KR20200046216A - 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. More specifically, provided is a method for more easily controlling a temperature in a catalyst layer by making the flow of a refrigerant in a cooling layer flow at a right angle in the catalyst layer and varying flow rate of the refrigerant depending on the portion of the cooling layer. When the heat exchange microchannel reactor is used, it is possible to increase the CO conversion rate and the selectivity of C5+ hydrocarbons in the Fischer-Tropsch reaction by controlling a hot spot due to the reaction heat.

Description

Microchannel reactor with controllability in reaction heat and control method thereof

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

The Fischer-Tropsch (FT) reaction is a reaction for preparing 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

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

The catalyst for the Fischer-Tropsch reaction is largely classified into cobalt and iron-based catalysts. The cobalt-based catalyst has a long catalyst life and is advantageous for obtaining a paraffin-type hydrocarbon having a linear chain, and has the advantage of generating less carbon dioxide. However, when the ratio of hydrogen to CO is high because it is sensitive to the composition gas composition, the selectivity of methane increases, and the selectivity of C5 + (hydrocarbons having 5 or more carbon atoms) decreases relatively. In addition, the C5 + selectivity is sensitive to the reaction temperature, so if the reaction temperature rises above 200-240 degrees C, the C5 + selectivity decreases rapidly, so reaction temperature control is essential. Since the cobalt-based catalyst is expensive, it should be used by dispersing a small amount well on the surface of the support. 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 the catalyst was cheaper than the cobalt-based catalyst, but the catalyst life was short, the methane selectivity was low at high temperatures, the olefin selectivity among hydrocarbons was high, and oxygenates (alcohols, aldehydes) By-products such as molecules containing oxygen atoms such as ketones).

The form of the Fischer-Tropsch reaction reactor that has been considered to date is 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 the fluidized bed reactor includes a circulating fluidized bed reactor and a fixed fluidized bed reactor. Since the reaction characteristics and the distribution of products vary depending on the reactor type, it must be appropriately selected according to the final product to be targeted. In the existing commercialized process of more than 10,000 BPD, a fluidized bed reactor (SASOL) and a multi-tube fixed bed reactor (Shell) have been mainly used. However, this type of reactor is suitable for a relatively large gas field, so a more compact and more efficient reactor is required for a process that requires a much smaller gas field or flare gas. And recently, it is designed to be able to produce by locating resources and unloading where there is demand. As interest in FPSO (floating production, storage and offloading) processes has increased, research on small-scale and high-efficiency processes has been conducted worldwide. Since such a GTL FPSO is to build a GTL plant on a ship with limited space, the smaller the volume of the reactor compared to the production is, the more favorable the reactor type of the micro-channel reactor or multi-channel reactor is considered as the most promising reactor type.

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

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

A multi-channel reactor (hereinafter referred to as a micro-channel reactor) is a reactor that maximizes heat transfer efficiency to enable reaction at a high space velocity, so it has a small volume compared to the production volume (1/5 ~ 1/2 level of the existing reaction process). As the cost of equipment and construction is low, and the production amount can be increased by the concept of number-up, scale-up is easy, and mechanical loss due to friction or collision of the catalyst is minimal. In addition, the change in reaction behavior that may occur during the movement of the device or loss due to the shaking of the catalyst is also negligible. However, in the case of a wash coat on the reactor wall, such as a wall reactor, there is a disadvantage in 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 filling the catalyst particles, catalyst replacement is relatively easy, but there is a disadvantage in that the heat transfer efficiency is inferior to that of a wash-coated reactor on the reactor wall.

Strong exothermic reactions at high temperatures, such as F-T reactions, are often difficult to control reaction heat, and are often restricted to increasing the yield of the desired product. 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 a reactant, which is an easy cooling method of scale-up. It is an object of the present invention to provide a microchannel reactor designed to easily control reaction heat in a 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 in which a refrigerant flows are alternately stacked, wherein the flow of the refrigerant in the cooling layer is the flow of the reactants in the reaction layer Heat transfer occurs from the reaction layer to the cooling layer through heat exchange in a direction perpendicular to the cooling layer, and divides the cooling layer into two or more compartments parallel to the refrigerant flow, and cools the refrigerant in the compartment containing a hot spot formed in the reaction layer. A heat exchange microchannel reactor characterized by adjusting the flow rate, flow rate, or both to be larger than other compartments that do not contain a hot spot.

