the unit price of production can be reduced when manufacturing the additive for coke.

The mixing drum 10 mixes pretreated coal and a solvent to form a coal slurry.
In the present embodiment, the solvent that is put into the mixing drum 10 uses the remaining oil after the additive is separated in the separation unit 40.

For this purpose, the supply line 50 is connected between the separation unit 40 and the mixing drum 10, and the oil remaining after the separation of the additive is recirculated and supplied as a solvent to the mixing drum 10 via the supply line 50. .
In this way, the liquid oil separated through the separation unit 40 is immediately supplied to the mixing drum 10 and reused as a solvent, whereby the equipment can be simplified and the process can be simplified to produce the additive. Cost can be reduced.

  The catalyst supply unit 20 is connected to the mixing drum 10 and supplied with a dispersed iron catalyst. As a result, the dispersed iron catalyst is uniformly mixed together with the coal and the solvent in the mixing drum 10.

In this embodiment, the dispersed iron catalyst may be Fe ₂ O ₃ . Thus, the reactivity at the time of a liquefaction reaction can be improved by throwing a dispersion-type iron catalyst and mixing with a coal slurry. As a result, even when COG (Cake Even Gas) or LNG (Liquid Natural Gas) is used as a cracking gas during the liquefaction reaction, the dispersion type iron catalyst increases the reactivity and sufficient reaction effect for additive production is achieved. Can be pulled out.

  The coal slurry mixed in the mixing drum 10 is transferred to the reactor 30 by a high pressure pump. In the process in which the coal slurry is transferred from the mixing drum 10 to the reactor 30, the heating amount 16 provided between the mixing drum 10 and the reactor 30 supplies heat to the coal slurry to set the coal slurry. Heat to temperature.

The reactor 30 is a container that sufficiently withstands high temperature and pressure and has a reaction space therein, and liquefies coal slurry under high temperature and pressure. A heater or the like for supplying heat energy to the reactor 30 is provided outside the reactor 30, and a stirrer is provided inside.
The gas supply unit 32 is connected to one side of the reactor 30 and supplies cracking gas to the reactor 30. In the present embodiment, the gas supply unit 32 supplies COG, LNG, or a combination thereof as a cracking gas.

  Thus, by using COG or LNG as the cracking gas, the apparatus of the present embodiment does not need to have a conventional hydrogen production facility. As is known, the hydrogen production facility is a complex facility, and the construction cost reaches 1/4 of the total facility cost, and the operation cost is also high. Therefore, in the case of the present embodiment, it is not necessary to install a hydrogen production facility, so that the scale of the whole factory can be reduced and the production cost of the additive can be greatly reduced.

The separation unit 40 includes a separator 42 that separates a gas component from a liquefied product, a filter device 44 that is connected to the separator and separates a liquid material and a solid material, and a liquid material separated by the filter device. A distiller 46 that separates the coke additive B by distillation.
The distiller 46 of the separation unit 40 is connected to the mixing drum 10 via a supply line 50. Thereby, the oil separated from the additive through the distiller 46 is supplied to the mixing drum 10 through the supply line. The distiller 46 may be a fractional distiller that separates additives using a difference in boiling points.

Thus, this apparatus can finally produce the additive B for coke through the separation unit 40.
Hereinafter, the manufacturing process of the additive according to this example will be described.
The steps for producing the additive include a coal pretreatment step in which coal is dispersed in a solvent to form a slurry, a step of introducing a dispersed iron catalyst during coal pretreatment, and a reaction between the coal slurry and cracking gas. The coal liquefaction step for liquefying the coal slurry, the step of supplying COG and / or LNG as cracking gas during the coal liquefaction step, the separation step for separating the additive from the liquefied product, and the liquid obtained in the separation step A recirculation step in which oil is supplied to the coal pretreatment step and used as a solvent.

The coal pretreatment process is a process of preparing and preparing coal, which is a raw material for additive production, and after pulverizing the coal, a process of drying the pulverized coal is performed.
Coal as a raw material is low-coking coal (or lower coal) with low or no caking property and low price, and lignite, subbituminous coal and the like can be used. Low-grade coal such as lignite and sub-bituminous coal is pulverized by a dusting machine. Coal can be pulverized to a size of 60 mesh or less, for example.

  The pulverized coal removes moisture by a drying process. The moisture of the coal hinders the mixing of the coal and the solvent, destabilizes the reactor pressure, and reduces the reaction efficiency. In a present Example, it dries so that the moisture content of coal may be 20 wt% or less by a coal drying process. When the water content of coal exceeds 20 wt%, the process efficiency is reduced as described above, and an additional waste gas treatment process is required.

The pulverized and dried coal is mixed with a solvent and slurried. In the present embodiment, the coal dried with respect to the solvent is mixed at a weight ratio of 1/1 to 1/4.
If the ratio of coal to solvent is greater than 1/1, the amount of solvent is small and coal slurry is not well produced. This also reduces the coal conversion rate in the reactor.
When the ratio of coal to the solvent is lower than ¼, the solvent is mixed excessively, the viscosity of the coal slurry is lowered, the throughput in each step is increased, and the scale of the equipment is increased. As a result, there is a problem that the cost of the apparatus increases due to an increase in apparatus cost and utility usage.

