JP2012005966A - Reactor and manufacturing method of reacted substance using the reactor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inexpensive reactor which is simple and excellent in heat removal effect, and hardly imparts an adverse affect to reaction when performing trickle bed type reaction by using the reactor filled with a solid catalyst, and to provide a manufacturing method of a reacted substance using the reactor.SOLUTION: The reactor comprises: a cylindrical reactor body 10 filled with the solid catalyst which is used at the trickle bed type reaction for performing air-liquid solid catalyst reaction by making the solid catalyst contact with gas and liquid under a trickle flow condition; and a heat transfer plate 20 which contacts with the internal peripheral face 18 of the reactor body 10, and is arranged substantially in parallel with the center axis X of the reactor body 10. A surface area of the heat transfer plate 20 in a reactor zone between arbitrary different two cross sections whose center axes X orthogonally cross each other in a region filled with the solid catalyst of the reactor body 10 is formed so as to be 8.0 to 100[m/m] with respect to a capacity of the reactor zone.

Description

  The present invention is carried out by using a reactor for filling a solid catalyst, which is used when a gas and a liquid are brought into contact with a solid catalyst under irrigation flow conditions to carry out a gas-liquid solid catalytic reaction, and the reactor. The present invention relates to a method for producing a reactant.

  Conventionally, a method (hereinafter referred to as trickle bed type reaction) in which gas phase and liquid phase reaction raw materials are circulated in a reactor filled with a solid catalyst under irrigation flow conditions is one of the embodiments for carrying out a gas-liquid solid catalyst reaction. Are known. The trickle-bed type is known for its excellent gas-liquid mass transfer. For example, industrially useful reactions such as reduction of a substrate by hydrogen and oxidation of a substrate by oxygen are carried out using a solid catalyst. In this case, it is possible to provide a favorable reaction environment in which a shortage of gas components such as hydrogen hardly occurs with respect to the substrate and the catalyst.

  On the other hand, in the trickle bed type reaction, the solid catalyst filled in most of the internal volume of the reactor occupies, but such a packed bed of solid is inferior in heat conduction as compared with liquid. For this reason, when exothermic reactions such as reduction and oxidation are carried out in the same manner, the heat of reaction cannot be completely removed, and a portion where the temperature has excessively increased (hereinafter referred to as a hot spot) is generated. The hot spot causes an increase in impurities due to side reactions and premature deterioration of the catalyst. Therefore, the formation of the hot spot causes an industrial disadvantage. Hot spot formation can occur particularly under scale-up conditions where the horizontal dimension of the packed bed is increased.

  In order to solve such a problem, Japanese Patent No. 2647486 (Patent Document 1) and Japanese Patent No. 3108736 (Patent Document 2) are similar to a multi-tube heat exchanger in which reaction tubes having relatively small diameters are bundled. It has been shown to control the temperature using a reactor. Japanese Patent Publication No. 6-99337 (Patent Document 3) discloses a temperature control method by a method such as introducing cooling hydrogen or cooling raw material oil in the middle of the height direction of the reaction tower.

  In addition to the methods described in Patent Documents 1 to 3, the reaction raw material is diluted with an inert solvent or the like, the reaction amount per unit amount of fluid supplied to the reactor is reduced, and the reaction unit volume per unit volume is reduced. A method of suppressing the heat generation amount is also conceivable.

Japanese Patent No. 2647486 Japanese Patent No. 3108736 Japanese Examined Patent Publication No. 6-99337

  However, the methods described in Patent Documents 1 and 2 have a problem that the equipment cost of the reactor becomes high, and the method described in Patent Document 3 has a problem that the equipment becomes complicated and the operation is complicated. have. In addition, in the method of diluting the reaction raw material with an inert solvent, the size of the reactor is increased, and a process for recovering and reusing the solvent must be added. There is a problem that an increase in cost is inevitable.

  The present invention has been made in view of these points. That is, in carrying out trickle bed type reaction with a reactor filled with a solid catalyst, an inexpensive reactor that is simple and excellent in heat removal effect and has little adverse effect on the reaction is provided. It aims at providing the method of using and manufacturing a reactant.

In order to achieve the above-mentioned object, the reactor according to the present invention is a solid used in a trickle bed type reaction in which a gas and a liquid are brought into contact with a solid catalyst under perfusion flow conditions to perform a gas-liquid solid catalytic reaction. A cylindrical reactor main body filled with a catalyst; and a heat transfer plate in contact with an inner wall surface of the reactor main body and provided substantially parallel to the central axis of the reactor main body. In the reactor section between any two different cross sections perpendicular to the central axis in the region of the reactor body filled with solid catalyst, the surface area of the heat transfer plate is 8 relative to the volume of the reactor section. It is provided so that it may become 0.0-100 [m < ² > / m < ³ >]. Here, the term “substantially parallel” indicates that an inclination caused by a lack of accuracy in manufacturing and assembling of the reactor is allowed, and is regarded as parallel as a whole. The inclination between the heat transfer plate and the central axis can be set within an allowable range up to about 5 degrees.

