KR101759327B1 - Method and apparatus for producing binder for coke - Google Patents

Abstract

Separating step of separating the gaseous component from the liquefied product so as to maximize the solid-liquid separation efficiency with respect to the viscous liquefied slurry in preparing the additive for coke, separating the liquefied product through the separating step into a supercritical solvent Separating the supercritical fluid from the supernatant fluid, separating the supernatant fluid from the supercritical fluid, separating the supernatant fluid from the supercritical fluid, separating the supernatant fluid from the supernatant fluid, The method comprising the steps of:

Description

TECHNICAL FIELD [0001] The present invention relates to an additive for coke,

A manufacturing method and an apparatus for manufacturing an additive for coke used for improving coke strength are disclosed.

Generally, coke is produced through a coke making process using coking coal. The coking coal used to manufacture the coke is classified as hard-boiled and un-boiled, depending on the degree of cohesion. For stable operation of large blast furnaces, the use of high-strength coke is required. In order to produce a high-strength coke, it is advantageous to use strong coals having excellent cohesiveness or to use a large amount of coals compared to uncoated coals. In the meantime, a large amount of high-priced, high-priced strong coals has been used in the production of coke.

However, due to the rapid increase in demand for coking coal for metallurgical use globally and the limited reserves of hard-boiled coals, it has become increasingly difficult to secure strong coals, which has led to a surge in prices. Accordingly, the development of a technique for manufacturing high-strength coke while using low-cost and low-cost coking coal such as bituminous coal or lignite as coking coal is actively under way.

For example, a technique has been developed for producing a quality improving agent for coke production through a sales method in which a low-grade raw material is dissolved in an expensive supercritical solvent under a high-temperature and high-pressure condition to extract a cohesive substance.

However, nowadays, the focus is mainly on the production of oil from coal, so there is no optimized process for the extraction of additives, which is insufficient to produce additives effectively. In addition, there is a problem that the economical efficiency in production of additives is inferior due to frequent breakdown and new operating know-how by using existing coal direct liquefaction type process.

Accordingly, it is required to develop an optimized and differentiated technique capable of effectively producing additive for coke.

A method and an apparatus for manufacturing an additive for coke which are capable of more effectively separating additives for coke and residues in manufacturing additives for coke.

The present invention also provides a method and apparatus for manufacturing an additive for coke which can maximize the solid-liquid separation efficiency with respect to a viscous liquefied slurry.

The additive manufacturing method of this embodiment includes: a coal pretreatment step of dispersing coal into a slurry by dispersing it in a solvent; A step of adding a dispersed iron catalyst during the pretreatment of coal; A coal liquefaction process for liquefying coal slurry by reacting coal slurry with cracking gas; A step of supplying COG and / or LNG with a cracking gas during a coal liquefaction process; A separation step of separating the additive from the liquefied product; And a recycle process in which the liquid oil obtained in the separation process is supplied to the coal pretreatment process and used as a solvent.

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

The coal may comprise lignite or sub-bituminous coal.

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

The step of drying the coal may include drying the coal so that the moisture content of the coal is 10 wt% or less.

The coal pretreatment may be performed by mixing the dried coal with the solvent at a weight ratio of 1/1 to 1/4 to form a slurry.

The dispersed iron catalyst may be Fe ₂ O ₃ .

The dispersed iron catalyst may be added in an amount of 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 DEG C and a pressure of 30 to 120 bar.

The coal liquefaction process may be performed by heating the cracking gas at 400 to 600 ° C.

The separating step includes a separating step of separating the gas component from the liquefied product, a dissolving step of mixing the supercritical solvent into the liquefied product through the separating step to form a liquefied product as a supercritical fluid, And a separating step of separating the additive from the supercritical fluid through the first separation step.

The separation step may further include an oil separation step of separating the oil from the supercritical fluid through the additive separation step.

The separating step may further include a solvent separating step of separating the solvent from the supercritical fluid through the separating agent separation step.

The separation step may further include recycling the supercritical solvent separated from the oil through the oil separation step to the mixing step.

The supercritical solvent may be at least one selected from propane or pentane.

The residue separation step may include separating the solid matter from the supercritical fluid through at least one cyclone.

