KR20170114143A - Facilities and methods for synthesizing hydrocarbon from synthesis gas comprising carbonmonoxide and hygrogen - Google Patents

Abstract

The present invention relates to a process for regulating the molar ratio of carbon monoxide and hydrogen contained in a feedstock synthesis gas, wherein the molar ratio is such that the synthesis gas is separated into two streams, one of which converts carbon monoxide in the synthesis gas to hydrogen by an aqueous gasification reaction, A synthesis gas component control step of separating the hydrogen contained in the synthesis gas and the other one by bypassing and then mixing the synthesis gas with methane; Methanol; Or a mixture of diesel and wax, a step of synthesizing a hydrocarbon, a step of synthesizing a second methane and a step of synthesizing dimethyl ether (DME) according to the kind of hydrocarbon synthesized in the hydrocarbon synthesis step, And separating or removing the water after the synthesis of the hydrocarbon is bypassed to recover the hydrocarbon. When the synthesized hydrocarbon is methane, the reaction proceeds to the secondary methane synthesis reaction step. When the synthesized hydrocarbon is methanol, the DME synthesis reaction step , Wherein the hydrocarbon is bypassed when the synthesized hydrocarbon is a mixture of diesel and wax, and an apparatus suitable for performing the method is provided do.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a hydrocarbon production apparatus and method for selectively producing a heterogeneous hydrocarbon compound from a synthesis gas containing carbon monoxide and hydrogen. BACKGROUND ART [0002]

The present invention provides an apparatus and a method for producing various types of hydrocarbons by changing operating parameters and catalysts in one process.

As a method for producing a hydrocarbon compound using carbon monoxide and hydrogen, three methods are mainly used depending on the type of hydrocarbon to be obtained. This is shown in FIG. 1 to FIG.

As can be seen from Fig. 1, there is a methane synthesis process for synthesizing methane using synthetic natural gas. As shown in Fig. 2, a synthesis gas is produced by synthesizing methanol and dimethyl ether with synthetic natural gas And a process for producing diesel or wax using a Fischer-Tropsch reaction as shown in FIG. 3.

These three synthesis processes are common in that carbon monoxide and hydrogen are combined to produce hydrocarbons, which can be represented by the general equation (1).

_{nCO + nH 2 → C n H} 2n +2 + nH 2 O (1)

First, the methane synthesis process shown in FIG. 1 is carried out by mixing a synthesis gas composed of carbon monoxide and hydrogen at a ratio of about 1: 3, and then maintaining the reactor at about 250 ° C. in an aqueous gasification reactor containing a nickel-based catalyst . The equation (2) is shown below.

CO + 3H _{2 -} > CH ₄ + H ₂ O (2)

The methane thus synthesized has a calorific value of 9,500 Kcal per 1 Nm ³ and can be used as an alternative fuel for natural gas.

Next, in the gasoline synthesis step shown in Fig. 2, methanol is first synthesized by adjusting the ratio of carbon monoxide and hydrogen to 1: 2 as shown in the following formula (3), and then, After synthesizing the two methanol molecules as one dimethyl ether, the gasoline can be synthesized by further separating the water from the dimethyl ether as shown in the formula (5).

CO + 2H _{2 -} > CH ₃ OH (3)

2CH ₃ OH - > CH ₃ OCH ₃ + H ₂ O (4)

nCH ₃ OCH ₃ C _n H _{2n + 2} + nH ₂ O (5)

The synthetic gasoline thus obtained can be used as an energy source for an automobile fuel instead of gasoline produced by refining petroleum. The calorific value per kilogram is almost the same as that of gasoline.

Finally, the production process of diesel and wax using the Fischer-Tropsch reaction shown in FIG. 3 is a process in which carbon monoxide and hydrogen are mixed at a ratio of about 1: 2 as shown in the following formula (6) By heating to about 200 to 220 캜 under a post-iron or cobalt catalyst, a Fisher-Tropsch Liquid having a specific hydrocarbon distribution can be produced by a relatively simple process.

_{nCO + nH 2 → C n H} 2n + nH 2 O (6)

By the Fischer-Tropsch reaction, various hydrocarbons can be produced from methane having a carbon number of 1 to wax having a carbon number of 20 or more. At this time, diesel can be produced according to the characteristics of the catalyst, which can be controlled by operating conditions and catalyst selection.

As described above, according to the conventional method, if the hydrocarbon production facility is constructed as described above, a single item of hydrocarbons can not be produced.

As described above, conventionally, in the production of hydrocarbons using a synthesis gas composed of carbon monoxide and hydrogen, specific processes have been applied for the purpose of producing a single product.

In general, plants are intended for decades of operation, but in the case of fossil fuels such as hydrocarbons, especially petroleum, which depend on mining, plant availability is highly variable depending on market conditions and price fluctuations. In particular, such price fluctuations are more likely to be due to international conditions and artificial price controls than to exact demand and supply forecasts, so plants that have been planned for decades of operation will be shut down and shut down many.

In this case, even if the facility is restarted due to a rise in business performance, the plant is re-operated, it causes a lot of time and economic burden before the facility is laid down. Thus, a large cost is required for operation of the facility, It is too late to respond to the changing situation.

Accordingly, the present invention provides a method for producing various hydrocarbons through a single process, thereby increasing the operating rate and value of the equipment by producing hydrocarbons having the greatest added value at the time according to market changes have.

The present invention also provides a multi-hydrocarbon synthesis process capable of producing various kinds of hydrocarbons by varying the operating parameters and catalyst in one process.