Here, as the solvent, it is possible to use the remaining oil after finally separating the additive in the manufacturing process of the additive.
In the coal pretreatment process, a dispersed iron catalyst is introduced.
In this embodiment, the dispersed iron catalyst may be Fe ₂ O ₃ . Thus, the reactivity at the time of a liquefaction reaction can be improved by throwing a dispersion-type iron catalyst and mixing with a coal slurry.

The dispersed iron catalyst is added in an amount of 0.5 to 3.0 parts by weight with respect to 100 parts by weight of coal.
When the amount of the dispersed iron catalyst is less than the above range, the role as a catalyst cannot be sufficiently achieved, and when the above range is exceeded, recovery is difficult and there is an unfavorable effect because there are too many catalysts.

The coal slurried through the above process is transferred to a reactor and undergoes a coal liquefaction process. The coal slurry is heated to a desired temperature through a heating process while being transferred to the liquefaction process.
The coal liquefaction step is a step of liquefying the coal slurried in the pretreatment step at a sufficiently high temperature. Coal slurry and cracking gas are charged into the reactor, and the liquefaction reaction proceeds under the set temperature and pressure.

  In this embodiment, the coal liquefaction step is performed at a temperature of 250 to 450 ° C. and a pressure of 30 to 120 bar. The pressure inside the reactor can be controlled by adjusting the supply amount of cracking gas.

  By controlling the inside of the reactor within the temperature and pressure ranges, the liquefaction reaction proceeds with a mixture of coal and solvent, that is, coal slurry. At this time, the supplied cracking gas not only adjusts the pressure inside the reactor, but also serves to liquefy by linking broken rings between carbon atoms constituting the coal.

  In the coal liquefaction process, when the temperature is lower than 250 ° C, the coal is not melted, so the liquefaction process does not proceed. When the temperature exceeds 450 ° C, coal coking occurs and the coal hardens and reacts. Reduce.

  Further, when the reaction pressure is smaller than 30 bar in the coal liquefaction process, there is a problem that the pressure in the reactor is too low to supply hydrogen to the coal. On the other hand, when the pressure exceeds 120 bar, hydrogen is excessively donated to the coal, the production amount of the final product coke additive is reduced, and the production amount of undesired substances such as oil is increased.

In the coal liquefaction stage, COG, LNG, or a mixed gas thereof is supplied as the cracking gas.
Depending on the process conditions, either one of COG or LNG can be selectively used in the reactor, or both COG and LNG can be supplied into the reactor.
Thus, by using COG or LNG, the production amount of liquefied oil decreases in the coal liquefaction process, and the production amount of additives increases.

The cracking gas can be supplied by heating to 300 to 600 ° C. according to the internal temperature of the reactor in which the coal liquefaction reaction is performed. As a result, the change in the temperature inside the reactor when the cracking gas is introduced is minimized, and a decrease in reactivity can be prevented.
The product produced in the coal liquefaction step can be separated as a final target coke additive by the separation step.

  In this embodiment, the separation process is sequentially separated in a separating stage for separating a gas component from a liquefaction process product, a filtration stage for separating a liquid substance and a solid substance, and a filtration stage. A fractional distillation step in which the liquid material is distilled to separate the additive.

  The product liquefied through the coal liquefaction process includes all solid products, liquid products, and gaseous products. The liquid product can include coke additives and oil, and the gaseous product can include fuel gas, sulfur, ammonia, and the like.

The separating step separates the lightest gaseous components (C ₁ -C ₅ , H ₂ S, NH ₃ , H _2, etc.) in the material produced by the coal liquefaction process from the product. In the filtration step, the product is separated into a solid product and a liquid product.
The fractional distillation step subsequent to the filtration step is obtained by distilling the liquid product separated in the filtration step, and is finally obtained by separating the additive for coke.

In the present embodiment, the filtration step is performed at a temperature of 120 to 400 ° C.
The coke additive has a softening point of 120 ° C. inside or outside. Accordingly, when the temperature is lower than 120 ° C. in the filtration step, the coke additive is present as a solid product, which mixes the solid product with the coke additive, so that the coke is mixed. It becomes impossible to separate only the additive. Therefore, the filtration step is performed at a temperature of 120 ° C. or higher in consideration of the softening point of the coke additive.

  Further, as described above, since the coal liquefaction process is performed in a temperature range of 250 to 450 ° C., the product generated in the coal liquefaction process initially exists at a high temperature of 120 to 400 ° C. unless cooled. To do. Accordingly, when the filtration step is performed immediately after the coal liquefaction step without further heating the product in the filtration step, the filtration process can be performed at a temperature of 120 ° C. or more using the heat of the product. Accordingly, in the present embodiment, the filtration step needs to be performed immediately after the coal liquefaction process and before the product temperature falls to 120 ° C. or lower.