In the reactor according to the present invention, the heat transfer plate is provided in contact with the inner wall surface of the reactor main body, and the surface area relative to the volume of the reactor section is 8.0 to 100 [m ² / m ³ ]. Since the reaction heat generated by the reaction on the catalyst surface can be transferred to the wall surface of the reactor, the heat can be removed effectively, and the local hot in the catalyst packed bed can be obtained. Spot generation can be suppressed. In addition, the reactor according to the present invention is installed so that its central axis is parallel to the vertical direction, and is subjected to trickle bed type reaction. At this time, although the reaction raw material liquid gently flows down while connecting the catalyst packed bed by gravity, the reaction product falls by gravity because the heat transfer plate of the reactor according to the present invention is substantially parallel to the vertical direction. Heat can be removed without stagnation of the flow that goes through, and there is little adverse effect on the reaction.

Moreover, in the reactor according to the present invention, it is preferable that the heat transfer plate is provided so that a surface area with respect to the volume of the reactor section is 8.0 to 30.0 [m ² / m ³ ]. By providing in this way, it is possible to obtain an optimum heat removal effect and to prevent the reactor from becoming excessively complicated. Here, the surface area of the heat transfer plate can be set by appropriately adjusting the vertical length, the horizontal length, and the number of heat transfer plates.

  The diameter D of the cylindrical reactor body in the reactor according to the present invention is usually 0.2 to 1 [m], preferably 0.3 to 0.6 [m]. If the scale of production increases, multiple reactors with the diameter range specified here can be prepared and used in parallel, or a plurality of reactors can be bundled to create a structure similar to a multi-tube heat exchanger. It is also possible to do.

  Furthermore, in the reactor according to the present invention, the heat transfer plate is preferably formed of a material having a thermal conductivity of 10 [W / (m · K)] or more. In the reactor according to the present invention, the thermal conductivity of the material constituting the heat transfer plate and the inner wall of the reactor is important from the viewpoint of ensuring thermal conduction as the whole reactor, and the larger the better, W / (m · K)] or more is more preferable.

  In the method for producing a reactant according to the present invention, the reaction heat per weight of the reaction raw material liquid supplied to the reactor is adjusted to 450 to 600 [J / g_reaction raw material liquid] using the reactor. It is produced by carrying out a trickle bed type reaction. Here, when the reaction heat per weight of the reaction raw material liquid exceeds the upper limit of the above range, the reaction raw material liquid is diluted with a solvent inert to the reaction, and the weight of the liquid supplied to the reactor is reduced. Can be carried out by adjusting the heat of reaction in the above range. In such a case, it is necessary to add a process for recovering the solvent used for dilution, but by using the reactor according to the present invention, a small amount of solvent can be diluted, so that the equipment burden is minimized. I can do things.

  In the production method using the reactor according to the present invention, the supply amount LHSV [mL_solution / mL_catalyst / hr] of the reaction raw material liquid to the reactor can be set within a range satisfying the perfusion flow conditions. Although it is possible, it is usually 0.2 to 1.8, preferably 0.4 to 1.0. The range in which the irrigation flow can be realized is limited by the amount and speed of the reaction fluid supplied to the catalyst packed bed. For example, “Chemical Engineering Vol. 46, No. 4, pp. 215-220” (Yasuo Kato, The method described in Tsutomu Hirose, published in 1982) can determine whether or not the state of flow is within the perfusion flow range.

  Furthermore, the method for producing a reactant according to the present invention is characterized in that, using the above reactor, ester group hydrogenation is performed in a trickle bed type to obtain alcohols. In this case, the ester group is an ester group bonded to an aliphatic hydrocarbon chain having 4 to 11 carbon atoms, and the resulting alcohol is a mono-chain having an aliphatic hydrocarbon chain having 5 to 13 carbon atoms as a main chain. Alcohol or dialcohol is preferred. Furthermore, it is more preferable that the ester group is an ester group contained in 6-hydroxyhexanoic acid ester, and the resulting alcohol is 1,6-hexanediol.

  As described above, according to the present invention, when a trickle bed type reaction is carried out using a reactor packed with a solid catalyst, an inexpensive reactor that is simple, excellent in heat removal effect, and less adversely affecting the reaction can be obtained. And a method for producing a reactant using the reactor.