The present invention provides a hydrocarbon synthesis plant capable of selectively synthesizing hydrocarbons. The hydrocarbon synthesis plant according to an embodiment of the present invention is a synthesis system for synthesizing hydrocarbons by selectively synthesizing hydrocarbons by synthesizing carbon monoxide and hydrogen A hydrocarbon synthesis means for synthesizing hydrocarbons by reacting the synthesis gas controlled by the component in the synthesis gas component regulating means to obtain a hydrocarbon-containing synthesis gas, and a hydrocarbon synthesis gas regeneration means for regenerating the hydrocarbon- And a target product recovery means for separating and recovering the final target product,

The synthesis gas component control means includes an aqueous gasifier for performing an aqueous gasification reaction for converting carbon monoxide contained in the supplied raw material synthesis gas into hydrogen, a hydrogen separation facility for separating and removing the hydrogen contained in the raw synthesis gas, And a mixed gas bypass line for bypassing a part of the syngas in accordance with a molar ratio of carbon monoxide and hydrogen contained in the syngas,

The hydrocarbon synthesis means is supplied with the component-regulated synthesis gas discharged from the synthesis gas component regulating means, and hydrocarbons which synthesize hydrocarbons of methane, methanol or diesel and wax from the component-regulated synthesis gas to obtain a hydrocarbon- A DME synthesis reactor for synthesizing dimethyl ether from a hydrocarbon-containing synthesis gas containing methanol, and a DME synthesis reactor for synthesizing methane from a hydrocarbon-containing synthesis gas containing methane, Comprising two or more of the hydrocarbon bypass lines bypassing the hydrocarbon containing synthesis gas comprising diesel and wax,

The objective product recovery means separates and removes water from the product stream discharged from the methane synthesis reactor, the DME synthesis reactor, or the hydrocarbon bypass line, and recycles methane as the hydrocarbon; DME; Or a water separator for discharging diesel and wax, so that a variety of hydrocarbons can be selectively synthesized from the syngas.

The synthesis gas mixing unit may further include a synthesis gas mixing unit that mixes the synthesis gas passed through the water gasifier, the hydrogen separation unit, and the bypass line, and discharges a component-controlled synthesis gas having a predetermined molar ratio of carbon monoxide and hydrogen .

The hydrogen separation device may be a pressure conversion adsorber or a separation membrane.

And a heat exchanger for raising or lowering the temperature of the component-controlled synthesis gas supplied to the hydrocarbon synthesis reactor.

A gasoline synthesis reactor for synthesizing gasoline by the reaction of the equation (5) from the DME discharged from the water separator, and a second moisture separator for removing moisture as a by-product from the reaction product generated in the gasoline synthesis reactor and discharging gasoline can do.

nCH ₃ OCH ₃ C _n H _{2n + 2} + nH ₂ O (5)

A hydrogenation reactor in which hydrocarbons discharged from the water separator react with hydrocarbons containing hydrogen and wax to crack the diesel or wax to a predetermined length and a diesel and wax discharged from the hydrogenation reactor are fractionally distilled, And a fractionation distiller for separating and recovering the waxes and discharging the remaining hydrocarbons including naphtha to the hydrocarbon synthesis reactor.

The hydrogenation reactor is connected to the hydrogen separation facility, and the hydrogen separated from the hydrogen separation facility is supplied to the hydrogenation reactor.

The fractionation distillation unit is connected to the hydrocarbon synthesis reactor, and residual hydrocarbon including naphtha discharged from the fractionation unit may be supplied to the hydrocarbon synthesis reactor.

The hydrocarbon synthesis reactor is a fixed bed reactor in which two or more catalyst layers are supported on the catalyst in a direction perpendicular to the moving direction of a syngas stream in which a synthesis gas is injected in the upper portion of the reactor and a hydrocarbon- desirable.

The hydrocarbon synthesis reactor may include a heat exchange pipe disposed in a direction parallel to the catalyst layer for each catalyst layer, and the heat exchange medium may be transferred through the heat exchange pipe.

The catalyst layer may be a nickel catalyst for methane synthesis, a copper and ZnO containing catalyst for methanol synthesis, or an iron or cobalt catalyst for diesel and wax synthesis.

The present invention also provides a hydrocarbon synthesis method for selectively synthesizing a plurality of hydrocarbons from a synthesis gas. In the hydrocarbon synthesis method according to an embodiment of the present invention, the molar ratio of carbon monoxide and hydrogen contained in the synthesis gas is controlled, The molar ratio is obtained by separating the synthesis gas into two streams, one stream converting carbon monoxide in the synthesis gas to hydrogen by an aqueous gasification reaction, or separating the hydrogen contained in the synthesis gas and bypassing the other stream A synthesis gas component regulating step wherein the synthesis gas having the controlled molar ratio is reacted in the presence of a catalyst to produce methane; Methanol; Or a mixture of diesel and wax, a step of synthesizing a hydrocarbon, a step of synthesizing a second methane and a step of synthesizing dimethyl ether (DME) according to the kind of hydrocarbon synthesized in the hydrocarbon synthesis step, And separating or removing the water after the synthesis of the hydrocarbon is bypassed to recover the hydrocarbon. When the synthesized hydrocarbon is methane, it is transferred to the secondary methane synthesis reaction step. When the synthesized hydrocarbon is methanol, DME synthesis To the reaction step, and bypassing if the synthesized hydrocarbon is a mixture of diesel and wax.

The CO: H ₂ molar ratio of the syngas adjusted in the synthesis gas component control step is 1: 2.5 to 1: 3.5 when the hydrocarbon obtained in the step of synthesizing the hydrocarbon is methane, 1: 1.8 to 2.5 when the hydrocarbon is methanol, It is preferably 1: 5 to 2.

The catalyst may be a nickel catalyst for methane synthesis, a copper and ZnO containing catalyst for methanol synthesis, or an iron or cobalt catalyst for diesel and wax synthesis.

The hydrogen may be separated by pressure conversion adsorption or membrane separation.

And a heat exchange step of raising or lowering the temperature of the syngas whose molar ratio is controlled by heat exchange.

When the hydrocarbon obtained in the hydrocarbon synthesis step is methane or methanol, the heat exchange step is performed so that the molar ratio of the synthesis gas is controlled to be in the range of 250 to 300 ° C. When the mixture is a mixture of diesel and wax, The heat exchange step is preferably performed.

A gasoline synthesis step of synthesizing the gasoline by the reaction of the DME recovered in the hydrocarbon recovery step and the gasoline recovery step of removing moisture as a byproduct from the produced reaction product and discharging gasoline, have.

nCH ₃ OCH ₃ C _n H _{2n + 2} + nH ₂ O (5)

A hydrogenation step of reacting the mixture of diesel and wax with hydrogen to perform a hydrogenation process of cracking the diesel and wax with hydrocarbons of a predetermined length, and a step of subjecting the mixture of diesel and wax subjected to the hydrogenation process to fractional distillation to obtain diesel and wax And recovering the separated diesel and wax.

The hydrogen in the hydrogenation step may be hydrogen separated from the synthesis gas in the synthesis gas component control step.

Residual hydrocarbons including naphtha remaining after the fractional distillation can be discharged and reused as syngas in the hydrocarbon synthesis step.