The second aspect of the present invention provides a method for producing synthetic oil comprising the step of 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 at the top and bottom, and the catalytic reaction layer has a thickness of several millimeters. The micro-channel reactor has attracted attention as a reactor of a strong exothermic reaction or endothermic reaction because of its excellent heat exchange performance because the heat transfer area is 10 to 100 times larger than that of a conventional fixed-bed catalytic reactor.

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

In general, the refrigerant flow method in the right-angle direction has an advantage that the refrigerant flow path is simple and the flow path length is short, so that it can be economically applied to a large reactor. In addition, the structure in which the refrigerant has a cross flow direction compared to the reactants is easily scaled up. In general, when the refrigerant flows in the right angle direction in the exothermic reaction, the temperature tends to rise in the catalytic reaction layer corresponding to the downstream portion from which the refrigerant escapes (FIGS. 2, 4 and 6). This is because the heat accumulates and the temperature rises as the refrigerant goes toward the outlet.

In the fixed-bed tubular catalyst reactor, an exothermic reaction forms a hot spot due to overheating. In this specification, a hot spot refers to the highest temperature in the reaction layer with a catalyst.

In the exothermic reaction, the temperature of the catalytic reaction layer in the reactor is also influenced by the flow rate of the reactants, so that the high temperature point position 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 a small amount of gas goes to the rear end of the reactor, resulting in a hot spot at the top of the reactor (FIGS. 2 and 4). In the case, the reaction heat at the top of the reactor is pushed to the rear end by the reaction gas, thereby limiting the temperature rise, but at the rear end, the reaction heat accumulates to generate a high temperature point (FIG. 6).

Therefore, it is necessary to control the generation of high temperature generated in the refrigerant outlet portion in the flow method of the refrigerant in the right angle direction.

In the present invention, in a plate 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 in which a refrigerant flows are alternately stacked, and the flow of the refrigerant in the cooling layer is perpendicular to the flow of the reactants in the reaction layer. In other words, the cooling layer is divided into two or more sections parallel to the refrigerant flow, and the flow rate, flow rate, or both of the refrigerant in the section containing the hot spots formed in the reaction layer does not include the hot spots. It is characterized by a larger adjustment than the compartment. Through this, the present invention can not only increase the yield of the desired product in a high-temperature strong exothermic reaction, which is not easy to control the reaction heat (Table 1), it is possible to delay the shortening of the life of the catalyst due to the occurrence of a high point.

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, for example, experimental and / or computational fluid dynamics, CFD), predicted, (ii) the cooling layer is divided into two or more compartments parallel to the refrigerant flow, preferably no more than ten, and the compartment and the reaction layer comprising hot spots formed in the reaction layer. Divide the cooling layer compartments so as to include compartments each containing a hot spot formed in (iii), and maintain the flow rate of the total refrigerant used in predicting the high point, forming a hot spot formed in the reaction layer. The flow rate and / or flow rate of the refrigerant in the containing compartment can be adjusted to be larger than other compartments that do not contain a hot spot.

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

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

The cooling layer of the present invention is divided into two or more sections so that the flow rate and / or flow rate of the refrigerant are different, and in some cases, the temperature of the incoming refrigerant is different.

In the present invention, when dividing the cooling layer into two or more sections parallel to the refrigerant flow, the width of each section 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 also be composed of microchannels. In the reaction layer composed of microchannels, a catalyst may be inserted into the channel to be charged or attached to the inner wall of the reactor by coating or the like.

The cooling layer and / or the reaction layer may be provided with a plurality of microchannels to independently and / or independently control the flow rate and / or flow rate in each microchannel. The microchannels in the cooling layer and / or the reaction layer can control the flow rate and / or flow rate by equally or differently width and / or height from each other.

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

The high point in the present invention also includes a case in which the temperature is not higher than the undesired temperature that may occur in the catalytic reaction layer. In other words, the point of occurrence of an undesired temperature in the catalytic reaction layer also falls within the category of high points generated in the reaction layer in the present invention, and in this case, it is also controlled by increasing the flow rate and / or flow rate of the refrigerant in the corresponding refrigerant layer compartment. can do.

