WO2016088963A1 - Method and apparatus for manufacturing cokes additive - Google Patents

Abstract

Provided is a method and apparatus for manufacturing a cokes additive, which is optimized for extraction of a cokes additive and can easily and effectively manufacture the additive, the method comprising: a coal pre-processing step for bringing coal into slurry by dispersing the coal in a solvent; a step for introducing a dispersed iron catalyst while pre-processing the coal; a coal liquefying step for liquefying the coal slurry by reacting the coal slurry with a cracking gas; a step for supplying a COG and/or an LNG as the cracking gas in the coal liquefying step; a separation step for separating an additive from the liquefied product; and a recycling step for supplying liquid oil obtained in the separation step to the coal pre-processing step and using the liquid oil as the solvent.

Description

Additive manufacturing method and apparatus for coke

Disclosed is a method and apparatus for producing additives for coke that can improve the strength of coke.

Generally, coke is manufactured through coke manufacturing process using coking coal. Raw coal used to manufacture coke is classified into coking coal and coking coal according to the degree of coking property. Stable operation of large blast furnaces requires the use of high strength coke. In order to manufacture high-strength coke, it is advantageous to use strong coking coal or to use a large amount of hard coking coal compared to uncoking coal. In the meantime, high quality and expensive coking coal was used in the manufacture of coke in large quantities.

However, due to the rapid increase in the demand for coking coal for metallurgy worldwide and the limited reserves of hard coal, it is becoming more difficult to secure hard coal, which causes a problem of price spikes. Therefore, the development of the technology which can manufacture high-strength coke, using non-coking coal, such as subgrade bituminous coal or lignite, as a raw coal, is progressing actively.

For example, a technology has been developed for producing a quality improver for coke production through a solvent extraction method in which low-quality raw coal is dissolved in an expensive supercritical solvent under high temperature and high pressure conditions to extract a caking material.

However, the conventional structure has a disadvantage in that an investment cost is excessively required due to the construction of a large-scale facility, and expensive hydrogen must be continuously supplied. For this purpose, an expensive facility such as a hydrogenation facility is required, which increases production costs. there is a problem.

In addition, conventionally, the focus is mainly on the production of oil from coal, which is insufficient to produce additives in large quantities.

Provided is a method and apparatus for preparing additives for coke optimized for extracting additives for coke.

In addition, the present invention provides an additive manufacturing method and apparatus for coke, which enables to easily and effectively produce additives for improving coke strength through a coal liquefaction process optimized for additive extraction.

The present invention also provides an additive manufacturing method and apparatus for coke that can produce additives without building a large-scale facility such as a hydrogenation facility.

In addition, the present invention provides a method and apparatus for producing additives for coke, which can simplify the manufacturing process.

In addition, the present invention provides a coke additive manufacturing method and a manufacturing apparatus that is capable of producing an additive for coke using low-grade coal.

The additive manufacturing method of the present embodiment includes a coal pretreatment step of dispersing coal in a solvent and slurrying it; Inputting a dispersed iron catalyst during coal pretreatment; A coal liquefaction step of liquefying the coal slurry by reacting the coal slurry with the cracking gas; Supplying COG and / or LNG as a cracking gas during the coal liquefaction process; A separation step of separating the additive from the liquefied product; And a recycling step of supplying the liquid oil obtained in the separation step to the coal pretreatment step to use as a solvent.

The coal pretreatment process may further include grinding coal and drying the pulverized coal.

The coal may comprise lignite or sub-bituminous coal.

In the coal crushing step, coal may be pulverized to a size of 60 mesh or less.

The coal drying step may be a structure for drying so that the water content of the coal is 20wt% or less.

The coal pretreatment process may have a structure in which the dried coal to a solvent is mixed at a weight ratio of 1/1 to 1/4 to slurry.

The dispersed iron catalyst may be Fe ₂ O ₃ .

The dispersed iron catalyst may be added at 0.5 to 3.0 parts by weight based on 100 parts by weight of coal.

The coal liquefaction process may be performed at a temperature of 250 to 450 ° C and a pressure of 30 to 120 bar.

The coal liquefaction process may be supplied by heating the cracking gas to 300 to 600 ℃.

The separation process includes a separating step of separating a gas component from a liquefied product, a filtration step of separating a liquid substance and a solid substance, and a fractional distillation step of distilling the liquid substance separated in the filtration step to separate an additive. And, the recycling process may be a structure for supplying the oil separated from the additive in the fractional distillation step to the coal pretreatment process.

