WO2017111301A1 - Method and apparatus for preparing additive for coke - Google Patents

Abstract

Provided is a method for preparing an additive for coke, wherein, in order to further maximize the solid-liquid separation efficiency of viscous liquefied slurry in the preparation of the additive for coke, the method comprises: a feeding step for feeding an additional solvent to a liquefied product; a mixing step for mixing the liquefied product and the additional solvent to lower the viscosity of the liquefied product; and a filtering step for solid-liquid separating the liquefied product.

Description

Additive manufacturing method and apparatus for coke

Disclosed are a manufacturing method and a manufacturing apparatus for producing an additive for coke used for improving coke strength.

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, at present, the focus is mainly on the production of oil from coal, and there is no optimized process for extracting additives. In addition, by using the process of the direct coal direct liquefaction method, there is a problem that the economical efficiency in the additive production is reduced due to frequent failures and new operating know-how is required.

Accordingly, there is a need for the development of optimized and differentiated technologies that can effectively produce additives for coke.

The present invention provides a method and apparatus for manufacturing additives for coke, which enables to separate the coke additive and residue more effectively in manufacturing the additive for coke.

In addition, the present invention provides an additive manufacturing method and apparatus for coke, which can further maximize the solid-liquid separation efficiency for the viscous liquefied slurry.

In addition, the present invention provides an additive manufacturing method and apparatus for coke, which is capable of performing a continuous separation operation without clogging the filter when separating the additive for coke and the residue.

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 coal is less than 10wt%.

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 400 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. can do.

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 350 to 450 ℃.

The filtration step may further include a supplying step of supplying an additional solvent to the liquefied product, and a mixing step of lowering the viscosity of the liquefied product by mixing the liquefied product and the additional solvent.

The filtration step may further include a recovery step of recovering only the additional solvent from the liquid material after the solid-liquid separation.

The filtration step may further include a reuse step of transferring and supplying additional solvent recovered in the recovery step to the mixing step.

The additional solvent may be a solution having a different boiling point compared to the solvent mixed in the liquefaction product.

The additional solvent may be any one selected from toluene, nucleic acid, alcohol.

The filtration step is to alternately supply the liquefied product to the filter connected in parallel to at least two or more alternately from each filter to separate the liquid material and the solid material, the other filter that the filtering operation is completed when filtering through one filter An exchange step may be included in which the filter is exchanged.

It may further comprise an additional separation step of further separating the solvent remaining in the solid material filtered through the filter before the filter replacement.

The additional separation step may include heating the solid material, collecting the solvent gas evaporated from the solid material.

In the filtering step, the method may further include supplying a solvent to the liquefied product.

The additive manufacturing apparatus of the present embodiment, a mixer for mixing and slurrying pretreated coal and a solvent, a catalyst supply unit for supplying a dispersed iron catalyst to the mixer, a reactor for liquefying the coal slurry passed through the mixer, cracking gas in the reactor A gas supply unit for supplying COG and / or LNG to the reactor, a separation unit for separating additives from the liquefied product generated from the reactor, and an oil separated in the separation unit connected to the mixer and the mixer, as a solvent to the mixer It may include a supply line.

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 mixer through a distillation for supplying the oil separated from the additive to the mixer.

The filter device may be a filter for solid-liquid separation of a liquefied product into a liquid substance and a solid substance, a mixer connected to the filter inlet side to mix an additional solvent with the liquefied product and supply the filter to the filter, and a supply unit for supplying the additional solvent to the mixer. It may include.

The filter device may further include a recovery tower connected to the filter outlet side to recover additional solvent from the liquid material separated from the filter.

The apparatus may further include a recovery line connected between the recovery tower and the mixer to supply the recovered additional solvent to the mixer.

The additional solvent may be any one selected from toluene, nucleic acid, alcohol.

The filter device may include a filter that is alternately connected to at least two or more in parallel to drive the liquid product alternately by supplying liquefied products to each filter in order to sequentially separate the liquid and solid materials through each filter.

The filter unit is installed in a filter tank in which solid-liquid separation is selectively performed on the liquefied product, a filter detachably installed in the filtration tank to separate liquid and solid materials, and an inlet line for supplying the liquefied product to the filtration tank to open and close the inlet line. It may include a first valve for selectively supplying the liquefied product, the heating unit connected to the filtration tank to heat the solid material caught on the filter if necessary to extract the solvent gas.