In the hydrocarbon synthesis step, it is preferable to cool or heat the catalyst during the hydrocarbon synthesis reaction to maintain the activity of the catalyst through heat exchange between the catalyst and the cooling or heating medium.

Various hydrocarbon products can be produced from the synthesis gas through the present invention. In addition, it is possible to cope with changes in the composition of the raw material synthesis gas, thereby increasing the utilization of the production plant and improving the economical efficiency.

In addition, the present invention can intensively produce high-cost hydrocarbons in response to market conditions by controlling various operating parameters to produce various hydrocarbon compounds in one facility.

1 is a schematic view of a conventional methane synthesis process.
2 is a schematic view of a conventional volatilization process.
3 is a schematic view of a conventional diesel and wax synthesis process.
4 is a process for producing various kinds of hydrocarbon compounds according to an embodiment of the present invention.
5 is a schematic view of a hydrocarbon synthesis reactor for synthesizing various kinds of hydrocarbons.

In general, hydrocarbon compounds such as methane, natural gas, naphtha, gasoline, diesel, and wax fluctuate in price depending on international conditions and market conditions, and profitability falls sharply when the price of the product falls.

On the other hand, as shown in FIGS. 1 to 3, the process for producing hydrocarbon compounds with carbon monoxide and hydrogen has been limited to the synthesis of a specific single product for the purpose.

It is difficult to manufacture various hydrocarbons in a conventional hydrocarbon manufacturing apparatus. Therefore, hydrocarbons with the same chemical composition are difficult to change easily when the price fluctuates according to the market, so the operation profit of the facility is reduced or the economic loss is incurred.

In the present invention, the hydrocarbon is produced by reacting carbon monoxide with a synthesis gas containing hydrogen. The synthesis gas may be suitably used in the present invention as long as it contains hydrogen and carbon monoxide. For example, synthetic gas generated by gasification of coal, petroleum refining residues and biomass can be used, It can be used as synthesis gas.

Syngas through normal gasification includes carbon dioxide, hydrogen sulfide and nitrogen compounds, but they are removed through a pretreatment process. The synthesis gas thus obtained usually has a ratio of carbon monoxide to hydrogen of 1: 1. In addition, the synthesis gas obtained by reforming natural gas has a molar ratio of 1: 3. Therefore, it is necessary to control the molar ratio of carbon monoxide and hydrogen according to the types of hydrocarbons to be obtained and the synthesis gas to be used.

For example, in the synthesis of methane, it is preferable that the synthesis gas has a molar ratio of carbon monoxide to hydrogen of 1: 2.5 to 3.5, especially 1: 3. In the synthesis of methanol, dimethyl ether or gasoline, To 2.5, especially 1: 2, and in the production of diesel and wax, it is preferable to have a molar ratio of 1: 1.5 to 2.

Therefore, in the present invention, it is possible to carry out an aqueous gasification reaction for converting carbon monoxide to hydrogen to increase hydrogen in the synthesis gas, or a synthesis gas component adjustment step such as a hydrogen separation process for removing hydrogen in the synthesis gas.

As shown in FIG. 4, according to the present invention, an aqueous gasifier 4 for increasing hydrogen by performing a water gas shift (WGS) on the injected syngas 1 may be included. This water gasifier (4) is a reaction device for adjusting the ratio of carbon monoxide and hydrogen, which is the main component of the syngas, when the synthesis gas is supplied, and the reaction of the following formula (7) occurs.

CO + H ₂ O ↔ CO ₂ + H ₂ (7)

The aqueous gasification reaction shows a high dependence on temperature in an equilibrium reaction. That is, since the water gasification reaction is an exothermic reaction, the temperature continuously increases while the reaction proceeds, and accordingly, the reaction equilibrium constant decreases, so that the conversion rate of carbon monoxide is rather low. Therefore, while the aqueous gasification reaction is continued, the temperature in the water gasifier should be maintained at a constant temperature to improve the reaction efficiency.

The water gasification process can be roughly classified into low temperature shift (LTS) and high temperature shift (HTS). In the low-temperature aqueous gasification reaction, the reaction proceeds at 200 to 250 ° C using 32 to 33% of copper oxide catalyst.

In the present invention, a low temperature aqueous gasification reaction is used because the reaction starts at a temperature of 200 to 300 ° C. in most of the hydrocarbon synthesis processes, so that the reaction temperature difference between the low temperature aqueous gasification reaction and the hydrocarbon process is not large, There are advantages.

In general, about 96-98% of carbon monoxide is converted to hydrogen when the water gasification reaction is maintained in the optimum temperature range as described above. This means that the ratio of carbon monoxide to hydrogen in the downstream hydrocarbon synthesis reactor 8 should be adjusted in the range of 1: 1.5 to 1: 3.5 depending on the kind of hydrocarbon to be obtained as described above. Therefore, the conversion rate can be obtained by controlling the ratio of carbon monoxide and hydrogen by passing a part or the whole of the synthesis gas injected depending on the type of hydrocarbon to be produced through the water gasifier 4.

The amounts of synthesis gas injected into the water gasifier (4) for the types of hydrocarbons to be obtained are shown in Tables 1 and 2 below. Table 1 shows the case of using syngas by gasification of coal or biomass, and Table 2 shows the case of using syngas by natural gas reforming.

Composition of CO: H ₂ (mol%) of synthesis gas Production hydrocarbons WGS Bypass Ratio (%) 50:50 methane 51.54 DME 51.54 gasoline 51.54 Diesel oil 35.05 Wax 34.90

Composition of CO: H ₂ (mol%) of synthesis gas Production hydrocarbons WGS Bypass Ratio (%) 25:75 methane 0.1 DME 0.1 gasoline 0.1 Diesel oil - Wax -

From the above Table 1, the syngas 1 obtained by gasification of coal or biomass has a ratio of carbon monoxide to hydrogen of about 1: 1, and the molar ratio of hydrogen is insufficient for generating hydrocarbons. Thus, a portion of the synthesis gas 1 is sent to the water gasifier 4 to effect hydrogen conversion of the carbon monoxide by an aqueous gasification reaction, and another portion of the synthesis gas is passed through the bypass line 3 to an aqueous gasifier 4) is bypassed, and a syngas having a controlled ratio of carbon monoxide and hydrogen is mixed by the above-mentioned water gasifier and a bypassed synthesis gas in a mixed gas mixing tank 6 or the like, It is preferable to supply it to the obtained hydrocarbon synthesis reactor (8).

