KR102170654B1 - Microchannel reactor with controllability in reaction heat and control method thereof - Google Patents

Abstract

The present invention relates to a microchannel reactor for a Fischer-Tropsch synthesis reaction, wherein a flow of a refrigerant in a cooling layer flows in a direction perpendicular to the catalyst layer, and the flow rate of the refrigerant varies depending on the portion of the cooling layer, thereby controlling temperature in the catalyst layer. It provides a way to make it easier. In the case of using the heat exchange microchannel reactor, there is an effect of increasing the CO conversion rate and selectivity of C5+ hydrocarbons in the Fischer-Tropsch reaction by controlling the hot spot due to the reaction heat.

Description

TECHNICAL FIELD [Microchannel reactor with controllability in reaction heat and control method thereof]

The present invention relates to a method for effectively controlling the heat of reaction of an exothermic reaction in a microchannel reactor. As a representative high-temperature, strong exothermic reaction that can be carried out in a microchannel reactor, there is a Fischer-Tropsch synthesis reaction.

The Fischer-Tropsch (FT) reaction is a reaction for producing synthetic oil from synthesis gas (CO + H ₂ ). Syngas is mainly produced by gasification of coal or reforming of natural gas.

CO + 2H ₂ → -[CH ₂ ] _n- + H ₂ O ΔH ₂₉₈ = ~-160 kJ/mol

As shown in the above formula, the Fischer-Tropsch reaction is a strong exothermic reaction, and the heat of reaction control is important. If the heat of reaction is not controlled, the temperature of the reactor rises rapidly, causing serious problems in the safety of the reaction process and obtaining unwanted products.

Catalysts for Fischer-Tropsch reaction are largely classified into cobalt and iron catalysts. The cobalt-based catalyst is advantageous for obtaining a paraffinic hydrocarbon having a long catalyst life and a linear chain, and has the advantage of generating less carbon dioxide. However, if the ratio of hydrogen to CO is high because it is sensitive to the composition of the syngas, the selectivity of methane increases, and the selectivity of C5+ (hydrocarbons with 5 or more carbon atoms) is relatively reduced. In addition, C5+ selectivity is sensitive to the reaction temperature, so if the reaction temperature rises above 200 to 240 degrees Celsius, the C5+ selectivity decreases rapidly, so controlling the reaction temperature is essential. Since cobalt-based catalysts are expensive, a small amount must be well dispersed on the surface of the support before use. Alumina, silica, titania, etc. are used as the support, and noble metals such as Ru, Pt, and Re are used as cocatalysts to improve performance.

Iron-based catalysts were mainly used in the early stages, and catalysts are cheaper than cobalt-based catalysts, but their lifespan is short, methane selectivity is low at high temperatures, olefin selectivity among hydrocarbons is high, and oxygenates (alcohols, aldehydes, etc.) It produces by-products such as molecules containing oxygen atoms such as ketones).

The types of reactors for the Fischer-Tropsch reaction that are currently considered are a tubular fixed bed reactor, a fluidized bed reactor, a slurry phase reactor, and a microchannel reactor equipped with a heat exchanger ( It is divided into a microchannel reactor or a multi-channel reactor, and representative fluidized bed reactors include a circulating fluidized bed reactor and a fixed fluidized bed reactor. Since reaction characteristics and product distribution vary depending on the reactor type, it must be appropriately selected according to the target end product. In the existing commercialized processes of 10,000 BPD or more, a fluidized bed reactor (SASOL) and a multi-tubular fixed bed reactor (Shell) have been used. However, since this type of reactor is suitable for a relatively large gas field, a more compact and highly efficient reactor is required for a much smaller gas field or a process that requires the use of flare gas. And recently, it is designed to be able to produce while searching for resources, and to unload where there is demand. As interest in FPSO (floating production, storage and offloading) processes is very high, research on small scale and high-efficiency processes is being conducted worldwide. This GTL FPSO is to build a GTL plant on a line with limited space, so the smaller the volume of the reactor compared to the production volume is, the more advantageous the micro-channel reactor or the multi-channel reactor type among the above-mentioned reactors is considered as the most promising reactor type.