In the filter device, the first valves of the respective filters are alternately operated so that liquefied products are alternately supplied to each filter to perform solid-liquid separation, and the heating unit is driven during the first valve closing operation to filter the solid matter filtered through the filter. It may be a structure for heating.

The filter device may include a solvent supply unit connected to the filtration tank for additionally supplying a solvent into the filtration tank when the solid liquid is separated, and a second valve installed on the solvent supply line connecting the solvent supply unit and the filtration tank.

A decompression line connected to an inlet chamber of the filtration tank and an outlet chamber of a neighboring filtration tank to transfer solvent and apply depressurization force to each chamber, a decompression pump installed at the decompression line to apply abrupt pressure, and a decompression line installed at the decompression line It may include a third valve for selectively opening and closing the.

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

The coal may comprise lignite or sub-bituminous coal.

The pulverizer may crush coal to a size of 60 mesh or less.

The dryer may be a structure for drying coal so that the water content of the coal is less than 10wt%.

The catalyst supply unit may have a structure for supplying Fe ₂ O ₃ to the dispersed iron catalyst.

The catalyst supply unit may add 0.5 to 3.0 parts by weight of the dispersed iron catalyst 100 parts by weight of coal.

Thus, according to this embodiment, by adding a solvent to the liquefied slurry to lower the viscosity, it is possible to perform the solid-liquid separation more easily.

In addition, by performing the filtration operation more effectively while minimizing the clogging of the filter for the viscous liquefied slurry, it is possible to increase the productivity of the coke additive.

In addition, by continuously driving a plurality of filters to perform a solid-liquid separation process, it is possible to improve the process efficiency to increase the productivity of the coke additive.

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

2 is a schematic view showing a filter device of the additive manufacturing apparatus for coke according to the first embodiment.

Figure 3 is a graph showing the content of the additives and oil remaining in the solid material separated through the first embodiment in comparison with the prior art.

4 is a schematic view showing a filter device of the additive manufacturing apparatus for coke according to the second embodiment.

5 is a schematic view for explaining the operation of the filter device of the additive manufacturing apparatus for coke according to the second 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 term "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 Figure 1, the additive manufacturing apparatus of this embodiment is a mixer 10 for mixing and slurrying pretreated coal and a solvent, a catalyst supply unit 20 for supplying a dispersion catalyst to the mixer 10, the mixer Separating the additive from the reactor 30 for liquefying the coal slurry (10), the gas supply unit 32 for supplying the cracking gas to the reactor 30, the liquefied product produced from the reactor (30) And a supply line 50 connected between the separator 40 and the mixer 10 for supplying the oil separated in the separator to the mixer 10 as a solvent.

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

In the present embodiment, the solvent introduced into the mixer 10 is configured to utilize the remaining oil after finally separating the additives through the separator 40.

To this end, the supply line 50 is connected between the separator 40 and the mixer 10, and the oil remaining after the additive separation is recycled to the mixer 10 through the supply line 50 as a solvent.

As such, by supplying the liquid oil separated through the separation unit 40 directly to the mixer 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 mixer 10 to supply the dispersed iron catalyst. As a result, the dispersed iron catalyst is evenly mixed in the mixer 10 such as coal and a solvent.

In the present 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, the reactivity can be increased 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 mixer 10 is transferred to the reactor 30 by a high pressure pump. In the process of transferring the coal slurry from the mixer 10 to the reactor 30, the coal slurry is heated to a predetermined temperature by supplying heat to the coal slurry through the heating unit 16 installed between the mixer 10 and the reactor 30. can do.

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 mixer 10 through a supply line 50. Thus, the oil separated from the additive through the distillation 46 is supplied to the mixer 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.

In the additive manufacturing apparatus for coke of the structure described above, the filter unit 44 of the separator is configured to filter the liquefied product while minimizing the filter clogging phenomenon, to more effectively separate the solid product and the liquid product.

[First Embodiment]

2 illustrates the structure of the filter device according to the first embodiment. Hereinafter, the structure of the filter device of this embodiment will be described with reference to FIG. 2.

Coal liquefaction products are very viscous in the form of slurry and have solid particles, which are amorphous, non-liquefied coal residues, which are difficult to separate into liquids and solids, are easy to plug filters, and block pipes during transport. Can be generated.

Thus, the filter device 44 of the present embodiment has a structure in which solid-liquid separation can be more easily performed by additionally adding an additional solvent to the high-liquid liquefied product to lower the viscosity of the liquefied product to be solid-liquid separated and increase the amount of solvent. have.