On the other hand, as can be seen from Table 2, when diesel or wax is produced using synthesis gas by natural gas reforming, hydrogen is excessively contained in comparison with the molar ratio of carbon monoxide and hydrogen required for producing diesel or wax have. Therefore, in this case, it is desirable to remove excess hydrogen.

Accordingly, in one embodiment of the present invention, in the case of using a synthesis gas containing an excess amount of hydrogen in excess of a suitable level for the synthesis of hydrocarbons to be obtained as described above, hydrogen separation for separating hydrogen from the synthesis gas (1) And may include a facility 5.

The hydrogen separation equipment 5 may be a separation membrane or a pressure swing absorber (PSA). When hydrogen is to be removed from the syngas, the hydrogen gas separator (5) is driven without driving the water gasifier (4) to partially or totally pass the synthesis gas to remove hydrogen from the mixture gas, Can be controlled. In the case where only a part of the synthesis gas 1 is passed through the hydrogen separation equipment 5, a part of the synthesis gas is transferred through the bypass line 3 and then mixed in the synthesis gas mixing tank or the like to produce carbon monoxide and hydrogen A syngas having a controlled ratio can be obtained and then supplied to the hydrocarbon synthesis reactor 8.

The hydrogen separated by the hydrogen separator may be used in a cracking process for improving the quality of hydrocarbons produced in the hydrocarbon synthesis reactor. This will be described later.

Therefore, according to an embodiment of the present invention, there is provided an exhaust gas purification system comprising an aqueous gasifier (4) for performing an aqueous gasification reaction for converting carbon monoxide contained in the supplied raw material synthesis gas (1) into hydrogen, And a mixed gas bypass line (3) for bypassing a part of the synthesis gas.

This makes it possible to appropriately control the molar ratio of carbon monoxide and hydrogen depending on the hydrocarbon to be obtained by generating hydrogen which is deficient by the water gasification reaction depending on the kind of the raw material synthesis gas to be used or by separating and removing excess hydrogen.

At this time, selection of the place where the synthesis gas passes is not particularly limited, and can be carried out through appropriate opening and closing means. At this time, the synthesis gas is selectively supplied to any one of the water gasifier 4 and the hydrogen separation equipment 5, and if necessary, the synthesis gas may be supplied to the bypass line 3 together with the synthesis gas.

The syngas processed through the water gasifier (4) or the hydrogen separation plant (5) is mixed with the bypassed synthesis gas to obtain a synthesis gas having a molar ratio of carbon monoxide and hydrogen suitable for synthesizing the desired hydrocarbons. For this purpose, the synthesis gas mixing tank 6 may be included although not particularly limited.

Then, the synthesis gas in which the molar ratio of carbon monoxide and hydrogen is controlled is supplied to a hydrocarbon synthesis reactor 8 to produce a synthesis gas by the reaction of carbon monoxide and hydrogen. At this time, the syngas discharged through the water gasifier 4 has a temperature of 200 to 250 ° C., but it is mixed into the synthesis gas in the hydrocarbon synthesis reactor 8, The temperature of the supplied synthesis gas is lowered. Further, the syngas passing through the hydrogen separation facility 5 also has a low temperature.

On the other hand, the reaction initiation temperature of the hydrocarbon synthesis reaction is 200 to 300 ° C as shown in Table 3 below. The temperature range of the synthesis gas injected into the hydrocarbon synthesis reactor 8 according to the type of each hydrocarbon is shown in the following table.

Production hydrocarbons Reactor injection temperature (캜) methane 250-300 DME 250-300 gasoline 250-300 Diesel oil 200 ~ 220 Wax 200 ~ 210

That is, when the synthesis gas in which the molar ratio is controlled is introduced into the hydrocarbon synthesis reactor 8 and has a temperature falling within the target reaction start temperature range of the hydrocarbon, it can be directly introduced into the hydrocarbon synthesis reactor 8. However, when the temperature of the syngas deviates from the reaction starting temperature range of the hydrocarbon, it is preferable to raise or lower the temperature to within the above range through the heat exchanger (7).

However, since the reaction initiation temperature of the hydrocarbon synthesis depending on the kind of hydrocarbon to be obtained has a temperature range similar to the temperature of the synthesis gas whose molar ratio is controlled as described above, the thermal load to be controlled by the heat exchanger 7 is large not.

In the present invention, the synthesis gas in which the ratio of the carbon monoxide to the hydrogen is regulated is supplied to the hydrocarbon synthesis reactor (8). The hydrocarbon synthesis reaction is an exothermic reaction and the reaction rate is fast. Therefore, when the catalyst is charged, the reaction temperature rapidly increases at the portion of the catalyst layer which is mainly reacted. That is, when the syngas is initially supplied through the upper portion of the hydrocarbon synthesis reactor, the hydrocarbon synthesis reaction occurs rapidly in the upper layer of the catalyst, and thus the temperature of the catalyst located in the upper layer of the hydrocarbon synthesis reactor 8 mainly increases abruptly.

Generally, the synthesis of hydrocarbons proceeds as an exothermic reaction, and the reaction equilibrium is greatly affected by the reaction temperature. That is, the rapid temperature rise of the catalyst layer raises the surface temperature of the catalyst, thereby causing volatilization of the main catalyst component or sintering of the catalyst, thereby shortening the catalyst life. Therefore, it is preferable that the hydrocarbon synthesis reactor 8 is an isothermal reactor. It is preferable to keep the temperature inside the reactor constant by using an isothermal reactor to continuously remove the reaction heat generated during the reaction.

In the hydrocarbon synthesis reactor (8) of the present invention, a synthesis gas is injected in the upper portion of the reactor, and a synthesis gas containing hydrocarbon generated by the reaction is discharged through a synthesis gas outlet in the lower portion of the hydrocarbon synthesis reactor (8) The hydrocarbon synthesis reactor 8 is preferably provided with a catalyst layer in a direction perpendicular to the moving direction of the synthesis gas stream passing through the inside of the hydrocarbon synthesis reactor 8 as shown in Fig. At this time, the catalyst layer may be formed in two or more layers.

As a result, the synthesis gas injected through the inlet of the synthesis gas rapidly reacts with the hydrocarbon synthesis reaction in the catalyst layer of the uppermost layer contacting with the synthesis gas. As the reaction continues, the uppermost catalyst layer is deactivated first, whereby the synthesis gas in which the reaction has not occurred is catalyzed in the next catalyst layer to synthesize hydrocarbons, thereby effectively promoting the catalytic reaction in the hydrocarbon synthesis reactor 8 can do.