It is a partially notched schematic block diagram which shows the reactor which concerns on this embodiment. It is sectional drawing along the AA 'line of FIG. It is explanatory drawing which shows the experimental apparatus of hydrogenation experiment. It is explanatory drawing which shows the model used for experiment verification simulation. It is a graph which shows the catalyst packed bed center temperature of the catalyst packed bed depth direction in the hydrogenation experiment and CFD analysis, and the temperature distribution of the reactor main body outer side. 6A is an explanatory diagram showing an analysis model, and FIG. 6B is a cross-sectional view taken along the line CC ′ of FIG. 6A in the case of the first embodiment, and FIG. ) Is a cross-sectional view taken along the line CC ′ in FIG. 6A in the case of the comparative example 1, and FIG. 6D is a line CC ′ in FIG. 6A in the case of the comparative example 2. FIG. It is a graph which shows the relationship between the catalyst packed bed depth in Example 1 and Comparative Example 1 and the temperature in the catalyst packed bed. 6 is a graph showing the relationship between catalyst packed bed depth and reaction rate in Example 1 and Comparative Example 1. 10 is a graph showing the relationship between the catalyst packed bed depth and the temperature in the catalyst packed bed in Comparative Example 2. It is a graph which shows the relationship between reaction temperature and the density | concentration of the produced | generated HDL.

  Next, the reactor which concerns on one Embodiment of this invention is demonstrated based on drawing. As shown in FIGS. 1 and 2, the reactor 1 according to the present embodiment includes a reactor main body 10 formed in a cylindrical shape, and a heat transfer plate 20 provided inside the reactor main body 10. Yes.

  As shown in FIG. 1, the reactor main body 10 is made of a material such as stainless steel (SUS), for example, and is provided in an internal space 12 that can be filled with the solid catalyst 2 and an upper portion of the reactor main body 10. Are provided with an inflow portion 14 having holes through which reactants can flow, and an outflow portion 16 provided at the bottom of the reactor body 10 and having holes through which the reactants in the internal space 12 can flow out.

As shown in FIGS. 1 and 2, the heat transfer plate 20 is made of a material such as stainless steel (SUS), and the length in the horizontal direction is shorter than the radius of the internal space 12 of the reactor body 10. It is formed in the rectangular shape which has. When this heat transfer plate 20 is viewed in a sectional view as shown in FIG. 2, the heat transfer plate 20 is disposed parallel to the normal line at the contact point with the inner wall surface 18 of the reactor main body 10 and adhered to the inner wall surface 18. The main body 10 is provided so as to be substantially parallel to the central axis X connecting the central points of the openings 11a and 11b at both ends, and from the inner wall surface 18 of the internal space 12 of the reactor main body 10 to the central axis of the internal space 12 A plurality are provided at equal intervals so as to converge radially to X. Here, the phrase “substantially parallel to the central axis X” indicates that an inclination caused by lack of accuracy in manufacturing or assembling the reactor is allowed and regarded as parallel as a whole. The inclination between the heat transfer plate 20 and the central axis X can be considered as an allowable range of inclination up to about 5 degrees. By providing the heat transfer plate 20 so as to converge radially to the central axis X, a predetermined interval is provided between the tip of one heat transfer plate 20 and the tip of the other heat transfer plate 20 facing the heat transfer plate 20. As a result, the internal space 12 of the reactor body 10 is formed as one continuous space that does not have a closed space. The heat transfer plate 20 is formed by cutting the reactor main body 10 in any two cross sections perpendicular to the central axis X in the internal space 12 of the reactor main body 10 filled with the solid catalyst. The surface area of the heat transfer plate 20 in the reactor section surrounded by is 8.0 to 100 [m ² / m ³ ], more preferably 8.0 to 30.0 [m] with respect to the volume of the reactor section. ² / m ³ ]. The heat transfer plate 20 may be formed as a long rectangle whose length in the vertical direction extends from the upper end to the lower end of the internal space 12 of the reactor main body 10. Within a satisfactory range, the length in the vertical direction per sheet can be shortened and divided into a plurality of pieces. Here, when the heat transfer plate 20 is attached to the reactor main body 10 by welding, there is no gap in the contact portion between the inner wall surface 18 of the reactor main body 10 and the heat transfer plate 20, so that the heat removal efficiency is further improved. Can be preferred.

  Next, the usage method of the reactor 1 which concerns on this embodiment is demonstrated. First, the reactor main body 10 is installed so that the central axis thereof is parallel to the vertical direction. Next, a catalyst-packed layer is formed by filling the internal space 12 with a solid catalyst, and gas and liquid as reactants are allowed to flow from the inflow portion 14 of the reactor body 10 so as to satisfy the perfusion flow conditions. Then, the gas and the liquid that have flowed into the catalyst packed bed of the reactor main body 10 are parallel to the downstream side of the catalyst packed bed of the reactor main body 10 while contacting the solid catalyst with the gas as the continuous phase and the liquid as the dispersed phase. And react in the catalyst packed bed. Thereafter, the reacted product obtained in the catalyst packed bed of the reactor main body 10 flows out from the outflow portion 16.