The apparatus for producing an additive according to this embodiment comprises a mixer for mixing a pretreated coal and a solvent into a slurry, a catalyst supply unit for supplying the dispersed iron catalyst to the mixer, a reactor for liquefying the coal slurry through the mixer, A separator for separating the additive from the liquefied product generated from the reactor, a separator connected between the separator and the mixer for supplying the oil separated from the separator to the mixer as a solvent, And a supply line for supplying the supply voltage.

The separator includes a separator for separating the gas component from the liquefied product, a dissolving unit connected to the separator to form a supercritical fluid in the liquefaction product passed through the separator to form a supercritical fluid, a supercritical fluid connected to the dissolving unit, And an additive separator connected to the residue separator and separating the additive from the supercritical fluid in which the solid material is separated.

Wherein the dissolving unit comprises a mixing mixer for mixing a liquefied product and a supercritical solvent to form a supercritical fluid, a pressurizing pump installed on the liquefied product supply line of the mixed mix for pressurizing the liquefied product to a supercritical fluid critical pressure, To a supercritical fluid critical temperature.

The separator may further include an oil separator connected to the additive separator and separating the oil from the supercritical fluid from which the additive is separated.

The separator may further include a solvent separator connected to the additive separator to separate the solvent from the supercritical fluid from which the additive is separated.

The supercritical solvent may be at least one selected from propane or pentane.

The residue separation unit may include at least one cyclone separating the supercritical fluid and the solid matter.

The additive separator may include a first container in which the supercritical fluid flows into the first separator and an additive is separated in response to a change in temperature, and a first heat exchanger installed in the inflow line of the first container to increase the temperature of the supercritical fluid.

Wherein the solvent separator comprises a second container in which the supercritical fluid flows into the second separator and the solvent is separated according to a change in temperature, a second compressor installed in an inflow line of the second container to regulate the pressure and temperature of the supercritical fluid, A heat exchanger.

Wherein the oil separator comprises: a third container in which supercritical fluid flows into the oil separator and the oil is separated according to a change in temperature; a third compressor installed in an inflow line of the third container to adjust the pressure and temperature of the supercritical fluid; A heat exchanger.

And a recovery line connected between the oil separation unit and the dissolution unit to supply the supercritical solvent from which oil has been separated to the dissolution unit.

A first compressor installed in the recovery line for transferring the supercritical solvent and controlling the pressure, and a heat exchanger for lowering the temperature.

The manufacturing apparatus may further include a crusher for crushing coal for pretreatment of coal, and a drier for drying the crushed coal.

The coal may comprise lignite or sub-bituminous coal.

The pulverizer can pulverize coal to a size of 60 mesh or less.

The dryer may be configured to dry the coal so that the moisture content of the coal is 10 wt% or less.

The catalyst supply unit may be configured to supply Fe ₂ O ₃ as a dispersed iron catalyst.

The catalyst supply unit may be charged with 0.5 to 3.0 parts by weight of the dispersed iron catalyst per 100 parts by weight of coal.

As described above, according to this embodiment, the liquefied product having a high viscosity can be supercritical fluidized to improve the separation efficiency for the main products such as solid phase materials, additives, various oils, and the like, and separate the components into higher purity.

In addition, since the filter is not used, problems such as clogging of the filter are prevented from occurring, and the separation operation is performed more effectively, so that the productivity of the coke additive can be increased.

1 is a schematic structural view showing an apparatus for producing additive for coke according to this embodiment.
2 is a schematic view showing a filter device of an apparatus for producing additive for coke according to this embodiment.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. The singular forms as used herein include plural forms as long as the phrases do not expressly express the opposite meaning thereto. Means that a particular feature, region, integer, step, operation, element and / or component is specified, and that other specific features, regions, integers, steps, operations, elements, components, and / And the like.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the 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.

Fig. 1 schematically shows the construction of an apparatus for producing additive for coke according to this embodiment.

As shown in FIG. 1, the additive manufacturing apparatus of the present embodiment includes a mixer 10 for mixing a pretreated coal and a solvent into a slurry, a catalyst supply unit 20 for supplying a dispersion catalyst to the mixer 10, A reactor 30 for liquefying a coal slurry through the reactor 10, a gas supply 32 for supplying a cracking gas to the reactor 30, a separator 30 for separating the additive from the liquefied product generated from the reactor 30, And a supply line 50 connected between the separator 40 and the mixer 10 to supply the oil separated from the separator to the mixer 10 as a solvent.