The FT reactor is mainly suitable for producing diesel, lubricating base oil, wax, etc., and the low temperature F-T process is mainly operated. In the low-temperature FT process, more than 60% of hydrocarbons with a higher boiling point than diesel are produced, so diesel is additionally manufactured through subsequent processes such as hydrocracking, and the wax component is converted into a high-quality lubricant base oil through a dewaxing process. Switch to use.

The typical multi-tubular fixed bed reactor and slurry-phase reactor for low-temperature F-T reactions have several advantages, but they have a large burden on volume and weight compared to micro or multi-channel reactors. The multi-tubular fixed bed reactor has the advantage of low scale-up and low mechanical loss of the catalyst, but the volume occupied by the process is very large and the equipment cost and construction cost are high because the reactor has the largest volume compared to the production volume. In addition, it is difficult to control the reaction due to relatively low heat and mass transfer efficiency inside the catalyst layer. The slurry reactor is inexpensive in equipment and construction costs and has good heat and mass transfer efficiency, but it is difficult to design because it can be scaled up only by analyzing the dynamics inside the complex reactor, and there is a mechanical loss of the catalyst due to friction or collision.

Multi-channel reactors (hereinafter referred to as microchannel reactors) are reactors with maximized heat transfer efficiency to enable reaction at high space velocity, and have a relatively small volume compared to production (1/5 to 1/2 of the existing reaction process). As a result, equipment and construction costs are low, and production can be increased with the concept of number-up, so scale-up is easy, and mechanical loss due to friction or collision of the catalyst is minimal. In addition, the loss due to shaking of the catalyst or the change in reaction behavior that may occur during the movement of the device is insignificant. However, in the case of a wash coat on the wall of the reactor like a wall reactor, there is a disadvantage that it is very difficult or almost impossible to replace the catalyst at the end of its life due to deactivation of the catalyst. In the type of charging catalyst particles, catalyst replacement is relatively easy, but there is a disadvantage in that the heat transfer efficiency is inferior to that of a reactor in which the reactor wall is washed-coated.

Strong exothermic reactions at high temperatures, such as F-T reactions, are often restricted in increasing the yield of the desired product because it is not easy to control the heat of reaction. In the present invention, in controlling the reaction heat of a strong exothermic reaction in a microchannel reactor in which the catalytic reaction layer and the cooling layer are alternately stacked, the refrigerant has a cross flow direction compared to the reactant, which is a cooling method that is easy to scale-up. It is intended to provide a microchannel reactor designed to facilitate reaction heat control in the structure.

The first aspect of the present invention is a plate-type heat exchange microchannel reactor in which a reaction layer in which an exothermic reaction occurs through a catalyst while a reactant flows and a cooling layer through which a refrigerant flows are alternately stacked, and the flow of the refrigerant in the cooling layer is the flow of the reactant in the reaction layer. Heat transfer occurs from the reaction layer to the cooling layer through heat exchange while being in a direction at right angles to, and the cooling layer is divided into two or more partitions parallel to the flow of the refrigerant, and the refrigerant is formed in a partition including a hot spot formed in the reaction layer. It provides a heat exchange microchannel reactor characterized in that the flow rate, flow rate, or both are controlled to be greater than that of other compartments that do not contain hot spots.

A second aspect of the present invention provides a method for producing synthetic oil comprising converting syngas through a Fischer-Tropsch reaction in the heat exchange microchannel reactor of the first aspect.

Hereinafter, the present invention will be described in detail.

In general, a microchannel reactor has a structure in which plates are stacked, and the layer with the catalytic reaction layer has a cooling layer above and below it, and the catalytic reaction layer has a thickness of about several millimeters. Microchannel reactors have been attracting attention as reactors for strong exothermic reactions or endothermic reactions because they have excellent heat exchange performance because the heat transfer area is 10 to 100 times larger than that of conventional tube-type fixed bed catalytic reactors.