The filtration step may be performed at a temperature of 120 to 400 ℃.

The fractional distillation step may be performed at a temperature of 200 to 350 ℃.

The production apparatus of the present embodiment is a mixing drum for mixing and slurrying the pretreated coal and the solvent, a catalyst supply unit for supplying a dispersion catalyst to the mixing drum, a reactor for liquefying the coal slurry passed through the mixing drum, cracking gas into the reactor A gas supply unit for supplying, a separation unit for separating an additive from the liquefied product generated from the reactor, and a supply line connected between the separation unit and the mixing drum to supply oil separated in the separation unit as a solvent to the mixing drum. It may include.

The separation unit is a separator for separating gaseous components from the liquefaction process product, a filter device connected to the separator to separate the liquid material and the solid material, and distilled liquid material separated from the filter device to separate the additives and the supply line It may be connected to the mixing drum through may include a distillator for supplying the oil separated from the additive to the mixing drum.

The manufacturing apparatus may further include a pulverizer for crushing coal for coal pretreatment, and a dryer for drying the pulverized coal.

The catalyst supply unit may have a structure for supplying a distributed iron catalyst.

The gas supply unit may have a structure for supplying COG and / or LNG.

Thus, according to this embodiment, it is possible to implement an optimized additive manufacturing process.

In addition, by optimizing the additive manufacturing process it is possible to produce coke additives more economically and efficiently.

In addition, by simplifying the process it is possible to reduce the cost to reduce the additive manufacturing cost.

In addition, it is not necessary to build a facility for producing hydrogen can lower the production cost.

1 is a schematic configuration diagram showing an additive manufacturing apparatus for coke according to the present embodiment.

The terminology used below is merely to refer to specific embodiments, and is not intended to limit the present invention. As used herein, the singular forms “a,” “an,” and “the” include plural forms as well, unless the phrases clearly indicate the opposite. As used herein, the meaning of “comprising” embodies a particular characteristic, region, integer, step, operation, element, and / or component, and other specific characteristics, region, integer, step, operation, element, component, and / or group. It does not exclude the presence or addition of.

Hereinafter, exemplary embodiments of the present invention will be described with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art can easily understand, the embodiments described below may be modified in various forms without departing from the concept and scope of the present invention. Accordingly, the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

1 schematically shows a configuration of an additive manufacturing apparatus for coke according to the present embodiment.

As shown in FIG. 1, the manufacturing apparatus of this embodiment includes a mixing drum 10 for slurrying a mixture of pretreated coal and a solvent and a catalyst supply unit 20 for supplying a dispersion catalyst to the mixing drum 10. In the reactor 30 for liquefying the coal slurry passed through the mixing drum 10, the gas supply unit 32 for supplying the cracking gas to the reactor 30, and additives in the liquefaction product generated from the reactor 30. Separator 40 for separation, and the supply line 50 is connected between the separator 40 and the mixing drum 10 to supply the oil separated in the separator to the mixing drum 10 as a solvent. Include.

The manufacturing apparatus may further include a crusher 12 for pulverizing coal and a dryer 14 for drying the pulverized coal in order to pretreat the coal.

Coal, which is a raw material for preparing an additive in the present embodiment, may include low grade non-coking coal such as lignite or sub-bituminous coal. Low-grade coal such as lignite and sub-bituminous coal has low physical properties such as cohesiveness, but abundant reserves and low cost, thereby lowering the production cost in the manufacture of additives for coke.

The mixing drum 10 mixes the pretreated coal and a solvent to form a coal slurry.

In the present embodiment, the solvent introduced into the mixing drum 10 is configured to utilize the remaining oil after finally separating the additive through the separation unit 40.

To this end, the supply line 50 is connected between the separation unit 40 and the mixing drum 10 so that the oil remaining after the additive separation is recycled to the mixing drum 10 through the supply line 50 as a solvent and supplied. .

As such, by supplying the liquid oil separated through the separating part 40 directly to the mixing drum 10 and recycling it as a solvent, the facility can be simplified and the process can be simplified to lower the additive production cost.