The manufacturing apparatus may further include a crusher 12 for crushing coal and a drier 14 for drying the crushed coal to pretreat coal.

In this embodiment, the raw material for the additive manufacturing coal may include low-grade non-coking coal such as lignite and sub-bituminous coal. Low-grade carbon such as lignite and bituminous coal has low physical properties such as cohesiveness, but it is rich in resources and low in cost, so that it is possible to lower the production cost when manufacturing additive for coke.

The mixer 10 mixes the pretreated coal with a solvent to form a coal slurry.

In the present embodiment, the solvent introduced into the mixer 10 is structured such that the additive is finally separated through the separator 40 and the remaining oil is utilized.

To this end, the feed line 50 is connected between the separator 40 and the mixer 10 so that the oil remaining after the additive separation is recycled as solvent to the mixer 10 via the feed line 50.

As described above, the liquid oil separated through the separator 40 is directly supplied to the mixer 10 and recycled as a solvent, so that the facility can be simplified, and the process can be simplified to reduce the cost of producing the additive.

The catalyst supply unit 20 is connected to the mixer 10 to supply a dispersed iron catalyst. Thus, the dispersed iron catalyst is evenly mixed with the coal and the solvent in the mixer 10.

In this embodiment, the dispersed iron catalyst may be Fe ₂ O ₃ . By adding the dispersed iron catalyst to the coal slurry in this way, the reactivity in the liquefaction reaction can be increased. Accordingly, even when COG or LNG is used as the cracking gas in the liquefaction reaction, the dispersed iron catalyst can increase the reactivity and can obtain a sufficient reaction effect for the production of the additive.

The mixed coal slurry in the mixer 10 is conveyed to the reactor 30 by a high-pressure pump. The coal slurry is supplied to the coal slurry through the heating unit 16 provided between the mixer 10 and the reactor 30 in the process of transferring the coal slurry from the mixer 10 to the reactor 30, can do.

The reactor 30 is a vessel which is sufficiently resistant to high temperature and high pressure and has a reaction space therein, and liquefies the coal slurry under high temperature and high pressure.

A heater or the like for applying thermal energy to the reactor 30 is installed outside the reactor 30, and an agitator may be installed therein. 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.

Thus, by using COG or LNG as the cracking gas, the apparatus of this embodiment does not need to be provided with a conventional hydrogen production facility. The hydrogen production facility is very complicated as it is known. The construction cost is 1/4 of the total installation cost and the operation cost is also high. Therefore, in the case of this embodiment, since it is not necessary to construct a hydrogen production facility, the entire plant scale can be reduced and the production cost of the additive can be greatly reduced.

The separator 40 is connected to the mixer 10 via a supply line 50. Thus, the oil finally separated from the additive through the separator is supplied to the mixer 10 via the feed line. Thus, the apparatus can finally produce the coke additive (B) through the separator (40).

In the present embodiment, the separator 40 has a structure capable of maximizing separation efficiency by separating solid and liquid components in a supercritical fluid state using a supercritical solvent.

2 illustrates the structure of the separator according to the present embodiment. Hereinafter, the structure of the separator of this embodiment will be described with reference to FIG.

The coal liquefied product is in the form of a slurry and has a very high viscosity and solid residue which is an indefinite non-liquefied coal waste, so that it is difficult to divide easily into a liquid and a solid, and in the case of a separation device using a conventional filter, A phenomenon may occur that the piping is closed during the transferring process. In addition, in the case of the structure using the conventional filter, since the oil component including the additive accounts for more than 50% of the separated solid matter, the productivity of the additive is lowered and the additive and the oil are additionally added Extraction process is required.

Accordingly, the separation unit 40 of the present embodiment increases the separation efficiency of the main products such as solid-phase materials, additives, various oils, etc. by making supercritical fluid having a high viscosity, Or more in terms of high purity.

For this purpose, the separator 40 of this embodiment includes a separator 41 for separating the gas component from the liquefied product, a supercritical fluid which is connected to the separator 41 to mix the supercritical solvent with the liquefied product passing through the separator 41, A residue separation part 43 connected to the dissolution part and separating the solid matter not dissolved in the solvent in the supercritical fluid, and a residue separation part 43 connected to the residue separation part 43, And an additive separator 44 for separating the additive from the supercritical fluid.