A general isothermal reactor is equipped with a cooling pipe for injecting a cooling medium in a vertical direction, that is, in a direction parallel to the direction in which the synthesis gas moves from the synthesis gas injection port toward the synthesis gas discharge port. In the hydrocarbon synthesis reactor used in the present invention, As shown in FIG. 5, it is preferable to provide a plurality of catalyst layers in the horizontal direction and to install cooling / heating pipes, that is, heat exchange pipes in parallel with the catalyst layer, that is, in the direction perpendicular to the direction of movement of the synthesis gas desirable. By providing such heat exchange pipes in the respective catalyst layers, it is possible to selectively cool the catalyst layers whose temperature has been raised by the hydrocarbon synthesis reaction.

For example, when the synthesis gas is initially supplied through the upper portion, the temperature of the upper layer of the catalyst sharply increases. At this time, the temperature of the catalyst upper layer can be adjusted by adjusting the valve and flowing a large amount of cooling medium through the uppermost cooling pipe.

On the other hand, as the reaction is continued, the performance of the catalyst which mainly proceeds in the early stage is lowered, and thus the catalyst in the uppermost lower layer is involved in promoting the reaction. Accordingly, the portion having the highest temperature in the catalyst layer gradually moves from the uppermost stage to the lower stage according to the elapsed operation time of the reactor.

Therefore, when the lifetime of the catalyst layer is one year, the main hydrocarbon synthesis layer moves slowly from the upper part to the lower part according to the change of the catalytic activity. Accordingly, the part mainly generating the reaction heat also moves from the upper part to the lower part. It is possible to cool the catalyst layer by supplying the cooling medium to the heat exchange pipe that flows through the catalyst layer in the portion where the reaction heat is generated.

In the present invention, the hydrocarbon synthesis reactor (8) may be horizontally divided into a plurality of catalyst layers in consideration of the reaction heat generation characteristics of the hydrocarbon synthesis reaction, and a cooling pipe may be provided for each catalyst layer. Thus, the heat of reaction can be controlled by increasing the flow of the cooling medium to the periphery of the catalyst layer causing the maximum heat generation.

Horizontal heat exchange piping is installed considering the reaction characteristics of hydrocarbons, and the supply amount of the main cooling medium is controlled by monitoring the temperature change of the catalyst layer of the hydrocarbon synthesis reactor. When the catalyst activation degree is continuously changed by using the hydrocarbon synthesis reactor (8), the supply amount of the cooling medium is shifted from the initial uppermost stage to the maximum supply amount and then gradually to the lower cooling pipe.

On the other hand, when the gasoline is the main product, the syngas after the water gasification process is injected into the hydrocarbon reactor (8) and synthesized with methanol. Such methanol synthesis reaction should be externally supplied with heat of reaction as an endothermic reaction. Therefore, it is preferable that a heating medium other than the cooling medium is injected into the heat exchange pipe provided in the hydrocarbon reactor. The heating medium is not particularly limited, but temperature control can be performed using steam. Steam is injected into the heat exchange pipe as a heating medium and cooled by supplying the heat of reaction and discharged.

The hydrocarbon synthesis reactor 8 may be provided with a meshed support for fixing a catalyst layer in the form of a fixed bed reactor and a synthesis gas. As a result, the catalyst in the form of a pallet is filled from the top, and hydrocarbons generated from the syngas are discharged to the bottom through the pores of the meshed support plate.

At this time, the catalyst may vary depending on the hydrocarbon to be obtained, but the catalyst to be used can be suitably used in the present invention. Specifically, when methane is synthesized in the hydrocarbon synthesis reactor, the catalyst may be a nickel-based catalyst. Therefore, for example, when a synthesis gas having a ratio of carbon monoxide and hydrogen of 1: 3 is supplied to the hydrocarbon synthesis reactor, methane is synthesized by reacting as in the formula (2) under a nickel catalyst.

On the other hand, when methanol, dimethyl ether and petrol are to be synthesized, a catalyst containing copper and ZnO can be used. For example, when a synthesis gas having a ratio of carbon monoxide and hydrogen of 1: 2 is supplied to a hydrocarbon synthesis reactor, methanol is synthesized by reaction with a catalyst containing copper and ZnO as shown in formula (3), whereby dimethylether and gasoline Can be synthesized.

Further, when diesel and wax are to be produced using the Fischer-Tropsch reaction, an iron or cobalt catalyst may be used. More specifically, a cobalt catalyst can be used as a main component of diesel, and an iron catalyst can be used as a main component of wax.

As described above, since the catalyst used differs depending on the kind of hydrocarbon to be obtained, in the present invention, the catalyst layer is a structure capable of exchanging the catalyst so that the optimum catalyst can be used in accordance with the product to be obtained through the reaction .

In the hydrocarbon synthesis reactor (8), hydrogen in the synthesis gas and carbon monoxide react. Specifically, when the hydrocarbon product to be obtained is methane, the reaction of the formula (2) occurs in the hydrocarbon synthesis reactor.

CO + 3H _{2 -} > CH ₄ + H ₂ O (2)

Further, in order to improve the synthesis efficiency of methane, an endothermic reactor may be further provided as a secondary methane synthesis reactor for methane synthesis at the downstream of the hydrocarbon synthesis reactor as the isothermal reactor. The secondary methane synthesis reactor is not particularly limited as long as it is an adiabatic reactor commonly used for synthesizing methane from syngas, which can be suitably applied in the present invention.

The synthesis of methane can be performed at a high yield through the hydrocarbon synthesis reactor or the hydrocarbon synthesis reactor 8 and the secondary methane synthesis reactor 13. Thereafter, water can be separated and removed from the reaction product to recover methane.

On the other hand, when the hydrocarbon product to be obtained is methanol, the reaction of the formula (3) takes place in the hydrocarbon synthesis reactor 8 from which methanol can be obtained.

CO + 2H _{2 -} > CH ₃ OH (3)

On the other hand, when dimethyl ether (DME) is to be synthesized from methanol obtained by the reaction of the formula (3), dimethyl ether can be synthesized by carrying out the reaction of the formula (4).

2CH ₃ OH - > CH ₃ OCH ₃ + H ₂ O (4)

Therefore, a DME synthesis reactor 14 may be provided at the downstream of the hydrocarbon synthesis reactor 8 for the synthesis of dimethyl ether by the reaction of the formula (4). The DME synthesis reactor (14) is not particularly limited, and a commonly used reactor can be suitably used in the present invention.