Depending on the flow direction of the reactants in the catalytic reaction layer, the flow of the refrigerant can be divided into co-current, counter-corrent, and cross-current flows. This may be determined by the flow rate of the reactant, the calorific value, the size of the reactor, and the like.

In general, the flow method of the refrigerant in a right-angle direction has the advantage of being economically applicable to a large reactor because the refrigerant flow path is simple and the flow path length is short. In addition, the structure in which the refrigerant has a cross flow direction compared to the reactant is easy to scale-up. In general, when the refrigerant flows in a perpendicular direction in the exothermic reaction, the temperature tends to increase in the catalytic reaction layer corresponding to the downstream portion from which the refrigerant exits (FIGS. 2, 4 and 6 ). This is because heat accumulates as the refrigerant goes toward the outlet and the temperature rises.

In the case of exothermic reaction in the fixed bed tubular catalytic reactor, hot spots are formed due to overheating. In the present specification, a hot spot refers to the highest temperature in a reaction bed equipped with a catalyst.

In the exothermic reaction, the temperature of the catalytic reaction bed in the reactor is also affected by the flow rate of the reactant, so that the location of the high point temperature is changed. For example, when the flow rate of the reactant is very slow, most of the reaction occurs at the top of the catalyst layer and the amount of gas that goes out to the rear end of the reactor is small, so a hot spot occurs at the top of the reactor (Fig. 2 and Fig. 4). Conversely, the flow rate of the reactant is very high. In this case, the reaction heat at the top of the reactor is pushed to the rear stage by the reaction gas, limiting the temperature increase, but the reaction heat accumulates at the rear stage, resulting in a high temperature region (Fig. 6).

Therefore, it is necessary to control the generation of high temperatures at the outlet of the refrigerant in the flow method of the refrigerant in a right angle direction.

In the present invention, a reaction layer in which an exothermic reaction occurs through a catalyst as a reactant flows and a cooling layer through which a refrigerant flows are alternately stacked, and the flow of refrigerant in the cooling layer is in a plate-type heat exchange microchannel reactor in a direction perpendicular to the flow of the reactant in the reaction layer. , The cooling layer is divided into two or more divisions parallel to the refrigerant flow, but the flow rate, flow rate, or both of the refrigerant in the division including the hot spot formed in the reaction layer are not included in the hot spot. It features a larger adjustment than the compartment. Through this, the present invention can not only increase the yield of a target product in a strong exothermic reaction at a high temperature where it is not easy to control the heat of reaction (Table 1), but also can delay the shortening of the life of the catalyst due to the occurrence of high points.

In one embodiment of the present invention, (i) when the flow rate and/or flow rate conditions at each point are the same when the refrigerant is injected, the high point generated in the catalytic reaction layer is determined, for example, by experiment and/or computational fluid dynamics (Computational Fluid Dynamics, CFD), predicting, (ii) the cooling layer is divided into two or more partitions parallel to the refrigerant flow, preferably 10 or less, but the partition and the reaction layer including hot spots formed in the reaction layer The cooling layer partitions are divided to include each partition including hot spots formed in (iii) the hot spots formed in the reaction layer while maintaining the flow rate of the total refrigerant used in the prediction of the high point. In the containing section, the flow rate and/or the flow rate of the refrigerant can be adjusted to be greater than that of other sections that do not contain a hot spot.

For example, another compartment that does not include a hot spot may include a catalytic reaction layer having the lowest average temperature of the reaction bed temperature corresponding to the corresponding compartment or the lowest temperature downstream of the refrigerant flow (reactant Based on the flow direction, the third section of Fig. 2, the third section of Fig. 4, and the first section of Fig. 6).

In order to control the amount of heat generated in the catalytic reaction layer, the thickness of the catalytic bed in the reaction layer located between the two adjacent cooling layers for heat exchange is within the range of 1 to 5 mm, and the thickness of the cooling layer is within the range of 0.5 to 3 mm. Can be adjusted.