Here, the supercritical solvent is a supercritical solvent for dissolving the liquefied product into a supercritical fluid. Supercritical fluid refers to a substance that has reached a critical state, which is characterized by gas and liquid properties, beyond the limits of a certain high temperature and high pressure, which is generally referred to as a supercritical point, in a liquid or gaseous state.

In this embodiment, the supercritical solvent may be at least one selected from light gases including propane or pentane.

The separation unit 40 may further include an oil separation unit 46 connected to the additive separation unit 44 and separating the oil from the supercritical fluid from which the additive is separated.

The separator 40 may further include a solvent separator 45 connected to the additive separator 44 to separate the solvent from the supercritical fluid from which the additive is separated.

The separation unit 40 may further include a recovery line 47 connected between the oil separation unit 46 and the dissolution unit 42 to supply supercritical solvent separated from the oil to the dissolution unit have.

The dissolving unit 42 includes a mixing mixer 421 that mixes the liquefied product and the supercritical solvent to form a supercritical fluid, and a supply line 422 that is provided on the supply line 422 of the mixing mixer to convert the liquefied product into a supercritical fluid critical pressure A pressurizing pump 423 for pressurizing the liquid product, and a heat exchanger 424 for controlling the liquefied product to a supercritical fluid critical temperature.

The mixing mixer 421 mixes the liquefied product and the supercritical solvent under a predetermined temperature and pressure to form a liquefied product in a supercritical fluid state. The mixture mixer 421 is connected to the separator 41 through a supply line 422 and the liquefied product passing through the separator 41 is transferred to the mixing mixer 421 through a supply line 422. The pressurizing pump 423 provided on the supply line 422 transfers the liquefied product and pressurizes the liquefied product to a supercritical fluid threshold pressure or higher of the solvent. In addition, the heat exchanger 424 installed on the supply line 422 regulates the liquid product to an appropriate temperature for forming the supercritical fluid.

A recovery line 47 for supplying a supercritical solvent into the mixing mixer 421 is connected to one side of the mixing mixer 421. The supercritical solvent or the supercritical solvent that has been recovered through the process is supplied into the mixing mixer 421 through the recovery line 47. The liquefied product in the slurry state introduced into the mixing mixer 421 through the supply line is mixed with the supercritical solvent in the mixing mixer 421 and dissolved in the supercritical solvent at an appropriate pressure and temperature to form a supercritical fluid.

The residue separator 43 may include at least one cyclone 431 separating the supercritical fluid and the solid matter. The supercritical fluid passes through the cyclone 431 and the solid matter is separated and discharged, and the rest is discharged upward, and the solid matter is separated.

As shown in FIG. 2, in the present embodiment, the residue separator 43 may have a structure in which three cyclones 431 are organically coupled. By performing the separation process by arranging the plurality of cyclones in multiple stages in this way, the recovery efficiency of the solid phase material can be further increased.

The supercritical fluid transferred to the residue separation unit 43 is separated from the solid particles while passing through the plurality of cyclones 431. Solids are coal particles that remain unreacted and do not dissolve in the supercritical solvent. They are not easily separated because they are very small in size. Thus, the supercritical fluid in which the solid matter is separated first through the cyclone is further separated from the solid matter through the next cyclone. By separating the solid material again through the plurality of cyclones 431, the separation efficiency can be maximized. The separated supercritical fluid is transferred to the additive separator 44 along the process line.

A separate line 432 is connected between the residue separation unit 43 and the recovery line 47 so that part of the supercritical fluid delivered to the additive separation unit 44 is returned to the recovery line 472 through the line 432, (47), is returned to the mixing mixer (421) through the recovery line, and passes through the residue separation unit (43) again. Thus, it is possible to separate the solid matter that is not dissolved in the supercritical solvent with high purity through the residue separator 43.

The supercritical fluid passing through the residue separation section 43 is separated into various substances depending on the components including additives in accordance with the change of solubility.

In this embodiment, the additive separator 44, the solvent separator 45, and the oil separator 46 are sequentially connected to the separator 40. The solubility of propane or pentane in supercritical solvents varies with temperature. Accordingly, when the supercritical fluid is transferred to each separating unit 40 while changing the temperature, the additives and the solvent oil in the range of boiling point, which is not dissolved, are precipitated. Accordingly, the supercritical fluid from which the solid matter is removed while passing through the separator 40 is obtained by sequentially separating the high-purity additive, the solvent and the oil. Hereinafter, the structure of each component will be described according to the order of separation of various components.