Further, in the present invention, diesel and wax may be produced using the synthesis gas in which the molar ratio is controlled. The diesels and waxes can be produced using the Fischer-Tropsch reaction as shown in Formula (6). This reaction can be synthesized using the hydrocarbon synthesis reactor (8) of the present invention, which is a single isothermal reactor.

_{nCO + nH 2 → C n H} 2n + nH 2 O (6)

Thus, depending on the type of hydrocarbon synthesized in the hydrocarbon synthesis reactor 8, the methane yield can be increased or the DME can be produced by a methane synthesis reactor, a DME reactor, or the like.

On the other hand, since the reaction products produced in the hydrocarbon synthesis reactor 8 contain moisture, they include a water separator 15 for removing moisture from the reaction products. Whereby methane, DME or diesel and wax can be recovered.

Thus, the hydrocarbon synthesis plant of the present invention includes a water separator 15 for removing moisture. The water separator 15 is connected to the water separator 15 via the bypass line 12 when the product produced in the hydrocarbon synthesis reactor or the DME reactor or the product produced in the hydrocarbon synthesis reactor is diesel and wax Transfer. At this time, depending on the type of hydrocarbons synthesized in the hydrocarbon synthesis reactor 8, it is possible to appropriately select from among the three movement routes.

The hydrocarbon to be obtained can be recovered by removing moisture from the hydrocarbon compound as a reaction product produced in the hydrocarbon synthesis reactor 8 by the water separator 15. At this time, the water removal is not particularly limited, and a conventional method of separating water from the isohydrocarbon compound by condensing water can be applied. As an example, a water separator 15 such as a knock-out drum may be used although not limited thereto. In particular, when the synthesis gas to be obtained is methane or DME, a target product can be obtained.

On the other hand, gasoline can be synthesized from DME through an additional reaction. To this end, the obtained DME is supplied to a gasoline synthesis reactor (16). Thus, in the gasoline synthesis reactor 16, the reaction as shown in the following equation (5) is carried out to synthesize gasoline.

nCH ₃ OCH ₃ C _n H _{2n + 2} + nH ₂ O (5)

Subsequently, water is finally removed from the reaction product of the formula (5) to finally obtain gasoline. For this purpose, according to an embodiment of the present invention, it may further include a second moisture separator 17, which may be the same as the moisture separator 15 described above. Therefore, the moisture removal is not particularly limited as long as the same method as the above-described water removal can be applied.

Meanwhile, diesel and wax are simultaneously produced by the Fischer-Tropsch reaction process. Therefore, it is possible to obtain the object to be obtained by controlling the length of the hydrocarbon ring synthesized according to whether the desired hydrocarbon compound is diesel or wax. However, as described above, the water produced in the Fischer-Tropsch reaction is removed by the water separator 15, and then the hydrogen reforming process is performed to adjust the length of the hydrocarbon rings in the reaction product. The hydrogen reforming is a step of cracking the hydrocarbon ring using hydrogen, and may include a hydrogenation reactor (18).

The hydrogen used in the hydrogenation reaction may be hydrogen separated from the hydrogen separation equipment 5. As described above, when the molar ratio of hydrogen in the synthesis gas is excessive relative to the molar ratio required to produce the hydrocarbon, such as when diesel or wax is produced using natural gas reforming synthesis gas, The hydrogen separated in the hydrogen reforming reactor 5 may be supplied to the hydrogenation reactor 18 through which the hydrogen reforming process is performed to be used for hydrogen reforming.

The diesel and wax are recovered from the hydrocarbons whose hydrocarbon ring length is controlled by the hydrogenation reactor (18). The separation and recovery of the diesel and the wax can be performed by a fractional distillation method using a fractional distillation unit (19).

The unreacted synthesis gas in the hydrocarbon synthesis reactor 8 and the hydrocarbon compound or naphtha having a length shorter than the length to be obtained in the hydrogen reforming process in the hydrogenation reactor 18 are recovered by fractional distillation In addition to the wax and diesel, it is possible to carry out the Fischer-Tropsch reaction process by recycling to the hydrocarbon synthesis reactor 8 through the recycle line 20.

Hereinafter, the process for producing a heterogeneous hydrocarbon compound according to the present invention will be described in more detail with reference to the drawings.

First, as shown in Fig. 4, in order to produce a desired hydrocarbon from the synthesis gas 1 containing carbon monoxide and hydrogen as main components, a synthesis gas is branched and a part thereof is supplied to the water gasifier 4, Is transferred to the bypass line (3), is injected into the synthesis gas mixing tank (6), and mixed to control the molar ratio of carbon monoxide and hydrogen in the synthesis gas. At this time, the ratio of the stream into the water gasifier (4) and the bypass stream can be adjusted as shown in Table 1 above. Therefore, if it is not necessary to adjust the ratio of hydrogen to carbon monoxide, it is possible to transfer all of the synthesis gas through the bypass line 3.

On the other hand, when the hydrogen content of the raw syngas is higher than that required for the synthesis of hydrocarbons, a portion of the synthesis gas is passed through the hydrogen separation facility 5, To control the ratio of carbon monoxide and hydrogen in the syngas.

Specifically, when diesel or wax is produced by converting methane as shown in Table 2, it is not necessary to supply excess hydrogen to the synthesis gas and supply it to the water gasifier 4, It is injected into the hydrogen separation facility 5 to separate only the hydrogen component from the syngas and sent to the hydrogenation reactor 18 to be used in the hydrogen-cracking process of the diesel and wax components.

The temperature of the synthesis gas discharged from the heat exchanger 7 through the heat exchanger 7 is controlled by adjusting the temperature of the synthesis gas so as to synthesize the respective hydrocarbons. (3). ≪ tb >< TABLE >

As shown in FIG. 5, the hydrocarbon synthesis reactor 8 has a catalyst bed fixed in the form of a fixed bed reactor, a mesh support for reaction of the synthesis gas is installed at the bottom, And the hydrocarbons generated from the syngas are discharged to the lower end through the pores of the meshed support plate.

Meanwhile, as can be seen from FIG. 5, a horizontal heat exchange pipe is installed in consideration of the reaction characteristics of hydrocarbons, and the temperature change of the reactor catalyst layer is monitored to control the supply amount of the main cooling medium.