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

In this embodiment, the dispersed iron catalyst may be Fe ₂ O ₃ . In this way, by adding a dispersed iron catalyst and mixing in the coal slurry, it is possible to increase the reactivity during the liquefaction. Thus, even when COG or LNG is used as the cracking gas in the liquefaction reaction, the dispersed iron catalyst may increase the reactivity to draw a sufficient reaction effect for the additive production.

The coal slurry mixed in the mixing drum 10 is transferred to the reactor 30 by a high pressure pump. In the process of transferring the coal slurry from the mixing drum 10 to the reactor 30, the coal slurry is supplied by supplying heat to the coal slurry through the heating unit 16 installed between the mixing drum 10 and the reactor 30. Heat to

The reactor 30 is a container sufficiently resistant to high temperature and high pressure and having a reaction space therein, and liquefyes the coal slurry under high temperature and high pressure. A heater for applying thermal energy to the reactor 30 is installed outside the reactor 30, and an agitator may be installed inside the reactor 30. The gas supply unit 32 is connected to one side of the reactor 30 to supply a cracking gas to the reactor (30). In the present embodiment, the gas supply unit 32 supplies COG (Coke Oven Gas), LNG (Liquefied Natural Gas), or a combination thereof as a cracking gas.

In this way, by using COG or LNG as the cracking gas, the apparatus of this embodiment does not need to be equipped with a conventional hydrogen production facility. Hydrogen production facilities, as is known, are very complex, costing one-quarter of the total installation and operating costs. Therefore, in the present embodiment, since it is not necessary to build a hydrogen production equipment, it is possible to reduce the overall plant size and significantly reduce the production cost of the additive.

The separator 40 includes a separator 42 for separating gaseous components from the liquefied product, a filter device 44 connected to the separator to separate liquid and solid materials, and a liquid material separated from the filter device. Distillation 46 to distill to separate the additive for coke (B).

The still 46 of the separator 40 is connected to the mixing drum 10 through a supply line 50. Thus, the oil separated from the additive through the distillation 46 is supplied to the mixing drum 10 through a supply line. The distillation 46 may be used as a fractional distillation to separate the additive using the difference in boiling point.

In this way, the apparatus can finally produce the coke additive (B) through the separation unit 40.

Hereinafter, the additive manufacturing process according to the present embodiment will be described.

The additive manufacturing process includes a coal pretreatment process in which coal is dispersed in a solvent and slurried, a process of injecting a dispersed iron catalyst during coal pretreatment, a coal liquefaction process in which coal slurry and a cracking gas are liquefied, and coal Supplying COG and / or LNG as a cracking gas during the liquefaction process, a separation process for separating the additives from the liquefaction product, and a recycling process for supplying the liquid oil obtained in the separation process to the coal pretreatment process and using it as a solvent. do.

The coal pretreatment process is a process of preparing coal, which is a raw material for preparing an additive, and then grinding the coal and then drying the coal.

Coal, which is a raw material, is low coking coal (or lower coal) having low or no cohesiveness, and lignite, sub-bituminous coal and the like can be used. Low-grade coal, such as lignite and sub-bituminous coal, is crushed through a grinder. The pulverization of coal can be pulverized to a size of, for example, 60 mesh or less.

The pulverized coal is dried to remove moisture. Moisture in the coal interferes with coal and solvent mixing and destabilizes the reactor pressure, reducing the reaction efficiency. In this embodiment, the coal is dried to a water content of 20wt% or less through a coal drying process. When the water content of coal exceeds 20wt%, such process efficiency is lowered and an additional waste gas treatment process is required.

The pulverized and dried coal is mixed with the solvent and slurried. In the present embodiment, the dried coal to the solvent is mixed at 1/1 to 1/4 by weight.

When the ratio of coal to solvent is greater than 1/1, the amount of solvent is small so that coal slurry is not produced well. This will lower the coal conversion in the reactor. If the ratio of coal to solvent is lower than 1/4, the solvent is mixed so much that the viscosity of the coal slurry decreases, and the throughput increases in each process, thereby increasing the size of the plant. This leads to an increase in device cost and utility usage, resulting in cost problems.

Here, the solvent may use the oil remaining after the additive is finally separated through the additive manufacturing process.

In the coal pretreatment, a dispersed iron catalyst may be added.

In this embodiment, the dispersed iron catalyst may be Fe ₂ O ₃ . As such, by adding a dispersed iron catalyst and mixing the coal slurry, the reactivity can be increased during the liquefaction.