  Here, in the conventional reactor, a local hot spot due to reaction heat is generated, particularly in the central portion of the catalyst packed bed, and the temperature tends to be high. However, in the reactor 1 according to this embodiment, the heat transfer plate 20 is provided in the internal space 12 of the reactor main body 10, so that the heat generated by the reaction in the catalyst packed bed is transferred to the inside of the reactor main body 10. Since it can be transmitted to the wall surface 18 and the reaction heat can be dispersed, the generation of local hot spots due to the reaction can be prevented, and heat can be removed efficiently. Further, the heat transferred to the entire reactor main body 10 by the heat transfer plate 20 can be easily removed by performing a process such as installing a jacket on the outermost outline of the reactor main body 10 and circulating an appropriate medium. I can do it. Furthermore, the heat transfer plate 20 is provided so as to have a surface that is substantially parallel to the central axis X, that is, parallel to the flow direction of the liquid, thereby preventing liquid drift and flow stagnation. it can. For this reason, it acts effectively on the maintenance of the perfusion flow state in the reactor, and the adverse effect on the reaction due to disturbance of the flow state can be reduced.

  In the reactor 1 according to the present embodiment, the heat transfer plate 20 is provided by being bonded to the reactor main body 10, but is not limited thereto, and the heat transfer plate 20 is provided in contact with the reactor main body 10. It only has to be done. In this case, the reactor 1 further includes a removable inner member provided in close contact with the inner wall surface 18 of the reactor main body 10, and the inner member and the heat transfer member 20 are integrally formed of the same material. It's okay.

  Moreover, in the reactor 1 which concerns on this embodiment, although the heat exchanger plate 20 was formed in the elongate rectangular shape, it is not limited to this, A various shape is employable. In addition, although a plurality of heat transfer plates 20 are provided, the present invention is not limited to this, and only one heat transfer plate 20 may be provided.

  Furthermore, in the reactor 1 according to the present embodiment, the heat transfer plate 20 is formed of stainless steel, but is not limited thereto, and is inert to the reaction raw materials and products performed in the reactor 1. Any material may be used. In this case, the heat transfer plate 20 is preferably formed of a material having a thermal conductivity of 10 [W / (m · K)] or more, more preferably 15 [W / (m · K)] or more. . The heat transfer plate 20 may be made of a material different from that of the inner wall surface 18 of the reactor 1. When the heat transfer plate 20 is formed of a metal such as stainless steel, the heat transfer plate 20 can be easily manufactured and processed.

  Furthermore, in the reactor 1 according to this embodiment, the heat transfer plate 20 is provided so as to converge radially from the inner wall surface 18 of the inner space 12 of the reactor body 10 to the central axis X of the inner space 12. However, it is not limited to this, For example, you may provide so that the heat exchanger plate 20 may become mutually parallel. That is, the arrangement of the heat transfer plate 20 is substantially in contact with the central axis X that is provided in contact with the inner wall surface 18 of the reactor body 10 and connects the center points of the openings 11a and 11b at both ends of the reactor body 10. If provided so as to be parallel to each other, the surface area required per volume in the reactor section is satisfied, and the internal space 12 of the reactor main body 10 is formed as one continuous space having no closed space. The range can be arbitrarily determined. In such an arrangement, the horizontal length of the heat transfer plate 20 need not be shorter than the radius of the internal space 12 of the reactor body 10.

Next, examples of the reactor according to the present invention will be described with reference to FIGS. In the present example, by the hydrogenation reaction shown in the following reaction equation (1), 1, ester of 6-hydroxyhexanoic acid, ester of 6-hexanediol (molecular formula: HO (CH ₂ ) ₅ COO (CH ₂ ) ₆ OH, 1,6-hexanediol (hereinafter referred to as “HDL”) was produced from “HAE”. In this example, an analysis simulation was performed by fluid analysis (CFD [Computational Fluid Dynamics] analysis and description, hereinafter referred to as “CFD analysis”) using commercially available fluid analysis software (SCRYU / Tetra V7).

  The amount of reaction of the raw material can be expressed by using the sv value [= mg_KOH / g_HAE] obtained by quantifying the ester group by saponification with KOH. When the reaction rate is xA, xA = 1− (sv value / raw material sv value). Indicated. This sv value was measured according to JIS K0070, and the initial sv value of this HAE was 241 [mg_KOH / g].

  The reaction of the above formula (1) is an exothermic reaction, and ΔH = −525 [J / g_HAE] is obtained from experiments. ΔH was measured by the following experimental method.