To this end, the filter device 44 of the present embodiment is provided with a filter (not shown) inside the filter 440 for solid-liquid separation of the liquefied product into a liquid material and a solid material, connected to the filter 440 inlet side And it may include a mixer for mixing the additional solvent to the liquefied product to supply to the filter 440, the supply unit for supplying the additional solvent to the mixer.

In addition, the filter device may further include a recovery tower 447 connected to the filter 440 exit side to recover additional solvent from the liquid material separated from the filter 440.

Accordingly, the liquefied product in which the gas is separated while passing through the separator 42 of the separator is mixed with an additional solvent through the mixer 443, thereby lowering the viscosity and increasing the amount of the solvent, and then separating the solid through the filter 440. In the process of reducing the burden on the filter it is easier to separate the solid and liquid materials.

The filter 440 may have a pore size of 5 to 10 μm of a filter provided therein. The filter 440 passes only the liquid material and the solvent in the liquid state smaller than the pore size of the filter. The solids, which are coal scum larger than the pore size, cannot pass through the filter and are separated into solids as they are filtered.

The mixer 443 is installed between the separator 42 and the filter 440 of the separator. The mixer 443 may have a structure for uniformly stirring the liquefied product and the additional solvent. For example, the mixer 443 may include a stirring blade for mixing the liquefied product and the additional solvent and a driving motor for rotating the stirring blade. The mixer 443 is applicable to both the structure of stirring the liquefied product and the additional solvent evenly.

A supply unit 445 for supplying additional solvent is connected to the mixer 443. The supply unit 445 inputs an appropriate amount of additional solvent to the mixer 443. In the present embodiment, the supply unit 445 may be a structure for supplying a solution having a different boiling point than the solvent mixed in the liquefied product as an additional solvent. The liquefied product, as mentioned, is mixed in a slurry state with coal and solvent via a mixer 443.

In the present embodiment, the additional solvent may be a solvent having a different boiling point than the solvent mixed in the liquefaction product. As such, by mixing the liquefied product using an additional solvent having a different boiling point compared to the solvent of the liquefied product, it is possible to easily recover only the additional solvent excluding the solvent by using the boiling point of the solution in the recovery tower 447 later.

In the present embodiment, the additional solvent may be any one selected from toluene, nucleic acid, alcohol having a lower boiling point than the solvent mixed in the liquefaction product.

The recovery tower 447 is a structure for separating and recovering only the additional solvent from the liquid mixture by using a difference in boiling point, for example, a fractional distillation may be used. The recovery tower 447 is connected between the filter 440 and the distillation unit 46 of the separation unit to recover additional solvent from the liquid material separated through the filter 440. The liquid material passed through the recovery tower 447 is transferred to the still.

In addition, a recovery line 449 may be installed between the recovery tower 447 and the mixer 443 to supply the additional solvent recovered from the recovery tower 447 to the mixer 443. Accordingly, the additional solvent separated from the recovery tower 447 is supplied to the mixer 443 through the recovery line 449 and reused.

Since the additional solvent is recovered from the recovery tower 447 and supplied to the mixer 443 through the recovery line 449, the supply unit 445 is not completely recovered from the recovery tower 447, and has passed to the subsequent process together with the liquid material. Only the amount of additional solvent can be replenished and supplied to the mixer 443.

As such, the filter device 44 of the present embodiment lowers the viscosity of the liquefied product and increases the amount of the solvent, thereby effectively reducing the solid-liquid separation operation with less load while reducing the clogging of the filter in the course of passing through the filter 440. Will be able to perform

Hereinafter, the process of manufacturing the additive 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 10 wt% or less through a coal drying process. When the water content of coal exceeds 10wt%, 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 400 to 600 ° C. in accordance with the reactor internal temperature at which the coal liquefaction reaction 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, H2S, NH3, H2, 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.

Here, the filtration step may further include a supplying step of supplying an additional solvent to the liquefied product, and a mixing step of lowering the viscosity of the liquefied product by mixing the liquefied product and the additional solvent.

The filtration step may further include a recovery step of recovering only the additional solvent from the liquid material after the solid-liquid separation. In addition, the filtration step may further include a reuse step of transferring the additional solvent recovered in the recovery step to the mixing step and resupply.