The cooling layer of the present invention is divided into two or more partitions so as to vary the flow rate and/or flow rate of the refrigerant and, in some cases, to vary the temperature of the incoming refrigerant.

In the present invention, when the cooling layer is divided into two or more partitions parallel to the refrigerant flow, the width of each partition can be made equal (FIGS. 2 to 7) or uneven.

In the present invention, the cooling layer and/or the reaction layer may be composed of a plurality of microchannels (FIG. 1). While the refrigerant layer is composed of microchannels, the catalytic reaction layer may be composed of a slab type fixed layer, or the reaction layer may be composed of microchannels. In the reaction layer composed of microchannels, a catalyst may be inserted into the channel to be filled or attached to the inner wall of the reactor by a method such as coating.

The cooling layer and/or the reaction layer may be provided with a plurality of microchannels, so that the flow rate and/or flow rate in each microchannel can be independently and/or dependently adjusted. The microchannels in the cooling layer and/or the reaction layer may have the same or different width and/or height from each other to adjust the flow rate and/or flow rate.

Therefore, each compartment of the cooling layer may be composed of one microchannel or a plurality of microchannels. By varying the volume, shape, and/or number of microchannels used for each compartment, the refrigerant flow rate for each compartment may be differently adjusted.

In the present invention, the high point also includes the case where it is higher than the undesirable temperature that can occur in the catalytic reaction layer. That is, the point of occurrence above the undesired temperature in the catalytic reaction layer belongs to the category of the high point generated in the reaction layer in the present invention, and even in this case, control by increasing the flow rate and/or flow rate of the refrigerant in the corresponding refrigerant layer section can do.

For example, in the present invention, the cooling layer is divided into three or more partitions parallel to the refrigerant flow, but the flow rate of the refrigerant and/or in the partition including the undesired high temperature occurrence point or less than the temperature of the hot spot in the catalytic reaction layer The flow rate can be adjusted to be greater than that of other sections including the catalytic reaction layer having the lowest average temperature of the reaction bed temperature corresponding to the corresponding section or the lowest temperature downstream of the refrigerant flow.

In the present invention, the cooling layer is divided into three or more compartments parallel to the refrigerant flow, and the lower the average temperature corresponds to the average temperature of the reaction bed temperature corresponding to the corresponding compartment, the lower the flow rate, flow rate, or both of the refrigerant in the compartment. It can be adjusted (Figs. 3 and 5).

In addition, the present invention divides the cooling layer into three or more partitions parallel to the refrigerant flow, and the partition corresponding to the upstream in the flow direction of the reactant among the other two adjacent partitions of the partition including a hot spot formed in the reaction layer. The flow rate, flow rate, or both of the refrigerant in may be adjusted to be the largest than other sections (the second section in FIG. 7 based on the reactant flow direction).

By applying the various heat of reaction control methods of the present invention described above so that the temperature difference between the highest point and the lowest point in the reaction layer equipped with the catalyst is within 10°C, the flow rate, flow rate, or both of the refrigerant can be differently adjusted for each section of the cooling layer. have.

Even if the various heat of reaction control methods of the present invention described above are used, the temperature (T ₁ ) at an arbitrary point of the heating layer is higher than the temperature (T ₂ ) at the point of the cooling layer corresponding thereto, thereby preventing heat exchange throughout the heating layer. It is preferable that heat transfer can occur from the reaction layer to the cooling layer through.

In the following, a heat exchange microchannel reactor for the Fischer-Tropsch (FT) reaction, which is a high-temperature, strong exothermic reaction that is not easy to control the heat of reaction, is a representative example. The flow rate, flow rate, or both of the refrigerant in the compartment including the hot spot formed in the FT reaction layer by dividing the cooling layer into two or more compartments in a direction perpendicular to the FT reaction layer than other compartments not including the hot spot A method of manufacturing synthetic oil by converting syngas using a heat exchange microchannel reactor with a larger control will be described.