<Measurement experiment of calorific value>
A hydrogenation experiment of HAE is performed using the experimental apparatus shown in FIG. 3 and the following <hydrogenation experiment>, and the calorific value under the reaction conditions is determined from the temperature distribution. The calculation formula is expressed by the following formula (2), and the obtained calorific value can be regarded as the reaction heat (ΔH) of formula (1).

  Q1 is calculated from the amount of change in the heat of the process fluid (liquid and gas) between the inlet and outlet of the reactor. Q2 is the heat radiation in the direction orthogonal to the liquid gas flow, that is, in the radial direction of the reactor body, and the temperature difference (ΔT) between the center temperature and the outer wall of each height of the catalyst packed bed and the inside of the reactor body. The surface area (A) and the overall heat transfer coefficient U between the catalyst packed bed and the reactor main body wall are calculated from the following formula (3). In addition, U used the value calculated | required by the following <calculation experiment of the general heat transfer coefficient U>.

<Hydrogenation experiment>
A laboratory scale experiment of the reaction of the above reaction equation (1) was performed using an experimental apparatus 30 shown in FIG. The experimental apparatus 30 heats a cylindrical stainless steel reactor main body 33 (thickness 3 mm) formed in an inner diameter of 19 mm × height 600 mm (catalyst packed bed height 300 mm) and a catalyst packed bed 36 of the reactor main body 33. Thus, an electric heating furnace 35 provided outside the reactor main body 33 and a thermocouple for measuring the center temperature of the catalyst packed bed 36 of the reactor main body 33 are inserted and removed. The one provided with a possible thermocouple sheath tube 40 was used.

  A raw material liquid inflow portion 31 capable of supplying HAE and a hydrogen gas inflow portion 32 capable of supplying hydrogen gas are formed in the upper portion of the reactor main body 33, and a reaction fluid is provided in the lower portion of the reactor main body 33. A reaction fluid outflow portion 39 capable of flowing out was formed. In the central portion of the reactor body 33 in the axial direction, a copper catalyst (CuO: 47.6 wt%, ZnO: 47.3 wt%) molded into a cylindrical shape having a diameter of 3 mm and a height of 3 mm is 300 mm high. In the region between the upper part of the reactor main body 33 and the catalyst packed layer 36, a preheating region 34 that is filled with alumina particles and preheats the fluid to be supplied is provided. . The thermocouple sheath tube 40 is inserted with a catalyst center temperature measuring thermocouple 37 for measuring the center temperature of the catalyst packed bed 36 of the reactor main body 33, and between the reactor main body 33 and the electric heating furnace 35. Is provided with a reactor body outer wall temperature measuring thermocouple 38 for measuring the temperature of the outer wall of the reactor body 33. HAE and hydrogen gas were supplied from the raw material liquid inflow portion 31 and the hydrogen gas inflow portion 32 of the reactor main body 33 in a gas-liquid descending parallel flow.

  Hereinafter, LHSV represents the liquid supply amount [mL liquid / mL_catalyst / hr], GHSV represents the gas supply amount [mL_gas / mL_catalyst / hr], and the volume is 20 ° C. and atmospheric pressure conditions. In the experiment, first, the output of the electric heating furnace 36 is adjusted and fixed so that the center temperature of the catalyst packed bed becomes 200 to 260 ° C. under “hydrogen atmosphere”, and then HAE and hydrogen gas are supplied to supply the raw materials. The temperature of the thermocouple sheath tube 40 installed at the center of the layer and the temperature of the reactor body wall were measured in the height direction when the catalyst packed bed temperature and the reaction rate reached a steady state.

<Calculation experiment of overall heat transfer coefficient U>
Using the apparatus shown in the above <hydrogenation experiment>, 1,5-pentanediol (hereinafter referred to as PDL) is used instead of HAE as a model fluid that does not cause a hydrogenation reaction. A hypothetical heat generation state was created by heating and supplying to the catalyst, and U was obtained by measuring and analyzing the temperature distribution of the catalyst packed bed and the outer wall in the steady state at intervals of 2.5 cm. Specifically, under a pressure of 25 MPa hydrogen, the temperature of the catalyst packed bed was first adjusted to 200 ° C., and a predetermined amount of PDL and hydrogen heated to 230 ° C. were fed thereto. Table 1 shows the temperature distribution data obtained by the experiment. The liquid supply load per catalyst [g / mL_catalyst / hr] condition is 1.0 for distribution 1 and 2.0 for distribution 2, and GHSV [mL_gas / mL_catalyst / hr] is distribution 1 Both are 500.