The liquefied product from which the gaseous components are separated through the separating process is evenly mixed with the additional solvent supplied before the filtration process, so that the viscosity becomes lower and the amount of the solvent increases, resulting in a thinner state. Thus, the solid-liquid separation can be made more effectively while reducing the burden on the filter in the subsequent filtration process.

The additional solvent further mixed in the liquefaction product in this embodiment is a solution having a lower boiling point compared to the solvent mixed in the liquefaction product, for example, toluene, nucleic acid, alcohol. The additional solvent has a lower boiling point than the solvent mixed in the liquefaction product, so that only the additional solvent can be recovered more easily in the subsequent recovery process.

Through filtration, the liquefied product is separated into solid and liquid materials.

The separated liquid material is recovered through a recovery process before separating the additives through a fractional distillation process to recover additional solvent. Since the boiling point of the solvent and the additional solvent in the liquid material is different in the recovery process, only the additional solvent can be distilled and recovered by heating the liquid material in accordance with the boiling point temperature of the additional solvent. The recovered additional solvent is transferred to the mixing step and reused as additional solvent mixed with the liquefied product. After the additional solvent is recovered, the remaining liquid material is then subjected to fractional distillation to finally produce coke additives.

Figure 3 shows the content of the additives and oil remaining in the solid material separated through the separation process according to the present embodiment compared with the prior art.

3 shows an additive and an oil content remaining in the solid material after the separation process by mixing the additional solvent in the liquefied product as mentioned, Comparative Example without mixing the additional solvent in the liquefied product as in the prior art It shows the additive and oil content remaining in the solid material after the separation process.

Toluene was used as an additional solvent in the examples.

As a result of the experiment, as shown in FIG. 3, the content of the additive and the oil component remaining in the solid material at a temperature of less than 260 ° C. was 33%, indicating that solid-liquid separation was not effectively performed. On the other hand, in the case of the embodiment it can be confirmed that the solid-liquid separation is very effective to reduce the additives and oil components remaining in the solid material to 4% at a temperature of less than 260 ℃.

Therefore, while the liquid-liquid separation efficiency is as low as 67% in the conventional structure as in the comparative example, the solid-liquid separation efficiency can be increased to 96% in the case of the structure in which the liquefied product is diluted with additional solvent as in the example.

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.

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 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 may be performed at a temperature of 350 to 450 ℃. Since the oil in the liquid product has a boiling point lower than 350 to 450 ° C., the additive for the coke may 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 350 ° C to 450 ° C in the fractional distillation step, the oil is evaporated and only the additive for coke can be separated 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 recirculation process is to supply the oil obtained through the fractional distillation step directly to the mixer of the coal pretreatment process. As such, the oil separated in the separation process is directly recycled to the coal pretreatment process, thereby simplifying the process.

Second Embodiment

Fig. 4 illustrates the structure of the filter device according to the second embodiment, and Fig. 5 schematically illustrates the operating state of the filter device. Hereinafter, the structure of the filter device of the present embodiment will be described with reference to FIGS. 4 and 5.

Coal liquefaction products have a high viscosity in the form of slurries and solid particles, which are amorphous, non-liquefied coal residues, making it difficult to carry out continuous filtration by clogging the filter as solid particles accumulate on the filter.

Accordingly, the filter device 44 of the present embodiment may have a structure in which at least two filter units are connected in parallel and alternately driven. The filter device alternately supplies the liquefied product to each filter to sequentially solidify the liquefied product through each filter. As a result, each filter is alternately driven and solid-liquid separation is continuously performed, so that the filter can be exchanged in the filter in which the solid-liquid separation is completed while the solid-liquid separation is in progress with one filter.

In the present embodiment, a structure in which two filter units are provided in parallel will be described as an example. The filter device is not limited to a structure having two filter units, and a structure having three, four or more filter units is also applicable.

For convenience of description, the two filters will be referred to as a first filter 441 and a second filter 442, respectively. Since the first filter 441 and the second filter 442 have the same structure and only operate alternately, the configuration thereof will be described as an example of the first filter, and the same number will be given to the second filter. The detailed description thereof is omitted.

The first filter 441 is a filter tank 450 in which solid-liquid separation is selectively performed on the liquefied product, and a filter 451 detachably installed in the filter tank 450 to separate liquid and solid materials, and the filter tank ( It may include a first valve 453 installed in the inlet line 452 for supplying the liquefied product to 450 to selectively open and close the inlet line.