The dispersed iron catalyst may be added at 0.5 to 3.0 parts by weight based on 100 parts by weight of coal.

If the input of the dispersed iron catalyst is less than the above range can not play a role as a catalyst properly, if it exceeds the above range is difficult to re-recovery and too many catalysts have a bad effect.

Coalized slurried through the above process is transferred to the reactor through a coal liquefaction process. The coal slurry is heated to a desired temperature through a heating step in the transfer to the liquefaction process.

The coal liquefaction process is a step of liquefying coal slurried to a sufficiently high temperature in the pretreatment process. Coal slurry and cracking gas are introduced into the reactor, and liquefaction is performed at a set temperature and pressure.

In this embodiment, the coal liquefaction process may be performed at a temperature of 250 to 450 ℃, and a pressure of 30 to 120 bar. The pressure inside the reactor can be controlled by adjusting the flow rate of the cracking gas.

As the inside of the reactor is formed at the above temperature and pressure ranges, a liquefaction reaction proceeds in a mixture of coal and a solvent, that is, a coal slurry. In this case, the cracking gas supplied serves to liquefy the broken ring between the carbon atoms constituting the coal as well as the pressure control inside the reactor.

In the coal liquefaction process, if the temperature is lower than 250 ℃ coal is not melted (melting), the liquefaction process does not proceed, and if the temperature exceeds 450 ℃ coking of coal occurs and the coal hardens to lower the reaction.

In addition, when the reaction pressure is less than 30 bar in the coal liquefaction process, the pressure in the reactor is low, there is a problem that the donation of hydrogen to the coal does not occur. When the pressure exceeds 120 bar, hydrogen is excessively donated to coal, which reduces the output of coke additives, the final product, and increases the production of unwanted substances such as oil.

COG, LNG or a mixture thereof may be supplied to the cracking gas in the coal liquefaction step.

Depending on the process conditions, either the COG or LNG may be selectively used, or both the COG and LNG may be supplied into the reactor.

As such, by using COG or LNG, the amount of liquefied oil is reduced in the coal liquefaction process and the amount of additive is increased.

The cracking gas may be heated and supplied to 300 to 600 ° C. in accordance with the temperature inside the reactor in which the coal liquefaction is performed. Thus, when the cracking gas is added, changes in the temperature inside the reactor are minimized, thereby preventing a decrease in reactivity.

The product produced in the coal liquefaction process may be separated into the additive for coke as a final target through the separation process.

In the present embodiment, the separation process is a step of sequentially separating the gas component in the liquefaction process product (separating step), the filtration step of separating the liquid material and the solid material, and the liquid material separated in the filtration step to distill the additive Fractional distillation step of separating;

Products liquefied through a coal liquefaction process include all solid products, liquid products and gaseous products. Liquid products include additives for coke and oils, and gaseous products may include fuel gases, sulfur, ammonia, and the like.

The separating step separates the lightest gaseous components (C1 to C5, H ₂ S, NH ₃ , H _2, etc.) of the materials produced through 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 following the filtration step is to distill the liquid product separated in the filtration step, and finally, the additive for coke is separated and obtained.

In this embodiment, the filtration step may be performed at a temperature of 120 to 400 ℃.

The coking additive has a softening point of about 120 ° C. Therefore, when the temperature is lower than 120 ° C in the filtration step, the additive for coke is present as a solid product, and thus, only the additive for coke cannot be separated because the solid product and the additive for coke are mixed. Thus, the filtration step is performed at a temperature of 120 ℃ or more in consideration of the softening point of the additive for coke.

In addition, as mentioned, the coal liquefaction process is performed at a temperature of 250 to 450 ° C., so that the initial product produced in the coal liquefaction process is present at a high temperature of 120 to 400 ° C. unless cooled. Therefore, when the filtration step is performed immediately after the coal liquefaction process without further heating the product in the filtration step, the filtration process may be performed at a temperature of 120 ° C. or more using the heat of the product. Thus, in this embodiment, the filtration step needs to be performed immediately after the coal liquefaction process before the temperature of the product is lowered below 120 ° C.

In the fractional distillation step, the liquid product separated through the filtration step may be distilled using a distillation to obtain an additive for coke.

As mentioned, the liquid product separated in the filtration step contains oil as well as additives for coke, and may further include some fuel gas, sulfur, ammonia, etc. depending on the temperature.