<U calculation method>
For the calculation, 0.80 [cal / g / K] was used as the specific heat of PDL, and 3.5 [cal / g / K] was used as the specific heat of hydrogen. U was calculated by dividing the catalyst packed bed into 2.5 cm sections (however, the section until the temperature just before the stable state). The calculation formula is as shown in the following formula (4), and Q (heat release) is calculated from “flow rate × specific heat × temperature change in 2.5 cm section” as a heat amount corresponding to the temperature drop of PDL and hydrogen in each section. . Note that the temperatures of the PDL, hydrogen, and catalyst packed bed reached thermal equilibrium at any position in the catalyst packed bed, and all three assumed the same temperature. The average value was calculated by dividing the total value of U in each section by the number of sections, and this value was defined as U under the experimental conditions. As a result of analyzing the temperature data of the 0-15 cm section of the catalyst layer of Table 1, distribution 1, U = 76 [kJ / m ² / hr / K] was obtained, and 0-17 of the catalyst layer of Table 1, distribution 2 was obtained. As a result of analyzing the temperature data in the section of 5 cm, it was determined that U = 108 [kJ / m ² / hr / K].

<HAE hydrogenation experiment for calculation of reaction heat>
The hydrogenation experiment of HAE was performed using the apparatus shown in the above <Hydrogenation experiment>, and the calorific value of the reaction was obtained by measuring and analyzing the temperature distribution of the catalyst packed bed and the outer wall in a steady state at intervals of 2.5 cm. The experimental conditions were a hydrogen pressure of 25 MPa, a reaction start temperature (temperature immediately near the catalyst packed bed): 200 ° C., a liquid supply load per catalyst of 1.39 [g / mL_catalyst / hr], and a GHSV of 500. The temperature distribution data obtained by the experiment is shown in Table 2 as distribution 3.

<Calculation of reaction heat>
For the calculation, the specific heat of HAE: 0.538 [cal / g / K] and the specific heat of the hydrogenated solution: 0.757 [cal / g / K] were used. As the U value, the liquid supply load per catalyst calculated in the above <U calculation method> is 1.0 (Table 1, Distribution 1) and 2.0 (Table 1, Distribution 2). A prorated value corresponding to a load of 1.39: 89 [kJ / m ² / hr / K] was calculated and used. In the above formula (2), Q1 was calculated from the temperature difference between the process fluids (liquid and gas) at the inlet and outlet of the catalyst packed bed. About Q2, it calculated | required by calculating | requiring the heat radiation amount for every area of 2.5 cm, and adding them all. As a result, Q1 = 298 [J / g] and Q2 = 227 [J / g], and the heat of reaction (ΔH) under these reaction conditions was calculated to be 525 [J / g].

<Verification>
First, regarding the accuracy of analysis data by CFD analysis of the commercially available fluid analysis software used in this example, data (reaction rate) obtained by actual hydrogenation experiment and data (analysis reaction) obtained by CFD analysis Rate) and compared. The experimental conditions are shown in Table 3 below.

  When the sv value of the reaction liquid in the reaction fluid outflow portion 39 under the reaction conditions shown in Table 3 was measured, a reaction rate xA = 0.937 was obtained. FIG. 5 shows the catalyst packed bed center temperature in the catalyst packed bed depth direction and the temperature profile outside the reactor main body at this time.

<Experimental verification simulation>
Next, an experiment verification simulation by CFD analysis was performed using commercially available fluid analysis software. The analysis conditions are as shown in Table 4 below.

  For the analysis model, the reactor shown in FIG. 4 was used. FIG. 4A is an explanatory diagram showing a model used in the experiment verification simulation, and FIG. 4B is a cross-sectional view taken along the line BB ′ of FIG. The reactor is provided with a catalyst packed bed 53 having a height of 300 mm, a cylindrical reactor main body 50 formed with an inner diameter of 19 mm (wall thickness: 3 mm), and coaxially within the reactor main body 50. And a cylindrical temperature measuring tube 54 having an inner diameter of 4 mm (wall thickness: 1 mm). The reactor main body 50 and the temperature measuring tube 54 are made of stainless steel (SUS304). An inflow portion 51 through which a fluid can flow is formed in the upper part of the reactor main body 50, and an outflow portion 52 through which the reaction fluid can flow out is formed in the lower portion of the reactor main body 50.

  Here, the catalyst packed bed model with built-in CFD and the calculation method of the chemical reaction are shown in the following formula (5) (Ergan formula) and Table 5 (catalyst packed bed physical properties table) and Table 6 (reaction rate parameter), formula (6) ( Reaction rate formula), (7) formula (Arrhenius formula) and (8) formula (steady advection diffusion equation).

In the equation (5), dP / dx is the pressure loss per distance [Pa / m], μ is the fluid viscosity, ρ _f is the fluid density, and U is the fluid superficial equivalent flow velocity [m / s].

Here, C1 is the concentration [mol / m ³ ] of the reactant (here HAE).

  Einstein's sum rules apply to the suffix in the formula.