Synthetic oil production method according to the present invention

The FT reaction layer in which the FT exothermic reaction occurs through the FT catalyst while the syngas reactant flows, and the cooling layer through which the refrigerant flows are alternately stacked, and the flow of the refrigerant in the cooling layer is perpendicular to the flow of the reactant in the reaction layer, and the cooling layer Is divided into two or more partitions parallel to the refrigerant flow, and the flow rate, flow velocity, or both of the refrigerant in the partition including the hot spot formed in the FT reaction layer are greater than the other partitions not including the hot spot. Converting the syngas through a Fischer-Tropsch reaction in a controlled heat exchange microchannel reactor; And

And optionally performing a hydrocracking process and/or a dewaxing process on the product of the Fischer-Tropsch reaction.

The optimum reaction temperature of most cobalt-based FT reaction catalysts is around 200~240℃, and the selectivity and CO conversion of C ₅ + hydrocarbon compounds are high near this reaction temperature, and CO conversion is low below 200℃, and above 240℃. C ₅ + hydrocarbon selectivity is greatly reduced.

The C5+ selectivity is sensitive to the reaction temperature, so if the reaction temperature rises above 240°C, the C5+ selectivity rapidly decreases, so controlling the reaction temperature is essential.

The optimum reaction pressure of the cobalt-based FT reaction catalyst is 10 to 40 atmospheres (bar), the molar ratio of hydrogen to CO is 2.0, and the space velocity may be 1000 to 20,000 cc/(g _cat h).

In the heat exchange microchannel reactor according to the present invention, the temperature control of the F-T reaction layer may be controlled by the amount of refrigerant injected and the refrigerant temperature relative to the converted syngas. When the injection amount of cooling water increases, the temperature of the F-T reaction layer may decrease.

However, when the temperature of the FT reaction layer is decreased by increasing the injection amount of the refrigerant, the overall temperature of the FT reaction layer is too low to reduce the conversion rate of the synthesis gas.If the injection amount of the refrigerant is decreased, the temperature of the FT reaction layer is decreased. The conversion rate of synthesis gas increases due to excessive increase, but the C5+ selectivity decreases due to the increase in methane.

In addition, even if an appropriate amount of refrigerant is injected, the temperature gradient of the catalyst layer varies depending on the thickness of the catalyst layer, the structure of the cooling layer, and the method of refrigerant injection, so that the selectivity of the product is affected.

In the F-T exothermic reaction, when the refrigerant flows in a right angle direction, heat accumulates as the refrigerant goes toward the outlet, and the temperature rises. Therefore, the temperature rises in the catalyst layer corresponding to the part where the refrigerant exits.

In the present invention, the flow of the refrigerant in the cooling layer existing above and below the catalytic reaction layer flows in a direction perpendicular to the flow of the reactant to facilitate scale-up, but to control the amount of heat generated in the catalytic reaction layer, in the cooling layer It is characterized by differently adjusting the flow rate and/or flow rate of the refrigerant.

Therefore, according to the present invention, if the flow rate and/or flow rate of the refrigerant is changed according to the position of the high point of the catalyst layer in the microchannel F-T reactor of the refrigerant flow in a right angle direction, the temperature in the catalytic reaction layer can be uniformly controlled (Table 1).

Specifically, in order to vary the flow rate and/or flow rate of the refrigerant according to the position of the high point of the catalyst layer, the cooling layer is divided into two or more partitions parallel to the refrigerant flow, and in the cooling layer divided into two or more partitions, the FT reaction layer is By controlling the flow rate, flow rate, or both of the refrigerant in the compartment containing the hot spot to be larger than that of the other compartments not including the hot spot, the reaction temperature of the reaction bed with the FT catalyst is 220°C. It can be adjusted within the range of ±20 ℃, preferably the temperature in the reaction bed equipped with the FT catalyst can be adjusted so that the temperature difference between the highest point and the lowest point is within 10 ℃.