For example, the present invention divides the cooling layer into three or more compartments parallel to the refrigerant flow, but the flow rate and / or the flow of refrigerant in the compartment containing less than the hot spot temperature in the catalytic reaction layer or an unwanted high temperature generation point. The flow rate can be adjusted to be greater than the average temperature of the reaction bed temperature corresponding to the corresponding compartment, or larger than other compartments comprising the catalytic reaction bed having the lowest temperature downstream of the refrigerant flow.

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

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

In order to make the temperature difference between the highest point and the lowest point in the reaction layer provided with the catalyst be within 10 ° C, the various reaction heat control methods of the present invention described above can be applied to differently control the flow rate, flow rate, or both of refrigerant for each compartment of each cooling layer. have.

Even if various reaction heat control methods of the present invention described above are used, the temperature T ₁ at any point of the heating layer is higher than the temperature T ₂ at the point of the corresponding cooling layer to exchange heat across the heating layer. It is preferred that heat transfer can occur from the reaction layer to the cooling layer.

In the following, as a representative example of the heat exchange microchannel reactor for Fischer-Tropsch (FT) reaction, which is a high-temperature strong exothermic reaction that is not easy to control the reaction heat, the flow of refrigerant in the cooling layer according to the present invention is applied to the flow of reactants in the reaction layer. In the direction perpendicular to the cooling layer, the cooling layer is divided into two or more sections, and the flow rate, flow rate, or both of the refrigerants in the section including the hot spots formed in the FT reaction layer is higher than other sections that do not contain the hot spots. A method for producing synthetic oil by converting syngas using a heat exchange microchannel reactor that is more controlled will be described.

Synthetic oil production method according to the present invention

As the synthesis gas reactant flows, the FT reaction layer where the FT exothermic reaction occurs through the FT catalyst 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 compartments parallel to the refrigerant flow, and the flow rate, flow rate, or both of the refrigerants in the compartment containing the hot spots formed in the FT reaction layer is greater than other compartments that do not contain the hot spots. Converting 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 to 240 ° C, where the selectivity and CO conversion of C ₅ + hydrocarbon compounds are high near this reaction temperature, the CO conversion is low below 200 ° C, and above 240 ° C C ₅ + hydrocarbon selectivity is greatly reduced.

C5 + selectivity is also sensitive to the reaction temperature, so if the reaction temperature rises above 240 degrees C, the C5 + selectivity decreases rapidly, so control of the reaction temperature is essential.

The optimum reaction pressure of the cobalt-based FT reaction catalyst is 10 to 40 atm (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 can be controlled by the injection amount of the refrigerant and the refrigerant temperature compared to the converted synthesis gas. When the injection amount of the cooling water increases, the temperature of the F-T reaction layer may drop.

However, when the temperature of the FT reaction layer is decreased by increasing the injection amount of the refrigerant, the temperature of the FT reaction layer is excessively low, resulting in a decrease in the conversion rate of the synthesis gas. When the injection amount of the refrigerant is decreased, the temperature of the FT reaction layer is overall. Too high, the conversion rate of the syngas increases, but methane increases, resulting in a problem of decreasing C5 + selectivity.

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 refrigerant injection method, thereby affecting the selectivity of the product.

In the F-T exothermic reaction, when the refrigerant flows in the right angle direction, the temperature increases in the catalyst layer corresponding to the portion where the refrigerant escapes because heat accumulates as the refrigerant goes toward the outlet.

In the present invention, the flow of the refrigerant in the cooling layer existing above and below the catalytic reaction layer flows at right angles to the flow of the reactants to facilitate scale-up, but in the cooling layer, it is possible to control the amount of heat generated in the catalytic reaction layer. It is characterized by controlling the flow rate and / or flow rate of the refrigerant differently.

Therefore, according to the present invention, by varying the flow rate and / or flow rate of the refrigerant according to the location of the catalyst bed high point in the microchannel F-T reactor in the right-angle refrigerant flow, it is possible to uniformly control the temperature in the catalyst reaction layer (Table 1).