The additive separator 44 includes a first container 441 through which the supercritical fluid flows into the first separator 44 and the additive is separated according to a change in temperature, a second container 441 installed in the inflow line 442 of the first container 441, And a first heat exchanger 443 for increasing the temperature of the first heat exchanger 443.

The first container 441 has a tank-shaped container structure having a space in which a supercritical fluid is received, and its shape and size can be variously modified.

The first heat exchanger 443 heats the supercritical fluid flowing into the first container 441 and controls the temperature of the supercritical fluid to the temperature just before the additive can be precipitated before entering the first container 441 .

Since the solubility of the supercritical solvent of the present embodiment increases as the temperature increases, the additive can be precipitated in the supercritical fluid in high purity by raising the temperature of the supercritical fluid through the first heat exchanger 443.

As the supercritical fluid passes through the first vessel 441, the additive B is separated and precipitated to the bottom. The supercritical fluid from which the additive is separated is transferred to the solvent separator 45 along the process line.

The solvent separator 45 includes a second container 451 through which the supercritical fluid flows into the first separator 45 and the solvent is separated according to a change in temperature, a second container 451 installed in the inflow line 452 of the second container, A second compressor 453 and a second heat exchanger 454 for controlling the temperature.

The second container 451 is a tank-type container structure having a space in which a supercritical fluid is received, and its shape and size can be variously modified.

The second compressor 453 compensates for the pressure loss caused by the supercritical fluid being transferred. The supercritical fluid is pressurized by the second compressor and returned to the required pressure of the supercritical fluid while being transported through the inlet line of the second vessel. The second heat exchanger 454 installed in the inflow line 452 heats the supercritical fluid flowing into the second vessel so that the temperature of the supercritical fluid up to the temperature just before the solvent can be precipitated before entering the second vessel .

Since the solubility of the supercritical solvent of the present embodiment increases as the temperature increases, the solvent dissolved in the supercritical fluid can be precipitated by increasing the temperature of the supercritical fluid.

Through the second container 451, the supercritical fluid separates and separates the solvent downward. The supercritical fluid from which the solvent has been separated is transferred to the oil separator 46 along the process line.

The oil separator 46 includes a third container 461 through which the supercritical fluid flows into the first separator 46 and separates the oil according to the temperature change, And a third compressor 463 and a third heat exchanger 464 for controlling the temperature.

The third container 461 is a tank-type container structure having a space in which a supercritical fluid is accommodated, and its shape and size can be variously modified.

The third compressor 463 compensates for the pressure loss caused by the supercritical fluid being transferred. The supercritical fluid is pressurized by the third compressor while being transferred through the inlet line of the third vessel to recover the required pressure of the supercritical fluid. The third heat exchanger 464 installed in the inflow line 462 heats the supercritical fluid flowing into the third vessel to the temperature of the supercritical fluid to the temperature just before the oil can be precipitated before entering the third vessel .

Since the solubility of the supercritical solvent of the present embodiment increases as the temperature increases, the oil dissolved in the supercritical fluid can be precipitated by raising the temperature of the supercritical fluid.

The supercritical fluid separates and segregates the oil into the lower part through the third vessel 461.

A recovery line 47 is connected between the third vessel 461 and the mixing mixer 421. The supercritical solvent remaining after the oil is finally separated from the third vessel is supplied to the mixing mixer 421). A first compressor 471 and a heat exchanger 472 are provided on the recovery line 47 for controlling the pressure and temperature of the supercritical solvent. The first compressor 471 installed in the recovery line 47 transfers the supercritical solvent to the mixer and pressurizes the supercritical solvent to a critical pressure of the supercritical solvent. The heat exchanger 472 provided in the recovery line 47 lowers the temperature of the high-temperature supercritical solvent heated while passing through the separation unit 40, thereby increasing the solubility of the supercritical solvent.

As described above, the separation unit 40 of the present embodiment can dissolve the liquefied product with the supercritical solvent, thereby improving the separation efficiency of the solid-phase material and separating the oil of various components including the additive with high purity.

Hereinafter, a process for producing an additive according to this embodiment will be described.