As can be seen from Table 1, when the temperature in the catalyst layer becomes uniform (Examples 1 to 3), the CO conversion rate increases, and in particular, C5+ selectivity may increase.

Non-limiting examples of synthetic oils include diesel, lubricating base oil, wax, and the like, and additionally manufacture diesel through a subsequent process such as hydrocracking and/or undergo a dewaxing process so that the wax component is of high quality. It can be converted to lubricating base oil.

Each description and embodiment disclosed in the present invention can be applied to each other description and embodiment. That is, all combinations of various elements disclosed in the present invention belong to the scope of the present invention. In addition, it cannot be seen that the scope of the present invention is limited by the specific description described below.

According to the present invention, by using a heat exchange microchannel reactor designed to vary the flow rate and/or flow rate of the refrigerant according to the position of the high point of the catalyst layer, it is possible to uniformly control the temperature in the catalytic reaction layer by effectively controlling the heat generation of the FT reaction, which is an exothermic reaction. In addition, higher C5+ yields can be obtained.

1 shows the dimensions of the reactor used in the microchannel reactor computer simulation.
Figure 2 shows the temperature distribution in the microchannel reactor by the computational simulation performed by Comparative Example 1.
3 shows the temperature distribution in the microchannel reactor by computer simulation performed according to Example 1.
4 shows the temperature distribution in the microchannel reactor by computational simulation performed by Comparative Example 2.
5 shows the temperature distribution in the microchannel reactor by computer simulation performed in Example 2.
6 shows a temperature distribution in a microchannel reactor by computational simulation performed by Comparative Example 3.
7 shows the temperature distribution in the microchannel reactor by computer simulation performed according to Example 3.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.

Manufacturing example 1: Fisher- Tropsch Preparation of reaction cobalt catalyst

A solution obtained by mixing 29.5 g of cobalt nitrate (Co(NO ₃ ) ₂ ·6H ₂ O) in 33 mL of ethanol was impregnated with 20.0 g of gamma-alumina. After removing the solvent in a rotary pressure evaporator, the slurry was dried in an oven at 100° C. for 12 hours, and then calcined in an air atmosphere at 400° C. for 5 hours to prepare a 20wt% Co/Al ₂ O ₃ catalyst.

Experimental example One

A kinetic experiment was performed to prepare synthetic oil by FT reaction in syngas from the FT catalyst prepared in Preparation Example 1. In a 1/2-inch stainless steel fixed-bed reactor, 0.1 g of the cobalt-based catalyst prepared in Preparation Example 1 and 1 g of silicon carbide (SiC) as a diluent were mixed and charged, and under a hydrogen (5 vol% H ₂ /He) atmosphere at 400° C. for 5 hours It was subjected to reduction treatment. Reaction temperature 210~240 ℃, reaction pressure 5~30 kg/cm ² , The molar ratio of carbon monoxide: hydrogen: argon (internal standard), which is a reactant, was fixed at a ratio of 31.5: 63.0: 5.5 under various reaction conditions with a space velocity of 1000 to 30000 L/kg _cat /hr, and injected into the reactor. As for the reaction conditions, the kinetics of the FT reaction for the catalyst were obtained from the results obtained under the condition that the CO conversion rate did not exceed 30%.

Experimental example 2

Computational Fluid Dynamics (CFD) was performed on the microchannel reactor based on the kinetics of the F-T catalyst obtained in Experimental Example 1. The computer simulation was performed using COMSOL Multiphysics 5.3 (COMSOL, Inc), and the conditions are as follows. The detailed shape of the microchannel reactor used in the computational simulation is shown in Fig.1, and the flow of the refrigerant flows in a direction perpendicular to the flow direction of the reactant in the catalyst layer, and the refrigerant flow area is divided into three parts, and the flow rate of the refrigerant is different. The simulation was carried out.