<Calculation conditions>
The conditions for calculating the analytical reaction rate in the experiment verification simulation are as follows.
(1) The fluid is a two-phase flow of hydrogen gas and raw material HAE liquid. Here, the fluid was calculated as a phase-homogeneous system, and the physical properties were prorated by mass fraction. (2) The effective thermal conductivity K _er of the catalyst packed bed in the reaction bed is the same in the entire region of the catalyst packed bed regardless of the position in the axial direction or the radial direction. (3) The reactor temperature was assumed to be the same for all catalysts, liquids, and hydrogen gas. (4) The calculated value of the effective thermal conductivity K _er is calculated from a fluid and a catalyst packed bed by a well-known calculation method such as “Chemical Engineering Papers Vol. 2, No. 1, pages 53-59. It was estimated by the method described in “Academic Society 1976”). (5) As physical property data, the four physical properties of density, viscosity, single unit thermal conductivity, and specific heat are substituted for the HAE by the HDL ASPEN estimate. Measured physical properties described in "Page 94 (issued in August 1983, Japan Society of Mechanical Engineers)" (estimated by extrapolation when there is no physical property at the relevant temperature) were used, and an average of 220 to 260 ° C was used. Here, the ASPEN estimated value is an estimated value using a process simulator “ASPEN PLUS V7.1” manufactured by ASPEN TECHNOLOGY.

  The catalyst depth direction temperature profile obtained by this experiment verification simulation is shown by a solid line in FIG. 5 together with the result of the above <hydrogenation experiment>. Further, an analytical reaction rate xA = 0.919 was obtained, which almost coincided with the experimental value (xA = 0.937). As a result, it was confirmed that the experimental results could be explained with high accuracy by CFD analysis under these conditions.

<Analysis simulation>
Next, using a commercially available fluid analysis software, simulation by CFD analysis was performed, and the temperature distribution in the catalyst packed bed with and without the heat transfer plate provided in the reactor body, and the reactor body The surface area relative to the volume of the optimal catalyst packed bed of the heat transfer plate provided on the surface was determined.
CFD analysis of reactor inner diameter 0.42 m × height 12.7 m was performed in the same manner as in the above <Experimental verification simulation>. FIG. 6A is an analysis model diagram, FIG. 6B is a cross-sectional view taken along the line CC ′ of FIG. 6A in the case of Example 1, and FIG. 6A is a cross-sectional view taken along the line CC ′ of FIG. 6A in the case of the comparative example 1, and FIG. 6D is taken along the line CC ′ of FIG. It is sectional drawing.

As shown in FIGS. 6 (a) and 6 (b), the analysis model of Example 1 has a cylindrical shape in which a catalyst packed bed 63 having a diameter of 0.42 m and an axial length of 12.7 m is formed. In order to efficiently remove the reaction heat in the reactor main body 60 and the catalyst packed bed 63, the SUS is provided in the reactor main body 60 and has a width of 0.16 m and a thickness of 3 mm. And a heat transfer plate 64 made of metal. The surface area of the heat transfer plate relative to the reactor volume at this time is 18.5 [m ² / m ³ ].

  In the reactor main body 60, an inflow portion 61 into which the reaction fluid flows is formed in the upper portion, and an outflow portion 62 from which the reaction fluid flows out is formed in the lower portion. The heat transfer plate 64 has a surface parallel to the flow direction of the reactant flowing in the reactor main body 60 and is perpendicular to the inner wall surface of the reactor main body 60. It is assumed that eight are provided at equal intervals so as to converge radially from the inner inner wall surface to the inner central axis. The analysis model of Example 1 is configured to include such a heat transfer plate 64, so that the reaction heat flux generated by the reaction in the catalyst packed bed 63 is walled outwardly in the radial direction by the heat transfer plate 64. It was made into the structure which flows into.

The analysis simulation in Example 1, HAE liquid supply amount LHSV is 0.54, the effective thermal conductivity _{K er} is a 3.539 [W / m / K] , the reactor body wall temperature, below the reactor top end In the direction, the temperature was 181 ° C. to a depth of 4.5 m, and 220 ° C. from 4.5 m to 12.7 m.
Moreover, the conditions other than this used the same conditions as Tables 3-6.

In the above-described <hydrogenation experiment>, the HAE supply amount LHSV was 0.8 and the liquid supply load per catalyst was 0.2 [kg / m ³ _catalyst / s]. In Example 1 scaled up to 0.42 m, the HAE supply amount LHSV is 0.54 and the liquid supply load per catalyst is 0.15 [kg / m ³ _catalyst / s] in order to satisfy the perfusion flow condition. It was. The range in which the irrigation flow can be realized is limited by the amount and speed of the reaction fluid supplied to the catalyst packed bed. For example, “Chemical Engineering Vol. 46, No. 4, pp. 215-220” (Yasuo Kato, The method described in Tsutomu Hirose, published in 1982) can determine whether or not the state of flow is within the perfusion flow range.