Specifically, in order to vary the flow rate and / or flow rate of the refrigerant according to the location of the catalyst layer high point, the cooling layer is divided into two or more sections parallel to the refrigerant flow, and in the cooling layer divided into two or more sections, the FT reaction layer By controlling the flow rate, flow rate, or both of the refrigerant in the compartment containing the hot spot to be larger than other compartments not containing the hot spot, the reaction temperature of the reaction layer with the FT catalyst is 220 ° C. It can be adjusted within the range of ± 20 ℃, preferably, the temperature in the reaction layer with the FT catalyst can be adjusted so that the temperature difference between the highest and lowest points 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 particularly C5 + selectivity may increase.

Non-limiting examples of synthetic oils include diesel, lubricating base oil, wax, and the like, and further manufacturing diesel through a subsequent process such as hydrocracking, and / or dewaxing process, resulting in high-quality wax components. 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 the various elements disclosed in the present invention fall within the scope of the present invention. In addition, the scope of the present invention is not limited by the specific descriptions described below.

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

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

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

Experimental example  One

From the FT catalyst prepared in Preparation Example 1, a kinetic experiment was performed to prepare synthetic oil by FT reaction in synthetic gas. In a 1/2 inch stainless steel fixed bed reactor, 0.1 g of the cobalt catalyst prepared in Preparation Example 1 and 1 g of silicon carbide (SiC) as a diluent were mixed and charged, and 5 hours under an atmosphere of hydrogen (5% by volume H ₂ / He) at 400 ° C. Reduction treatment. Reaction temperature 210 ~ 240 ℃, Reaction pressure 5 ~ 30 kg / cm ² , The molar ratio of carbon monoxide: hydrogen: argon (internal standard) as a reactant under various reaction conditions at a space velocity of 1000 to 30000 L / kg _cat / hr was fixed at a ratio of 31.5: 63.0: 5.5 and injected into the reactor. The kinetics of the FT reaction to 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 kinetics for the F-T catalyst obtained in Experimental Example 1. Computer simulation used COMSOL Multiphysics 5.3 (COMSOL, Inc.), and the conditions are as follows. The detailed shape of the microchannel reactor used in the computer simulation is shown in FIG. 1, and the flow of refrigerant flows in a direction perpendicular to the flow direction of the catalyst bed reactant, and the area in which the refrigerant flows is divided into three parts to compute the refrigerant flow under different conditions. Reproduction was performed.

The temperature of the reactant injected into the catalyst layer is 233 ° C, the outlet pressure is 22 atmospheres, and the composition of the synthesis gas is H ₂ : CO: CO ₂ : Ar = 57: 28: 9: 6: 6 in a molar ratio. The inlet temperature in the refrigerant layer was 230 ° C, the inlet pressure was 27.7 atmospheres, and the baseline flux was set to 3.789 mm / s to perform computer simulation.

Comparative example  One

As in Experimental Example 2, computer simulation of the microchannel reactor was performed, and the space velocity of the synthesis gas was 11, 842 cc / (g _cat h), and the refrigerant flow rate in the refrigerant layer was equally injected in three regions. As a result of the simulation of the reactor, the temperature distribution in the reactor is shown graphically as shown in FIG. 2, and the reaction results are shown in Table 1.

Example  One

As in Comparative Example 1, computer simulation of the microchannel reactor was performed, 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 different regions. The proportion of the refrigerant injected into the upper portion of the refrigerant layer: the middle portion and the lower portion was 50%: 33.3%: 16.7%. As a result of the simulation of the reactor, the temperature distribution in the reactor is shown graphically as shown in FIG. 3, and the reaction results are shown in Table 1.

Comparative example  2

As in Experimental Example 2, computer simulation of the microchannel reactor was performed, and the space velocity of the synthesis gas was 9, 473.6 cc / (g _cat h), and the refrigerant flow rate in the refrigerant layer was equally injected in three regions. As a result of the simulation of the reactor, the temperature distribution in the reactor is shown graphically as shown in FIG. 4, and the reaction results are shown in Table 1.

Example  2

As in Comparative Example 2, computer simulation of the microchannel reactor was performed, 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 differently in three regions. The ratio of the refrigerant injected into the upper portion of the refrigerant layer: the middle portion and the lower portion was 53.3%: 33.3%: 13.3%. As a result of the simulation of the reactor, the temperature distribution in the reactor is shown graphically as shown in FIG. 5, and the reaction results are shown in Table 1.