In addition, the first filter 441 is installed in the filtration tank 450 to further extract the solvent from the solid matter caught by the filter 451 before replacing the filter 451, if necessary on the filter 451 It may further include a heating unit 454 for heating the solid material to extract the solvent.

In the present embodiment, the heating unit 454 is inserted into the filter tank 450, if necessary, to heat the solid material filtered by the filter 451. The heating unit 454 may be, for example, a pipe structure through which a gas is distributed so that heat can be applied using a high temperature gas such as nitrogen or argon. The heating unit 454 is installed on the side of the filter tank 450 so as to be movable in and out, and if necessary, is inserted into the filter tank 450 and disposed below the filter 451. To prevent interference with the liquid material passed through 451). The solid material is heated by the heat applied from the heating unit 454 to further evaporate the solvent remaining in the solid material. The heating unit 454 may be variously modified in structure that can heat a solid material, and all may be applicable.

In the filter device 44, the first valves 453 of the respective filters are alternately operated so that liquefied products are alternately supplied to the respective filters 441 and 442 to perform solid-liquid separation, and the heating unit 454 The first valve 453 may be driven during the closing operation to heat the solid material filtered by the filter 451.

Therefore, when the first valve 453 of the first filter 441 is opened and the first filter 441 is in solid-liquid separation, the first valve 453 of the second filter 442 is closed. The liquefied product is not supplied and the second filter 442 is driven by the heating unit 454 to extract additional solvent from the solid matter and to replace the filter 451.

In addition, the filter unit is connected to the filter tank 450, the solvent supply unit 455 for additionally supplying a solvent into the filter tank 450 when the solid-liquid separation, the solvent supply line connecting the solvent supply unit 455 and the filter tank 450 It may further include a second valve 457 installed on 456. The solvent supply unit 455 may supply a solvent as a solvent. As a solvent is additionally added to the liquefied product supplied to the filtration tank 450, the filtration efficiency of the liquefied product can be further increased.

The second valve 457 is opened when the filter unit is in a solid-liquid separation operation to supply additional solvent, and is closed when the filter unit is switched to the standby state in the solid-liquid separation operation and is a solid material heating operation or a filter 451 replacement operation. It works.

The filtration tank 450 is a container structure that is blocked from the outside and capable of internal pressure or pressure, and a filter 451 is installed therein to filter the liquid material from the liquefied product to filter the solid material. The interior of the filtration tank 450 is divided into two chambers, the upper and lower chambers by the horizontally arranged filter 451. For convenience of explanation, the chamber above the filter 451 is called the entrance chamber 458 and the chamber below is called the exit chamber 459.

The filter 451 may have a pore size of 5 to 10 μm. The filter 451 passes only the liquid material and the solvent in the liquid state smaller than the pore size. Residue, which is coal scum larger than the pore size, cannot pass through the filter 451 and is filtered out to remain on the filter 451.

For example, a perforated plate may be installed inside the filtration tank 450 to support and support the filter 451. The filter 451 is mounted in the filtration tank 450 while being supported on the perforated plate. The filtration tank 450 may have a structure in which the filter tank 451 is separated into an upper part and a lower part about the filter 451 to be detachably coupled to each other. Accordingly, if necessary, the upper part of the filtration tank 450 may be opened from the bottom to easily replace the filter 451 installed therein.

An inlet 460 through which the liquefied product is supplied, a solvent supply port 461 for additionally supplying a solvent, and a gas discharge port 462 for discharging the solvent gas are formed at an upper end of the filtration tank 450, and an entrance chamber 458 is formed. Communicating. A discharge port 463 is formed at a lower end of the filtration tank 450 through which a solid material is filtered through a filter 451. The outlet 463 of the filtration tank 450 is provided with an on-off valve 464 may discharge the filtered liquid material through the outlet 463 if necessary. In addition, a suction port 465 is formed at a side surface of the filtration tank 450 to be connected to the exit chamber 459 to apply a depressurizing force to the exit chamber 459.

Thus, the liquefied product supplied to the filtration tank 450 through the inlet 460 is separated from the solid matter and the liquid material through the filter 451, the solid material is caught on the filter 451 and remains on the filter 451, the liquid material The silver passes through the filter 451 and is discharged through the outlet 463 under the filtration tank 450.