The process for preparing the additive includes a coal pretreatment process in which coal is dispersed in a solvent to form a slurry, a process of adding a dispersed iron catalyst in coal pretreatment, a coal liquefaction process in which coal slurry is reacted with cracking gas to liquefy coal slurry, A process of supplying COG and / or LNG with cracking gas during the liquefaction process, a process of separating the additive from the liquefied product, and a recirculation process of supplying the liquid oil obtained in the separation process to the coal pretreatment process to use as a solvent do.

The coal pretreatment process is a process of preparing coal as a raw material for the preparation of additives by pulverizing the coal and then drying the pulverized coal.

Coal as raw material is low tin (or low grade) coal with low or no cohesion and low price, and lignite, bituminous coal can be used. Low-grade coal such as lignite and bituminous coal is crushed through a crusher. The pulverization of the coal can be carried out, for example, to a size of 60 meshes or less.

The pulverized coal is subjected to a drying process to remove moisture. Moisture of coal interferes with the mixing of coal and solvent and makes reactor pressure unstable, which lowers reaction efficiency. In this embodiment, the coal is dried so as to have a water content of 10 wt% or less through the coal drying process. When the water content of the coal exceeds 10 wt%, the process efficiency is lowered and additional waste gas treatment steps are required.

The pulverized and dried coal is mixed with a solvent and slurried. In this embodiment, the coal dried for the solvent is mixed at a weight ratio of 1/1 to 1/4.

When the ratio of coal to the solvent is larger than 1/1, the amount of the solvent is small and the coal slurry is not well formed. Thus, the conversion rate of coal in the reactor is also lowered. When the ratio of coal to solvent is lower than 1/4, the viscosity of the coal slurry is lowered by adding too much solvent, and the throughput is increased in each step, thereby increasing the scale of the equipment. As a result, equipment costs and utility usage are increased, resulting in cost problems.

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

The dispersed iron catalyst may be added during the coal pretreatment.

In this embodiment, the dispersed iron catalyst may be Fe ₂ O ₃ . As described above, by adding the dispersed iron catalyst and mixing it with the coal slurry, the reactivity in the liquefaction reaction can be increased.

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

When the amount of the dispersed iron catalyst is less than the above range, the catalyst can not be used as a catalyst. If the amount exceeds the above range, it is difficult to regenerate the catalyst and the catalyst is adversely affected.

The coal slurried through the above process is transferred to the reactor and subjected to a coal liquefaction process. The coal slurry is heated to the desired temperature through the heating process during the transfer to the liquefaction process.

The coal liquefaction process is a process of liquefying the coal slurried at a sufficiently high temperature in the pretreatment process. The coal slurry and the cracking gas are introduced into the reactor and the liquefaction reaction is carried out under the set temperature and pressure.

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

As the inside of the reactor is set to the above temperature and pressure range, a liquefaction reaction proceeds in a mixture of coal and a solvent, that is, a coal slurry. At this time, the supplied cracking gas not only regulates the pressure inside the reactor, but also serves to liquefy the broken loop between the carbon atoms constituting the coal.

When the temperature is lower than 250 ° C in the coal liquefaction process, the coal is not melted and the liquefaction process does not proceed. When the temperature exceeds 450 ° C, the coal is caulked and the coal is hardened and hardened.

Also, when the reaction pressure is less than 30 bar in the liquefaction process of coal, the pressure in the reactor is low so that donation of hydrogen to coal does not occur. If the pressure exceeds 120 bar, hydrogen will be excessively supplied to the coal, resulting in a reduction in the final production of coke additive, and an increase in the production of undesirable materials such as oil.

In the coal liquefaction step, COG, LNG, or a mixed gas thereof may be supplied as the cracking gas.

Depending on the process conditions, either COG or LNG can be selectively used in the reactor, or both COG and LNG can be used to feed the reactor.

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

The cracking gas may be supplied by heating at 400 to 600 ° C in accordance with the internal temperature of the reactor in which the coal liquefaction reaction is performed. Therefore, when the cracking gas is introduced, the change in the temperature inside the reactor is minimized, and the degradation of reactivity can be prevented.

The product produced in the coal liquefaction process can be separated into coke additive, which is the final target through the separation process.

In this embodiment, the separation step is a step of separating the gas component from the liquefied product, mixing and dissolving the separated liquefied product into the supercritical solvent to form a liquefied product into the supercritical fluid, The undissolved solid material is separated and separated to the high purity of the constituent materials including additives.