The results of the analysis simulation of Example 1 are shown in FIGS. In FIG. 7, the axial direction (catalyst packed bed depth) of the reactor main body and the temperature distribution ( ₀ , 0.10, 0.16 m in the radial direction from the center at positions r ₀ , r ₁ , r _{2 respectively.} Are indicated by solid lines. On the other hand, in FIG. 8, the reaction rate distribution is shown by a solid line. It was shown that the temperature in the catalyst packed bed 63 can be controlled to an appropriate range without exceeding 250 ° C. at any position by installing a heat transfer plate.

<Confirmation of product decomposition temperature>
The upper limit of the preferable reaction temperature range in this reaction was determined by the following experiment. An autoclave with an internal volume of 100 mL was charged with 40 g of HAE and 4 g of the same copper catalyst as used in the above <hydrogenation experiment>, and reacted for 2 hr at a hydrogen pressure of 25 MPa, a stirring rotational speed of 750 rpm, and a predetermined temperature. FIG. 10 shows the HDL concentration of the reaction solution when reacted at each reaction temperature. FIG. 10 shows that the HDL concentration decreases due to the decomposition reaction when the temperature exceeds 250 ° C. It is considered preferable that the reaction temperature of this reaction does not exceed 250 ° C.

Comparative Example 1

Next, an analysis simulation was performed for the case where no heat transfer plate was provided in the reactor body. The simulation conditions are the same as those in Example 1 except that there is no heat transfer plate in the catalyst packed bed 63. The obtained temperature profile in the depth direction and the reaction rate are shown by broken lines in FIGS. 7 and 8, respectively. Without the heat transfer plate, the temperature in the catalyst packed bed 63 exceeded 250 ° C. at any position, and the maximum temperature at the center (r ₀ ) reached 290 ° C.

  From the results of Example 1 and Comparative Example 1, it was found that the reaction heat generated in the catalyst packed bed can be efficiently removed by installing a heat transfer plate in the reactor.

Comparative Example 2

Next, an analysis simulation was performed for the case where the surface area of the heat transfer plate provided in the reactor main body was reduced. The analysis simulation was performed under the same conditions as in Example 1 except that the width of the heat transfer plate 64 ′ in the catalyst packed layer 63 was 1/3 of that in Example 1 (0.05 m). It was. The surface area of the heat transfer plate with respect to the reactor volume at this time is 5.8 [m ² / m ³ ]. The obtained temperature profile in the depth direction is shown by a broken line in FIG. It can be seen that the temperature at the positions r ₀ and r ₁ in the catalyst packed layer 63 exceeds 250 ° C. if the surface area of the heat transfer plate is not sufficient. In particular, the maximum temperature at the center (r ₀ ) reached around 280 ° C.

  From the result of Comparative Example 2, when the surface area of the heat transfer plate installed in the reactor is insufficient, the reaction heat generated in the catalyst packed bed cannot be sufficiently removed, and a hot spot is generated near the center. There was found.

DESCRIPTION OF SYMBOLS 1 Reactor, 10 Reactor main body, 12 Internal space, 14 Inflow part, 16 Outflow part, 18 Inner wall surface, 20 Heat-transfer plate

Claims (6)

A cylindrical reactor body filled with a solid catalyst used in a trickle-bed type reaction in which a gas and a liquid-catalyzed reaction are carried out by bringing a gas and a liquid into contact with the solid catalyst under perfusion flow conditions;
A heat transfer plate provided in contact with the inner wall surface of the reactor main body and substantially parallel to the central axis of the reactor main body,
In the reactor section between any two different cross sections perpendicular to the central axis in the region of the reactor body where the solid catalyst is packed, the surface area of the heat transfer plate is the volume of the reactor section. The reactor is provided so that it may become 8.0-100 [m < ² > / m < ³ >]. The reactor according to claim 1, wherein a surface area of the heat transfer plate with respect to the volume of the reactor section is 8.0 to 30.0 [m ² / m ³ ].   The reactor according to claim 1, wherein the heat transfer plate is made of a material having a thermal conductivity of 10 [W / (m · K)] or more.   Using the reactor according to any one of claims 1 to 3, the reaction heat per weight of the reaction raw material liquid supplied to the reactor is adjusted to 450 to 600 [J / g_reaction raw material liquid], and a trickle bed A method for producing a reactant, which is produced by performing a formula reaction.   A process for producing a reaction product, characterized in that, using the reactor according to any one of claims 1 to 3, hydrogenation of an ester group is carried out in a trickle bed system to obtain an alcohol.   6. The method for producing a reaction product according to claim 5, wherein the ester group is an ester group contained in 6-hydroxyhexanoic acid ester, and the resulting alcohol is 1,6-hexanediol.