On the other hand, when the hydrocarbon synthesis reactor 8 is continuously operated to lower the catalytic activity, the supply amount of the cooling medium through the heat exchange pipe to the catalyst layer is gradually reduced, and the supply amount of the cooling medium to the heat exchange pipe .

When the product is methane, the synthesis gas passing through the hydrocarbon synthesis reactor (8) is injected into the additional secondary methane synthesis reactor (13) to increase the methane conversion rate and then sent to the water separator (15) Remove. Whereby the desired methane can be recovered.

On the other hand, when gasoline is the main product, synthesis gas obtained by water gasification is injected into a hydrocarbon synthesis reactor (8) to synthesize methanol. The synthesis reaction of methanol is endothermic reaction heat must be externally supplied. Therefore, a heating medium, not a cooling medium, is supplied to the heat exchange pipe provided in the hydrocarbon synthesis reactor 8 to be flowed. The heating medium may be subjected to temperature control by using steam, and the supplied steam is supplied with reaction heat into the reactor as a heating medium, cooled, and discharged.

The methanol thus produced is injected into the DME synthesis reactor 14. Here, if the object of the reaction is dl dimethyl ether, it is discharged as dimethyl ether through the water separator 15. On the other hand, when it is desired to produce gasoline, the dimethyl ether is injected into the gasoline synthesis reactor 16 to synthesize gasoline. Since moisture is produced during the synthesis of the gasoline, the second moisture separator 17 can be roughened again at the rear end.

When diesel oil or wax is a main product, the synthesis gas passing through the hydrocarbon reactor 8 is bypassed to the water separator 15 through the bypass line 21 to condense and remove the water, 18). At this time, a hydrogen line 11 is supplied from the hydrogen separation unit to the hydrogenation reactor to perform a hydrogenation reforming reaction. The reformed hydrocarbons are then fractionally distilled in fractional distillation 19 to increase the yield of the desired diesel or wax and the remaining hydrocarbons are recycled to the hydrocarbon synthesis reactor 8 via recycle line 20.

According to the present invention, the yield of the finally produced methane is about 97 to 98% by weight of methane synthesis equilibrium, and the other products are mainly argon, Carbon dioxide which is not contained in the solution. The total calorific value of the methane produced thereby is about 80% of the total calorific value of the syngas.

When the final product is dimethyl ether or gasoline, methanol is produced in the hydrocarbon synthesis reactor (8) by adjusting the ratio of carbon monoxide and hydrogen of the synthesis gas to the water gasifier (4), thereby producing dimethyl ether and gasoline. Methanol Can be exported as an intermediate product to the outside of the process and sold as a product. Methanol is produced from methanol with 98% purity or higher, which is produced from dimethyl ether and mostly from dimethyl ether and petrol. Its purity is over 96%.

When producing diesel oil or wax, diesel oil and wax are produced at the same time and can not produce diesel oil or wax alone, which is characteristic of the Fischer-Tropsch reaction. Diesel or wax can be controlled to produce a large quantity of one product by adjusting the operating conditions according to which of the main products.

For example, if the reaction temperature is maintained as high as 220 ° C and a cobalt catalyst is used, about 60% by volume of the discharged Fischer Tropsch liquid can be produced as diesel oil, and the remaining 40% by volume is produced as naphtha and wax. On the other hand, if the reaction temperature is lowered to 210 ° C and an Fe catalyst is used, the wax can be produced at about 50% by volume or more. At this time, 20 vol% is produced as naphtha and 30 vol% is produced as diesel oil. Accordingly, the production fraction of the diesel in the final product produced can be controlled in the range of 30 to 50% by volume and the production fraction of the wax in the range of 20 to 50%.

As described above, according to the present invention, various types of hydrocarbons can be produced by using one hydrocarbon synthesis facility. Therefore, it is possible to selectively synthesize hydrocarbons favorable from the syngas in consideration of market conditions and the like.

1: Synthesis gas 3: Bypass line
4: Water gasifier 5: Hydrogen separation plant
6: Synthetic gas mixing tank 7: Heat exchanger
8: Hydrocarbon synthesis reactor 11: Hydrogen line
12: (Hydrocarbon) Bypass line 13: Secondary methane synthesis reactor
14: DME synthesis reactor 15: water separator
16: petrol reactor 17: second moisture separator
18: hydrogenation reactor 19: fractional distillation
20: recirculation line

Claims (22)