The temperature of the reactant injected into the catalyst layer is 233°C, the pressure at the outlet is 22 atm, and the composition of the syngas is H ₂ : CO: CO ₂ : Ar = 57: 28: 9: 6 in molar ratio. The inlet temperature in the refrigerant layer was 230°C, the inlet pressure was 27.7 atm, and the reference line speed was set to 3.789 mm/s to perform computational simulation.

Comparative example One

The microchannel reactor was simulated as in Experimental Example 2, and the space velocity of the syngas was 11, 842cc/(g _cat h), and the refrigerant flow rate in the refrigerant layer was equally injected in three regions. The results of the computational simulation of the reactor are shown in Figure 2 as a temperature distribution in the reactor, and the reaction results are shown in Table 1.

Example One

The microchannel reactor was simulated as in Comparative Example 1, and the total flow rate of the refrigerant in the refrigerant layer was injected in the same manner as in Comparative Example 1, but the flow rate in the injection region was injected in three regions. The ratio of the refrigerant injected into the upper part of the refrigerant layer: the middle part: the lower part was 50%: 33.3%: 16.7%. The results of the computational simulation of the reactor are shown in Figure 3 as a temperature distribution in the reactor, and the reaction results are shown in Table 1.

Comparative example 2

The microchannel reactor was simulated as in Experimental Example 2, the space velocity of the syngas was 9, 473.6cc/(g _cat h), and the refrigerant flow rate in the refrigerant layer was injected equally in three regions. The results of the computational simulation of the reactor are shown in Figure 4 as a temperature distribution in the reactor, and the reaction results are shown in Table 1.

Example 2

The microchannel reactor was simulated as in Comparative Example 2, and the total flow rate of the refrigerant in the refrigerant layer was injected in the same manner as in Comparative Example 2, but the flow rate in the injection region was injected in three regions. The ratio of the refrigerant injected into the upper part of the refrigerant layer: the middle part: the lower part was 53.3%: 33.3%: 13.3%. The results of the computational simulation of the reactor are shown in Figure 5 as a temperature distribution in the reactor, and the reaction results are shown in Table 1.

Comparative example 3

Computer simulation of the microchannel reactor was performed as in Experimental Example 2, the space velocity of the syngas was 59, 210cc/(g _cat h), and the refrigerant flow rate in the refrigerant layer was equally injected in three regions. The results of the computational simulation of the reactor are shown in Figure 6 as a temperature distribution in the reactor, and the reaction results are shown in Table 1.

Example 3

The microchannel reactor was simulated as in Comparative Example 3, and the total flow rate of the refrigerant in the refrigerant layer was injected in the same manner as in Comparative Example 3, but the flow rate in the injection region was different in three regions. The ratio of the refrigerant injected into the upper part of the refrigerant layer: the middle part: the lower part was 25%: 41.7%: 33.3%. The results of the computational simulation of the reactor are shown in Figure 7 as a temperature distribution in the reactor, and the reaction results are shown in Table 1.

Reactant space velocity (cc/(gcat h)
Refrigerant flow distribution

Peak temperature (℃) CO conversion rate (%)
Selectivity (%)
Top(%) Central (%) bottom(%) CH4 C2-C4 C5+ Example 1 11,842 50 33.3 16.7 233.99 58.463 8.3353 11.372 80.293 Example 2 9,473.6 53.3 33.3 13.3 233.04 67.52 8.2685 11.182 80.549 Example 3 59,210 25 41.7 33.3 235.06 16.447 8.4034 11.7246 79.872 Comparative Example 1 11,842 33.3 33.3 33.3 234.62 58.392 8.3558 11.432 80.212 Comparative Example 2 9,473.6 33.3 33.3 33.3 234.45 67.514 8.3062 11.293 80.401 Comparative Example 3 59,210 33.3 33.3 33.3 235.22 16.405 8.4163 11.771 79.812

As shown in the results performed in Comparative Examples 1 to 3, the flow of the refrigerant flows in a direction perpendicular to the flow direction of the reactant in the catalyst layer, and when the flow rate of the refrigerant is the same, a high temperature region appears in the catalyst layer. On the other hand, as performed in Examples 1 to 3 of the present invention, it can be seen that when the flow rate of the refrigerant in the reactor is applied differently for each region, the high temperature region in the catalyst layer is relieved. That is, in the region where the heat generation is severe, the flow rate of the refrigerant is increased to alleviate the high-point temperature portion, and in the low-temperature region, the flow rate is decreased, so that the temperature in the catalyst layer can be uniformly maintained.