A cover 466 may be further installed inside the filtration tank 450 to cover the suction port 465 above the suction port 465. The cover 466 extends sufficiently past the suction port 465 without blocking the suction port 465 to block the liquid material falling from the filter 451 and the suction port 465. By the cover, it is possible to apply a depressurizing force in the filtration tank 450 while preventing the liquid material passing through the filter 451 into the suction port 465.

In this embodiment, through the gas outlet 462 of the upper portion of the filtration tank 450 and the inlet 465 of the lower portion, the decompression force is applied to the inlet chamber 458 and the outlet chamber 459 of the filtration tank 450 as necessary. Can be added. When the filter is in the filtration operation, a pressure reduction force is applied to the exit chamber 459 to increase the filtering effect. When the filter unit is extracting the solvent gas, a pressure reduction force is applied to the entrance chamber 458 to increase the extraction effect.

To this end, in the first filter 441 and the second filter 442, a pressure reducing line 467 is connected to the entrance chamber 458 and the exit chamber 459 between neighboring filtration tanks 450, and The decompression line 467 is provided with a decompression pump 468 for applying a depressurizing force, and the decompression line 467 is provided with a third valve 469 for selectively opening and closing the decompression line 467. As shown in FIG. 4, the gas outlet 462 of the first filter 441 and the suction port 465 of the second filter 442 are connected to the pressure reducing pump 468 through the pressure reducing line 467. . The inlet 465 of the first filter 441 and the gas outlet 462 of the second filter 442 are also connected to the decompression pump 468 through a separate decompression line 467.

Accordingly, when the third valve 469 installed in each pressure reducing line 467 is opened and closed, pressure is applied to the outlet chamber 459 of the filtration tank 450 of each filter alternately, and the filtration tank of each filter The inlet chamber 458 of 450 also alternately applies a depressurizing force to apply the necessary depressurizing force in the filtration tank 450.

For example, when the first filter 441 is in the solid-liquid separation state and the second filter 442 is in the solid state heating state for further separation of the solvent, the inlet 465 of the first filter 441 The third valve 469 of the pressure reducing line 467 connected to the gas outlet 462 of the second filter 442 is opened. Therefore, the pressure reduction is applied to the exit chamber 459 of the first filter 441, so that the first filter 441 is solid-liquid separated more effectively, and the second filter 442 is connected to the entrance chamber 458. Decompression is applied to allow the solvent gas to evaporate more effectively from the solid phase. On the contrary, the third valve 469 of the pressure reducing line 467 connecting the gas outlet 462 of the first filter 441 and the suction port 465 of the second filter 442 is closed to reduce the pressure reducing line 467. Depressurization is not applied to the inlet chamber 458 of the first filter unit 441 and the outlet chamber 459 of the second filter unit 442 through the reference numeral). When the operations of the first filter 441 and the second filter 442 are alternately performed, and the second filter 442 performs the solid-liquid separation operation, the pressure reduction is performed in the opposite manner to the above to obtain the same effect.

Here, the solvent gas evaporated into the inlet chamber 458 of the filtration tank 450 during the solvent separation of the filter is carried out through the gas outlet 462 in the decompression process of the inlet chamber 458 of the filtration tank 450. To be discharged. Thus, one side of the decompression line 467 may be further provided with a solvent collecting unit 470 for collecting the solvent gas transferred through the decompression line 467.

As such, when the liquefied product is solid-liquid separated using the first filter 441 through the filter device of the present embodiment, and the solid material accumulates to some extent in the filter 451 of the first filter 441, the second filter By supplying the liquefied product to the group 442 and solid-liquid separation, the two filter units 441 and 442 can be alternately performed to perform filtration continuously. In addition, in the process of solid-liquid separation of the liquefied product by the second filter 442, the solvent is further extracted from the solid material filtered through the filter 451 of the first filter 441 to increase the recyclability of the solvent, By replacing the 451, it is possible to effectively carry out solid-liquid separation without clogging the filter in the later shift work.

Hereinafter, a process of manufacturing the additive according to the second embodiment is as follows.

Since the process of preparing the additive according to the present embodiment is the same as the first embodiment except for the filtration step, the filtration step according to the present embodiment will be described in detail below, and the same process as the first embodiment will be described. Omit.

The filtration step according to the present embodiment is a filtering step of alternately supplying a liquefied product to a filter connected in parallel to at least two or more to separate liquid and solid substances from each filter alternately, filtering at the time of filtering through one filter This may include an exchange step of replacing the filter in another completed filter.