Comparative example  3

As in Experimental Example 2, computer simulation of the microchannel reactor was performed, and the space velocity of the synthesis gas was 59 and 210 cc / (g _cat h), and the flow rate of the refrigerant in the refrigerant layer was equally injected in three regions. As a result of the simulation of the reactor, the temperature distribution in the reactor is shown graphically as shown in FIG. 6, and the reaction results are shown in Table 1.

Example  3

As in Comparative Example 3, computer simulation of the microchannel reactor was performed, 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 injected differently in three regions. The proportion of the refrigerant injected into the upper portion of the refrigerant layer: the middle portion and the lower portion was 25%: 41.7%: 33.3%. As a result of the simulation of the reactor, the temperature distribution in the reactor is shown graphically as shown in FIG. 7, 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 catalyst layer reactant, and when the flow rate of the refrigerant becomes the same, a high temperature region appears in the catalyst layer. On the other hand, as 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 relaxed. That is, it is possible to maintain the temperature in the catalyst layer uniformly by increasing the flow rate of the refrigerant in the region where the heat is severe to relieve the high-temperature temperature portion and decreasing the flow rate in the low-temperature region.

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

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

Claims (11)

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 in which a refrigerant flows are alternately stacked,
The flow of refrigerant in the cooling layer is perpendicular to the flow of reactants in the reaction layer, and heat transfer occurs from the reaction layer to the cooling layer through heat exchange.
The cooling layer is divided into two or more compartments parallel to the refrigerant flow, and in the compartment containing the hot spot formed in the reaction layer, the flow rate, flow rate, or both of the refrigerant is another compartment that does not contain the hot spot. Heat exchange microchannel reactor characterized by greater control. According to claim 1, Other compartments that do not include a hot spot (hot spot) is that the average temperature of the reaction layer temperature corresponding to the compartment is the lowest, or that includes a catalytic reaction layer having the lowest temperature downstream of the refrigerant flow Characterized heat exchange microchannel reactor. The heat exchange microchannel reactor according to claim 1, wherein the cooling layer is divided into two or more sections parallel to the refrigerant flow, but the width of each section is equal or uneven. The flow rate of the refrigerant in the compartment according to claim 1, wherein the cooling layer is divided into three or more compartments parallel to the refrigerant flow, further comprising a temperature below the hot spot in the catalytic reaction layer or an undesired high temperature generation point. , Heat exchange microchannel reactor characterized by controlling the flow rate or both to be larger than the other compartments containing the 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. . The method according to claim 1, wherein the cooling layer is divided into three or more compartments parallel to the refrigerant flow, and the lower the average temperature corresponding to the average temperature of the reaction layer temperature corresponding to the compartment, the more the flow rate, flow rate, or both of the refrigerant in the compartment. Heat exchange micro-channel reactor characterized by adjusting to lower. The method according to claim 1, wherein the cooling layer is divided into three or more compartments parallel to the refrigerant flow, and corresponds to upstream in the direction of reactant flow among the other two compartments of the compartment containing a hot spot formed in the reaction layer. A heat exchange microchannel reactor characterized in that the flow rate, flow rate, or both of the refrigerant in the compartment is controlled the most over other compartments. The heat exchange micro according to claim 1, wherein the temperature in the reaction layer provided with the catalyst is controlled by differently controlling the flow rate, flow rate, or both of the refrigerant for each compartment of the cooling layer so that the temperature difference between the highest point and the lowest point is within 10 ° C. Channel reactor. The heat exchange microchannel reactor according to claim 1, wherein the cooling layer, the reaction layer, or both are composed of microchannels. The heat exchange microchannel reactor for a Fischer-Tropsch reaction according to any one of claims 1 to 8, wherein the exothermic reaction is a Fischer-Tropsch reaction. A method for producing synthetic oil comprising the step of converting syngas through a Fischer-Tropsch reaction in the heat exchange microchannel reactor of any one of claims 1 to 8. The method of claim 10, further comprising the step of performing a hydrocracking process, a dewaxing process, or both on the product of the Fischer-Tropsch reaction.

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