As can be seen from Table 1, when the temperature in the catalyst layer becomes uniform (Examples 1 to 3), it can be seen that the CO conversion rate increases, and in particular, the C5+ selectivity increases.

From the above description, those skilled in the art to which the present invention pertains will be able to understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features thereof. In this regard, it should be understood that the embodiments described above are illustrative in all respects and not limiting. The scope of the present invention should be construed that all changes or modifications derived from the meaning and scope of the claims to be described later rather than the above detailed description and equivalent concepts are included in the scope of the present invention.

Claims (11)

For a plate-type heat exchange microchannel reactor in which an exothermic reaction occurs through a catalyst while a reactant flows and a cooling layer through which a refrigerant flows are alternately stacked,
Providing a reactant flow in one direction along the reaction bed,
Provides a flow of a refrigerant in a direction perpendicular to the flow of the reactant to perform heat transfer from the reaction layer to the cooling layer through heat exchange,
The cooling layer is divided into two or more divisions parallel to the flow of refrigerant, but in the division including the hot spot formed in the reaction layer, the flow rate, flow rate, or both of the refrigerant are not included in the hot spot. To be larger than that,
The cooling layer is divided into three or more partitions parallel to the refrigerant flow, and the lower the average temperature corresponds to the average temperature of the reaction bed temperature corresponding to the corresponding partition, the lower the flow rate, flow rate, or both of the refrigerant in the corresponding partition. and,
A method of operating a heat exchange microchannel reactor in which the flow rate, flow rate, or both of the refrigerant are differently adjusted for each section of the cooling layer so that the temperature in the reaction bed equipped with the catalyst is within 10° C. between the highest point and the lowest point. The method of claim 1, wherein the other compartment not including a hot spot includes a catalytic reaction bed having the lowest average temperature of the reaction bed temperature corresponding to the compartment or the lowest temperature downstream of the refrigerant flow. Features heat exchange microchannel reactor operating method The method of operating a heat exchange microchannel reactor according to claim 1, wherein the cooling layer is divided into two or more compartments parallel to the refrigerant flow, and the widths of each compartment are equal or uneven. The method of claim 1, wherein the cooling layer is divided into three or more partitions parallel to the flow of the refrigerant, and additionally, the refrigerant is less than a temperature of a hot spot in the catalytic reaction layer or an undesired high temperature generation point. Heat exchange microchannel characterized in that the flow rate, flow rate, or both are controlled to be larger than other compartments including the catalytic reaction bed having the lowest average temperature or the lowest temperature downstream of the refrigerant flow. How the reactor works. delete The method of claim 1, wherein the cooling layer is divided into three or more partitions parallel to the refrigerant flow, and corresponds to an upstream of the reactant flow direction among other two adjacent partitions of the partition including a hot spot formed in the reaction layer. A method of operating a heat exchange microchannel reactor characterized in that the flow rate, flow rate, or both of the refrigerant in the compartment are adjusted to be greater than that of other compartments. delete The method of operating a heat exchange microchannel reactor according to claim 1, wherein the cooling bed, the reaction bed or both are composed of microchannels. The method of claim 1, wherein the exothermic reaction is a Fischer-Tropsch reaction. The synthetic oil production method further comprising the step of converting the syngas through the Fischer-Tropsch reaction in the heat exchange microchannel reactor operation method of claim 1. The method of claim 10, further comprising performing a hydrocracking process, a dewaxing process, or both on the product of the Fischer-Tropsch reaction.

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