A syngas component adjusting means for adjusting a composition ratio of carbon monoxide and hydrogen contained in the supplied raw material synthesis gas; A hydrocarbon synthesis means for synthesizing hydrocarbons by reacting the synthesis gas controlled by the synthesis gas component regulating means to obtain a hydrocarbon-containing synthesis gas; And a target product recovery means for separating and recovering the final object to be obtained by post-treating the hydrocarbon-containing synthesis gas obtained by the hydrocarbon synthesis means,
The syngas component adjusting means
An aqueous gasifier for performing an aqueous gasification reaction for converting carbon monoxide contained in the supplied raw material synthesis gas into hydrogen; A hydrogen separation equipment for separating and removing hydrogen contained in the raw material synthesis gas; And a mixed gas bypass line for bypassing a part or all of the synthesis gas according to a molar ratio of carbon monoxide and hydrogen contained in the synthesis gas. At least two of them,
Wherein the hydrocarbon synthesis means comprises:
A hydrocarbon synthesis reactor in which a component-regulated synthesis gas discharged from the synthesis gas component regulating means is supplied and a hydrocarbon of methane, methanol or diesel and wax is synthesized from the component-regulated synthesis gas to obtain a hydrocarbon-containing synthesis gas; And
A methane synthesis reactor for supplying methane to the hydrocarbon-containing synthesis gas and synthesizing methane from the hydrocarbon-containing synthesis gas containing methane; A DME synthesis reactor for synthesizing dimethyl ether from a hydrocarbon-containing synthesis gas containing methanol; And a hydrocarbon bypass line bypassing the hydrocarbon-containing synthesis gas comprising the diesel and wax; , ≪ / RTI >
The target product collecting means includes:
Separating and removing water from the product stream discharged from the methane synthesis reactor, the DME synthesis reactor, or the hydrocarbon bypass line; DME; Or a water separator for discharging diesel and wax;
Wherein the synthesis gas is a hydrocarbon gas.
2. The method of claim 1, further comprising the steps of: supplying a synthesis gas having passed through said water gasifier, a hydrogen separation facility, and a bypass line, and supplying a synthesis gas having a predetermined molar ratio of carbon monoxide and hydrogen, ≪ / RTI >
The hydrocarbon synthesis device according to claim 1, wherein the hydrogen separation equipment is a pressure conversion adsorber or separation membrane.
The hydrocarbon synthesis apparatus according to claim 1, further comprising a heat exchanger for raising or lowering the temperature of the component-regulated synthesis gas supplied to the hydrocarbon synthesis reactor.
The gasoline synthesis reactor according to claim 1, wherein a gasoline synthesis reactor for synthesizing gasoline by the reaction of formula (5) from DME discharged from the water separator; And
nCH ₃ OCH ₃ C _n H _{2n + 2} + nH ₂ O (5)
A second moisture separator for removing moisture as a by-product from the reaction product produced in the gasoline synthesis reactor and discharging gasoline;
.
The method according to claim 1,
A hydrogenation reactor in which a hydrotreating process is performed in which a hydrocarbon containing diesel and wax discharged from the water separator reacts with hydrogen to crack the diesel or wax to a predetermined length; And
The diesel and wax discharged from the hydrogenation reactor are subjected to fractional distillation to separate and recover the diesel and the wax, respectively, and a residual distillate containing residual naphtha is discharged to the hydrocarbon synthesis reactor
.
7. The hydrocarbon synthesis apparatus according to claim 6, wherein the hydrogenation reactor is connected to the hydrogen separation facility, and hydrogen separated from the hydrogen separation facility is supplied to the hydrogenation reactor.
The hydrocarbon synthesis apparatus according to claim 6, wherein the fractionation distiller is connected to the hydrocarbon synthesis reactor, and the residual hydrocarbon including naphtha discharged from the fractionation distiller is supplied to the hydrocarbon synthesis reactor.
The process according to claim 1, wherein the hydrocarbon synthesis reactor
And a catalyst layer supported on the catalyst in a direction perpendicular to the moving direction of the syngas stream into which the synthesis gas is injected at the upper portion of the reactor and the hydrocarbon-containing synthesis gas is discharged through the lower portion of the reactor.
The hydrocarbon synthesis apparatus according to claim 9, wherein the hydrocarbon synthesis reactor comprises a heat exchange pipe arranged in a direction parallel to the catalyst layer for each catalyst layer, and the heat exchange medium is transferred through the heat exchange pipe.
10. The hydrocarbon synthesis device according to claim 9, wherein the catalyst layer is a catalyst layer comprising a nickel catalyst for methane synthesis, a copper and ZnO-containing catalyst for methanol synthesis, or an iron or cobalt catalyst for diesel and wax synthesis.
Wherein the molar ratio of the carbon monoxide and hydrogen contained in the raw synthesis gas is controlled such that the synthesis gas is separated into two streams, one of which converts carbon monoxide in the synthesis gas into hydrogen by an aqueous gasification reaction, A synthesis gas component adjustment step of separating the contained hydrogen and bypassing and mixing the other stream;
Reacting the synthesis gas with the molar ratio adjusted in the presence of a catalyst to produce methane; Methanol; Or a hydrocarbon synthesis of a mixture of diesel and wax;
Depending on the kind of the hydrocarbon synthesized in the hydrocarbon synthesis step, the reaction product may be subjected to a secondary methane synthesis reaction step and a dimethyl ether (DME) synthesis reaction step, followed by separating water from the reaction product, or by bypassing the synthesized hydrocarbon, And the hydrocarbon is recovered. When the synthesized hydrocarbon is methane, the reaction proceeds to the secondary methane synthesis reaction step. When the synthesized hydrocarbon is methanol, the reaction proceeds to the DME synthesis reaction step. When the synthesized hydrocarbon is a mixture of diesel and wax, Hydrocarbon recovery step that passes
Wherein the hydrocarbon is selected from the group consisting of hydrocarbons and hydrocarbons.
The method of claim 12, wherein the CO: H ₂ molar ratio of the syngas adjusted in the synthesis gas component adjustment step is 1: 2.5 to 1: 3.5 when the hydrocarbon obtained in the hydrocarbon synthesis step is methane, and 1: 1.8 to 2.5 In the case of a mixture of diesel and wax, and 1: 5 to 2 in the case of a mixture of diesel and wax.
13. The method of claim 12, wherein the catalyst is a catalyst layer comprising a nickel catalyst for methane synthesis, a copper and ZnO containing catalyst for methanol synthesis, or an iron or cobalt catalyst for diesel and wax synthesis.
13. The method of claim 12, wherein the separation of hydrogen is performed by pressure conversion adsorption or separation of membranes.
The hydrocarbon synthesis method according to claim 12, further comprising a heat exchange step of raising or cooling the temperature of the syngas controlled by the molar ratio by heat exchange.
17. The method according to claim 16, wherein the heat exchange is carried out in the case where the hydrocarbons obtained in the hydrocarbon synthesis step are methane or methanol, the heat exchange step is performed so that the molar ratio of the synthesis gas is controlled to be in the range of 250 to 300 占 폚, And the heat exchange step is carried out in the range of 200 to 210 캜.
The method according to claim 12, wherein the DME recovered in the hydrocarbon recovery step is a gasoline synthesis step of synthesizing gasoline by the reaction of formula (5); And
nCH ₃ OCH ₃ C _n H _{2n + 2} + nH ₂ O (5)
A gasoline recovery step of removing moisture as a by-product from the generated reaction product and discharging gasoline
≪ / RTI >
13. The method of claim 12,
A hydrogenation step of reacting the mixture of diesel and wax with hydrogen to perform a hydrogenation process of cracking the diesel and wax with hydrocarbons of a predetermined length; And
A diesel and wax recovery step in which the mixture of diesel and wax subjected to the hydrogenation process is fractionally distilled to separate and recover the diesel and wax, respectively
≪ / RTI >
20. The method of claim 19, wherein the hydrogen in the hydrogenation step is hydrogen separated from the synthesis gas in the step of controlling the synthesis gas component.
20. The hydrocarbon synthesis method according to claim 19, wherein residual hydrocarbon containing naphtha remaining after the fractional distillation is discharged and reused as synthesis gas in the hydrocarbon synthesis step.
The hydrocarbon synthesis method according to claim 12, wherein the hydrocarbon is synthesized during the hydrocarbon synthesis reaction by supplying a cooling or heating medium to the catalyst to maintain the activity of the catalyst through heat exchange between the catalyst and the cooling or heating medium.

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