In the filtering step, the method may further include supplying a solvent to the liquefied product.

The method may further include an additional separation step of further separating the solvent remaining in the solid material filtered through the filter before the filter replacement.

As shown in FIG. 3, the liquefaction product is supplied to the first filter and additionally, the solvent is supplied to perform a solid-liquid separation operation. When the first filter 441 is in the solid-liquid separation operation, the liquefied product is not supplied to the second filter 442 and is in the standby state.

The liquefied product supplied to the first filter 441 separates the liquid substance and the solid substance while passing through the filter. The liquid substance separated from the filter and the additionally supplied solvent are discharged to the bottom of the first filter unit. The solid material does not pass through the filter and is caught and gradually builds up on top of the filter. In this process, the outlet chamber of the first filter is depressurized, whereby the solid-liquid separation operation can be performed more effectively.

The second filter 442 separates the solvent from the solid matter loaded in the internal filter through an additional separation process in an atmospheric state where the liquefied product is not supplied.

In this embodiment, the method may include heating the solid material to further separate the solvent from the solid material, and collecting the solvent gas evaporated from the solid material.

Accordingly, by applying heat to the solid material of the second filter 442 in the air state with the heating unit, the solvent remaining in the solid material evaporates and is separated from the solid material. The inlet chamber of the second filter may increase the solvent evaporation efficiency in a state where the reduced pressure is applied through the reduced pressure line 467. Solvent gas separated from the solid material is discharged to the outside through the decompression line connected to the inlet chamber of the second filter is collected.

When the solvent addition collection operation of the second filter in the air is sufficiently completed, the filter of the second filter is replaced with a new filter.

When the filter replacement for the second filter is completed, and the solid material accumulates above a certain height in the filter of the first filter, the supply of the liquefied product and the solvent to the first filter 441 is stopped and the second filter ( 442) is further fed with liquefied product and solvent. The pressure reducing line connected to the exit chamber of the first filter and the entrance chamber of the second chamber is locked, and the pressure reduction line connected to the entrance chamber of the first filter and the exit chamber of the second chamber is opened to apply a pressure reducing force.

Thus, the liquefied product is supplied to the second filter to carry out the solid-liquid separation operation, and the first filter is converted to the atmospheric state to perform the solvent addition collection process and the filter exchange process as mentioned.

In this way, by replacing the filter, it is possible to continuously carry out the solid-liquid separation operation effectively without clogging the filter in a later shift operation.

In the conventional case, the filter is clogged by the high viscosity coal liquefied product, and the load is increased on the pump, and the liquid-liquid separation efficiency is lowered and a large amount of additives remain on the filter, resulting in a decrease in productivity.

On the other hand, in the present embodiment, by using a plurality of filters provided in parallel alternately, it is possible to effectively carry out the solid-liquid separation operation continuously while preventing the filter from being blocked by the high viscosity coal liquefaction product.

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 (28)