The products liquefied through the coal liquefaction process include both solid products, liquid products and gaseous products. The liquid product includes an additive for coke and an oil, and the gaseous product may include fuel gas, sulfur, ammonia, and the like.

The separation step is to separate from the rating of the light gas component (C1 to _{C5, H 2 S, NH 3} , H 2 , etc.) the product of the substance produced through the coal liquefaction process.

The liquefied product in which the gaseous components are separated through the separating process is mixed with the supercritical solvent to form a supercritical fluid. Thus, the liquefied product is completely dissolved in the supercritical solvent except for the solid matter that is not soluble in the solvent, and the solid matter can be completely separated from the sidewall, and the oils of various components including additives can be separated in high purity.

In the supercritical fluid, the solid matter which is not dissolved in the solvent through the cyclone is separated and removed. The supercritical fluid separated from the solid matter is separated into components by additives, solvents, and oils by changing the pressure and temperature conditions through the respective separation processes.

Ultimately, the oil is separated and the supercritical solvent is reused as a supercritical solvent that is transferred to the mixing stage through the recovery line and mixed with the liquefied product.

Table 1 below shows the content of each substance in each step of separating the liquefied product according to the present embodiment.

Mixed before Additive separation Before solvent separation Before oil separation Solid matter
(residue) 15 0 0 0 additive 12 15 0 0 Solvent 71 83 98 0 oil 2 2 2 100

In Table 1, the ratio of the supercritical fluid to the solid material is 10 to 15: 1 Vol%, and the unit of the value is wt% excluding the supercritical fluid. The term " pre-mixing " means the position before the mixing mixer of the dissolution part in FIG. 2, before the additive separation means the position of the first container in the additive separation part, and before the solvent separation, And before oil separation means the front position of the third container of the oil separator.

According to the present embodiment, supercritical fluid is analyzed for the supercritical fluid at each position in the process of separating each material component into a supercritical fluid.

As a result of the experiment, it can be seen that the solid material is separated at high purity through the cyclone as shown in Table 1, and is not shown at the subsequent stage. Thus, it can be seen that the separation efficiency of the solid material is improved in this embodiment.

Additive and solvent were not detected after the respective separation processes. Finally, only the oil was detected in the process before the oil separation and the other substances were not detected, so that the respective additives, the solvent and the oil Is separated at high efficiency.

Thus, by dissolving the liquefied product in a supercritical solvent to form supercritical fluid and separating each component material, the separation efficiency can be enhanced and each component can be separated with high purity as in the embodiment.

The oil obtained in the separation step is recycled to the coal pretreatment process and recycled as a solvent in the coal slurry process.

In this embodiment, the oil obtained through the oil separation step is directly supplied to the mixer of the coal pretreatment process. Thus, the oil separated in the separation step can be recycled directly to the coal pretreatment process, thereby simplifying the process.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Of course.

10: mixer 12: crusher
14: dryer 20: catalyst supplier
30: Reactor 32: Gas supply part
40: separator 41: separator
42: dissolution part 43: residue separation part
44: additive separator 45: solvent separator
46: oil separator 47: recovery line
50: feed line 421: mixing mixer
422: supply line 423, 443, 454, 464, 472: heat exchanger
424: Pressurizing pump 431: Cyclone
441: first container 451: second container
461: Third container 453,463,471: Compressor

Claims (23)