In the fractional distillation step, a conventionally used fractional distillation may be used.

In this embodiment, the fractional distillation step is operated in a vacuum state, it can be carried out at a temperature of 200 to 350 ℃. Since the oil in the liquid product has a boiling point lower than 200 to 350 ° C. under the pressure, the oil can be separated and removed from the liquid product using a fractional distillation method to obtain an additive for coke. That is, when the liquid product is heated to a temperature of 200 ℃ to 350 ℃ in the fractional distillation step, the oil (Eil) is evaporated and it is possible to separate only the additive for coke as a residue. Thus, the oil is separated through a fractional distillation step to finally obtain an additive for coke.

The recirculation process feeds the oil obtained in the separation process to the coal pretreatment process, whereby the oil is recycled into the solvent of the coal slurrying process.

In this embodiment, the recycle process is to supply the oil obtained through the fractional distillation step directly to the mixing drum of the coal pre-treatment process. As such, the oil separated in the separation process is directly recycled to the coal pretreatment process, thereby simplifying the process.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the range of.

Claims (16)

A coal pretreatment step of slurrying coal by dispersing it in a solvent; Inputting a dispersed iron catalyst during coal pretreatment; A coal liquefaction step of liquefying the coal slurry by reacting the coal slurry with the cracking gas; Supplying COG and / or LNG as a cracking gas during the coal liquefaction process; A separation step of separating the additive from the liquefied product; And Recirculation process in which the liquid oil obtained in the separation process is supplied to the coal pretreatment process and used as a solvent. Coke additive production method comprising a. The method of claim 1, The coal pretreatment process is a method for producing coke additives for mixing the dried coal with respect to the solvent in a weight ratio of 1/1 to 1/4. The method of claim 2, The dispersed iron catalyst is Fe2O3 coke additive production method. The method of claim 3, wherein The dispersion iron catalyst is a coke additive production method is added to 0.5 to 3.0 parts by weight with respect to 100 parts by weight of coal. The method according to any one of claims 1 to 4, The separation process includes a separating step of separating a gas component from a liquefied product, a filtration step of separating a liquid substance and a solid substance, and a fractional distillation step of distilling the liquid substance separated in the filtration step to separate an additive. and, The recycling process is a coke additive manufacturing method for supplying the oil separated from the additive in the fractional distillation step to the coal pretreatment process. The method of claim 5, wherein The filtration step is an additive manufacturing method for coke is carried out at a temperature of 120 to 400 ℃. The method of claim 6, The fractional distillation step is coke additive production method performed at a temperature of 200 to 350 ℃. The method of claim 7, wherein The coal pretreatment process further includes the step of pulverizing coal and drying the pulverized coal. The method of claim 8, The coal drying step is a coke additive manufacturing method for drying so that the water content of the coal is 20wt% or less. The method of claim 7, wherein The coal liquefaction process is a coke additive production method made at a temperature of 250 to 450 ℃, and a pressure of 30 to 120 bar. The method of claim 10, The coal liquefaction process is a coke additive production method for supplying a cracking gas heated to 300 to 600 ℃. Mixing drum for slurrying by mixing pretreated coal and solvent, Catalyst supply unit for supplying a dispersion catalyst to the mixing drum, Reactor for liquefying the coal slurry passed through the mixing drum, Gas supply unit for supplying the cracking gas to the reactor, A separator for separating the additive from the liquefied product produced from the reactor, and A supply line connected between the separation unit and the mixing drum to supply oil separated in the separation unit as a solvent to the mixing drum Additive manufacturing apparatus for coke comprising a. The method of claim 12, The separation unit is a separator for separating gaseous components from the liquefaction process product, a filter device connected to the separator to separate the liquid material and the solid material, and distilled liquid material separated from the filter device to separate the additives and the supply line Connected to the mixing drum through the additive manufacturing apparatus for coke comprising a distillation for supplying the oil separated from the additive to the mixing drum. The method of claim 13, The apparatus for producing coke additives further comprises a pulverizing coal for coal pretreatment, and a dryer for drying the pulverized coal. The method according to any one of claims 12 to 14, The catalyst supply unit additive manufacturing apparatus for coke having a structure for supplying a dispersed iron catalyst. The method of claim 15, The gas supply unit coke additive manufacturing apparatus of the structure for supplying COG and / or LNG.

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