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 a recycling step of supplying the liquid oil obtained in the separation step to the coal pretreatment step and using it as a solvent. 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. , The filtration step further includes a supplying step of supplying an additional solvent to the liquefied product, and a mixing step of lowering the viscosity of the liquefied product by mixing the liquefied product and the additional solvent. The method of claim 1, The additional solvent is a method for producing an additive for coke, the boiling point is different from the solvent mixed in the liquefaction product. The method of claim 2, The additional solvent is any one selected from toluene, nucleic acid, alcohol, coke additive production method. The method according to any one of claims 1 to 3, The filtration step further comprises a recovery step for recovering only the additional solvent in the liquid material after the solid-liquid separation. The method of claim 4, wherein The filtration step further comprises a reusing step of transferring the additional solvent recovered in the recovery step to the mixing step and re-supply. 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 a recycling step of supplying the liquid oil obtained in the separation step to the coal pretreatment step and using it as a solvent. 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. , The filtration step is to alternately supply the liquefied product to the filter connected in parallel to at least two or more alternately from each filter to separate the liquid material and the solid material, the other filter that the filtering operation is completed when filtering through one filter Method for producing an additive for coke comprising the exchange step of replacing the filter in the group. The method of claim 6, In the filtering step, the method for producing an additive for coke further comprising the step of further supplying a solvent to the liquefied product. The method according to claim 6 or 7, The method for producing an additive for coke further comprising a further separation step of further separating the solvent remaining in the solid material filtered through the filter before the filter replacement. The method of claim 8, The further separation step is a method for producing an additive for coke comprising heating the solid material, collecting the solvent gas evaporated from the solid material. The method according to claim 1 or 6, 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 according to claim 1 or 6, 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 according to claim 1 or 6, The dispersed iron catalyst is Fe ₂ O ₃ Coke additive manufacturing method. The method of claim 12, 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 claim 1 or 6, The filtration step is an additive manufacturing method for coke is carried out at a temperature of 120 to 400 ℃. The method according to claim 1 or 6, The coal pretreatment process further comprises the step of pulverizing coal, and drying the pulverized coal coke additive manufacturing method. The method of claim 15, The coal drying step is a coke additive manufacturing method for drying so that the water content of the coal is less than 10wt%. The method according to claim 1 or 6, The coal liquefaction process is a coke additive production method for supplying a cracking gas heated to 400 to 600 ℃. A mixer for slurrying by mixing pretreated coal and a solvent, a catalyst supply unit for supplying a dispersed iron catalyst to the mixer, a reactor for liquefying the coal slurry passed through the mixer, supplying COG and / or LNG as a cracking gas to the reactor A gas supply unit, 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 mixer to supply oil separated in the separation unit to the mixer as a solvent, 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 Is connected to the mixer through a distillation unit for supplying an oil separated from the additive to the mixer, The filter device may be a filter for solid-liquid separation of a liquefied product into a liquid substance and a solid substance, a mixer connected to the filter inlet side to mix an additional solvent with the liquefied product and supply the filter to the filter, and a supply unit for supplying the additional solvent to the mixer. Additive manufacturing apparatus for coke comprising. The method of claim 18, The filter device is connected to the filter outlet side coke additive manufacturing apparatus further comprises a recovery tower for recovering the additional solvent in the liquid material separated from the filter. The method of claim 19, An apparatus for producing coke additives further comprising a recovery line connected between the recovery tower and the mixer to supply the recovered additional solvent to the mixer. The method according to any one of claims 18 to 20, The additional solvent is any one selected from toluene, nucleic acid, alcohol, coke additive manufacturing apparatus. A mixer for slurrying by mixing pretreated coal and a solvent, a catalyst supply unit for supplying a dispersed iron catalyst to the mixer, a reactor for liquefying the coal slurry passed through the mixer, supplying COG and / or LNG as a cracking gas to the reactor A gas supply unit, 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 mixer to supply oil separated in the separation unit to the mixer as a solvent, 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 Is connected to the mixer through a distillation unit for supplying an oil separated from the additive to the mixer, The filter device includes at least two filters connected in parallel and alternately driven, by supplying liquefied products to each filter alternately to produce a coke additive structure for separating the liquid and solid materials sequentially through each filter Device. The method of claim 22, Each filter is installed in a filter tank in which solid-liquid separation is selectively performed on the liquefied product, a filter detachably installed in the filtration tank to separate the liquid and solid substances, and an inlet line for supplying the liquefied product to the filtration tank. And a heating unit connected to the filtration tank to selectively supply the liquefied product, and a heating unit configured to extract a solvent gas by heating a solid material caught by the filter if necessary. The method of claim 23, In the filter device, the first valves of the respective filters are alternately operated so that liquefied products are alternately supplied to each filter to perform solid-liquid separation, and the heating unit is driven during the first valve closing operation to filter the solid matter filtered through the filter. The additive manufacturing apparatus for coke of the structure which heats up. The method according to any one of claims 22 to 24, The filter device is connected to the filtration tank further comprises a solvent supply unit for supplying a solvent into the filtration tank when the solid-liquid separation, and a second valve installed on the solvent supply line for connecting the solvent supply unit and the filtration tank coke additive manufacturing apparatus. The method of claim 25, A decompression line connected to an inlet chamber of the filtration tank and an outlet chamber of a neighboring filtration tank to transfer solvent and apply depressurization force to each chamber, a decompression pump installed at the decompression line to apply abrupt pressure, and a decompression line installed at the decompression line Additive manufacturing apparatus for coke further comprising a third valve for selectively opening and closing the. The method of claim 18 or 22, Apparatus for producing additives for coke further comprising a mill for pulverizing coal for coal pretreatment, and a dryer for drying the pulverized coal. The method of claim 18 or 22, The catalyst supply unit for producing coke additives of the structure for supplying Fe ₂ O ₃ to the dispersed iron catalyst.

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