A coal pretreatment step of dispersing coal into a slurry by dispersing it in a solvent; A step of adding a dispersed iron catalyst during the pretreatment of coal; A coal liquefaction process for liquefying coal slurry by reacting coal slurry with cracking gas; A step of supplying COG and / or LNG with a cracking gas during a coal liquefaction process; A separation step of separating the additive from the liquefied product; And a recycle process in which the liquid oil obtained in the separation process is supplied to the coal pretreatment process and used as a solvent,
The separating step includes a separating step of separating the gas component from the liquefied product, a dissolving step of mixing the supercritical solvent into the liquefied product through the separating step to form a liquefied product as a supercritical fluid, And an additive separation step of separating the additive from the supercritical fluid through the first separation step,
Wherein the step of separating the additive comprises the step of raising the temperature of the supercritical fluid flowing into the first container in which the additive is separated according to the temperature change. The method according to claim 1,
Wherein the supercritical solvent is at least one selected from the group consisting of propane and pentane. The method according to claim 1,
Wherein the residue separation step comprises separating the solid matter from the supercritical fluid via at least one cyclone. 4. The method according to any one of claims 1 to 3,
Wherein the separating step further comprises an oil separating step of separating the oil from the supercritical fluid through the additive separating step. 5. The method of claim 4,
Wherein the separating step further comprises a solvent separating step of separating the solvent from the supercritical fluid through the separating agent separation step. 6. The method of claim 5,
Wherein the separating step further comprises the step of supplying recycle the supercritical solvent in which the oil has been separated through the oil separation step to the mixing step. The method according to claim 6,
Wherein the coal pretreatment step comprises mixing the dried coal to the solvent at a weight ratio of 1/1 to 1/4. The method according to claim 6,
Wherein the dispersed iron catalyst is Fe ₂ O ₃ . 9. The method of claim 8,
Wherein the dispersed iron catalyst is added in an amount of 0.5 to 3.0 parts by weight based on 100 parts by weight of coal. The method according to claim 6,
Wherein the coal pretreatment step further comprises pulverizing coal and drying the pulverized coal. 11. The method of claim 10,
Wherein the step of drying the coal is performed so that the water content of the coal is 10 wt% or less. The method according to claim 6,
Wherein the coal liquefaction process is performed by heating the cracking gas at 400 to 600 ° C. A mixer for mixing the pretreated coal and the solvent to form a slurry, a catalyst supply unit for supplying the dispersed iron catalyst to the mixer, a reactor for liquefying the coal slurry through the mixer, and a COG and / or LNG A separator for separating the additive from the liquefied product generated from the reactor, and a supply line connected between the separator and the mixer for supplying the oil separated from the separator to the mixer as a solvent,
The separator includes a separator for separating the gas component from the liquefied product, a dissolving unit connected to the separator to form a supercritical fluid in the liquefied product through the separator to form a supercritical fluid, a supercritical fluid connected to the dissolving unit, And an additive separator connected to the residue separator and separating the additive from the supercritical fluid in which the solid material is separated,
Wherein the additive separator comprises a first container in which supercritical fluid flows into the first separator and an additive is separated in accordance with a change in temperature, a first heat exchanger installed in an inflow line of the first container to increase the temperature of the supercritical fluid, Manufacturing apparatus. 14. The method of claim 13,
Wherein the supercritical solvent is at least one selected from the group consisting of propane and pentane. 14. The method of claim 13,
Wherein the residue separator comprises at least one cyclone separating the supercritical fluid and the solid phase material. delete 16. The method according to any one of claims 13 to 15,
Wherein the dissolving unit comprises a mixing mixer for mixing a liquefaction product and a supercritical solvent to form a supercritical fluid, a pressurizing pump installed on the liquefaction product supply line of the mixing mixer for pressurizing the liquefied product to a supercritical fluid critical pressure, To a supercritical fluid critical temperature. ≪ Desc / Clms Page number 13 > 18. The method of claim 17,
Wherein the separator further comprises an oil separator connected to the additive separator to separate the oil from the supercritical fluid from which the additive is separated. 19. The method of claim 18,
Wherein the separator further comprises a solvent separator connected to the additive separator to separate the solvent from the supercritical fluid from which the additive is separated. 20. The method of claim 19,
Wherein the oil separator comprises: a third container in which supercritical fluid flows into the oil separator and the oil is separated according to a change in temperature; a third compressor installed in an inflow line of the third container to adjust the pressure and temperature of the supercritical fluid; A device for manufacturing an additive for coke comprising a heat exchanger. 21. The method of claim 20,
Wherein the solvent separator comprises a second container in which a supercritical fluid is introduced into the solvent separator and the solvent is separated according to a change in temperature, a second compressor installed in an inflow line of the second container to adjust the pressure and temperature of the supercritical fluid, A device for manufacturing an additive for coke comprising a heat exchanger. 20. The method of claim 19,
And a recovery line connected between the oil separation unit and the dissolution unit to supply supercritical solvent separated from the oil to the dissolution unit. 23. The method of claim 22,
Further comprising: a first compressor installed in the recovery line for transferring the supercritical solvent and controlling the pressure; and a heat exchanger for lowering the temperature.

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