In the fractional distillation step, the liquid product separated through the filtration step can be distilled using a distiller to obtain a coke additive.
As described above, the liquid product separated in the filtration step contains not only the coke additive but also oil, and may further contain some fuel gas, sulfur, ammonia and the like depending on the temperature.

In the fractional distillation step, commonly used fractional distillation can be used.
In this embodiment, the fractional distillation stage is operated in a vacuum state and is performed at a temperature of 200 to 350 ° C. Since the oil in the liquid product has a boiling point lower than 200 to 350 ° C. under the pressure, the oil for coke can be obtained by separating and removing the oil from the liquid product using a fractional distillation method. . That is, when the liquid product is heated to a temperature of 200 ° C. to 350 ° C. in the fractional distillation step, the oil (Oil) evaporates and only the coke additive can be separated as a residue. This separates the oil in a fractional distillation step to finally obtain a coke additive.

In the recirculation step, the oil obtained in the separation step is supplied to the coal pretreatment step, whereby the oil is reused as a solvent for the coal slurrying step.
In this embodiment, the recirculation step immediately supplies the oil obtained by the fractional distillation step to the mixing drum of the coal pretreatment step.
Thus, the process can be simplified by immediately recirculating the oil separated in the separation process to the coal pretreatment process.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications may be made within the scope of the claims, the detailed description of the invention and the accompanying drawings. Of course, this is also within the scope of the present invention.

Claims (16)

A coal pretreatment step in which coal is dispersed in a solvent to form a slurry;
A step of producing a coal slurry by introducing a dispersed iron catalyst into the product of the coal pretreatment step;
A coal liquefaction step of reacting the coal slurry with a cracking gas to liquefy the coal slurry;
The product of the coal liquefaction process, comprising the steps of producing the L NG (Liquefied Natural Gas) supplies the liquefied product was further cracked gas,
Separating the coke additive from the liquefied product to produce a liquid oil;
A recirculation step in which the liquid oil obtained in the separation step is supplied to the coal pretreatment step and used as the solvent.   2. The method for producing a coke additive according to claim 1, wherein the coal pretreatment step mixes dry coal with respect to the solvent at a weight ratio of 1/1 to 1/4. The method for producing an additive for coke according to claim 2, wherein the dispersed iron catalyst is Fe ₂ O ₃ .   The method for producing an additive for coke according to claim 3, wherein the dispersed iron catalyst is added at a ratio of 0.5 to 3.0 parts by weight with respect to 100 parts by weight of coal. The separation step includes a separating step of separating a gas component from the liquefied product, a filtration step of separating a liquid substance and a solid substance, and the liquid substance separated in the filtration step. A fractional distillation step of separating the coke additive by distillation,
5. The recirculation process according to claim 1, wherein the oil separated from the coke additive in the fractional distillation stage is supplied to the coal pretreatment process. 6. The manufacturing method of the additive for cokes as described.   The method according to claim 5, wherein the filtering step is performed at a temperature of 120 to 400C.   The method for producing an additive for coke according to claim 6, wherein the fractional distillation step is performed at a temperature of 200 to 350 ° C. The method for producing an additive for coke according to claim 7, wherein the coal pretreatment process further includes a step of pulverizing the coal and a coal drying step of drying the pulverized coal.   The method for producing an additive for coke according to claim 8, wherein the coal drying step is performed such that the moisture content of the coal is 20 wt% or less.   The said coal liquefaction process is performed under the temperature of 250-450 degreeC, and the pressure of 30-120 bar, The manufacturing method of the additive for cokes of Claim 7 characterized by the above-mentioned.   The method for producing an additive for coke according to claim 10, wherein the coal liquefaction step supplies cracking gas by heating to 300 to 600 ° C. A mixing drum for mixing and slurrying the pretreated coal and solvent;
A catalyst supply unit for supplying a dispersion catalyst to the mixing drum;
A reactor for liquefying the coal slurry that has passed through the mixing drum;
A gas supply unit for supplying LNG (Liquid Natural Gas) as a cracking gas to the reactor;
A separation unit for separating the coke additive from the liquefied product produced in the reactor;
A supply line connected between the separation unit and the mixing drum and supplying oil separated by the separation unit to the mixing drum as a solvent;
An apparatus for producing an additive for coke, comprising:   The separation unit includes a separator that separates a gas component from a liquefaction process product, a filter device that is connected to the separator and separates a liquid material and a solid material, and a liquid material separated by the filter device. A distiller that separates the coke additive by distillation and is connected to the mixing drum via the supply line, and supplies the separated oil to the mixing drum. An apparatus for producing an additive for coke according to claim 12.   The additive for coke according to claim 13, wherein the manufacturing apparatus further includes a dusting machine for pulverizing coal and a dryer for drying the pulverized coal for coal pretreatment. manufacturing device.   The apparatus for producing an additive for coke according to any one of claims 12 to 14, wherein the catalyst supply unit is configured to supply a dispersed iron catalyst. The gas supply unit manufacturing apparatus coking additive according to claim 15, characterized in that the structure for supplying the L NG.

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