Pressure loss estimation method, reaction method for controlling pressure loss, pressure loss estimation derivation device, and pressure loss estimation program

Abstract

To provide a method for estimating secular change of pressure loss in a reactor with good accuracy, in a fixed floor distribution type reaction for distributing a gas or liquid one phase fluid, or gas or liquid two phases fluid to the reactor.SOLUTION: A method includes a step for obtaining impurities total amount Sin a fluid flowing in a reactor and impurities total amount Sin a product material flowed out from the reactor between any reaction passage time tand reaction passage time(t-t) and a step for deriving porosity εof a solid catalyst layer in the reaction at the reaction passage time tfrom porosity εof the solid catalyst layer in the reactor at the reaction passage time tby a formula (1), in which viscosity μ of the fluid, linear speed u of the fluid, density ρ of the fluid, and εat the reaction passage time tare assigned into a formula calculating pressure loss, ΔP, which is a calculated value of the pressure loss is derived, ΔPis assigned in a formula (2), and an estimated value ΔPof the pressure loss in the reactor at the reaction passage time tis calculated.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for estimating pressure loss in a fixed-bed flow reaction in which a gas and / or liquid fluid is circulated through a reactor packed with a solid catalyst to carry out a reaction, a reaction method for controlling pressure loss, a pressure loss estimation device, and a pressure loss estimation program. [Background technology]

[0002] Conventionally, a reaction method in which gaseous and / or liquid reactants are circulated through a reactor packed with a solid catalyst is known as a fixed-bed flow reaction. In a fixed-bed flow reaction reactor, the flow of a fluid containing reactants is lost due to resistance from the solid catalyst layer. This loss is expressed in terms of pressure and is called pressure loss.

[0003] Usually, the reactor used in the fixed bed flow reaction has an upper limit of pressure resistance determined by the material, structure, etc., and it is necessary to constantly monitor the pressure in the reactor so that the upper limit is not reached. That is, the reaction must be stopped before the pressure in the reactor reaches the upper limit of the reactor's pressure resistance. In particular, when the pressure loss increases suddenly, the reaction may have to be stopped urgently, which will have a significant adverse effect on the operation plan, etc. Therefore, from the viewpoint of stable operation, there is a high demand for a method for estimating the change in pressure loss over time.

[0004] When impurities are present in the fluid, they may accumulate on the solid catalyst layer. Also, when the fluid contains compounds containing carbon, coke may form in the reactor and accumulate on the solid catalyst layer. When impurities, coke, etc. accumulate on the solid catalyst layer, the pores in the solid catalyst layer gradually become clogged. This is thought to be one of the factors that cause an increase in pressure drop in fixed-bed flow-type reactions.

[0005] The Ergun equation is one of the well-known equations for calculating pressure loss when the fluid is a single phase of gas or liquid. The Ergun equation has a wide range of applicability, from laminar to turbulent flow, and has been widely used for a long time (Non-Patent Document 1). In addition, many equations have been proposed for calculating pressure loss when the Ergun equation is expanded to a two-phase system of gas and liquid, and the Ergun-Larkins equation is one such known equation (Non-Patent Document 2). [Prior art documents] [Non-patent literature]

[0006] [Non-Patent Document 1] Ergun, S., Chem. Eng. Prog., 48-2 (1952), 89-94. [Non-Patent Document 2] RP LARKINS et al., “Two-Phase Concurrent Flow in Packed Beds”, AI Ch. E. Journal, (1961) Vol. 7, No. 2, 231-239. Summary of the Invention [Problem to be solved by the invention]

[0007] The Ergun equation, Ergun-Larkins equation, etc. are equations that derive an estimated value of pressure drop by substituting necessary parameters such as the void fraction of the solid catalyst layer in the reactor, the fluid density, the fluid viscosity, and the fluid linear velocity into the equation.

[0008] However, it is difficult to obtain all the parameters required to derive an estimated value of pressure drop from the Ergun equation, the Ergun-Larkins equation, etc., over time while the reaction is proceeding, and therefore it is practically impossible to accurately estimate the change in pressure drop over time.

[0009] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a method for accurately estimating a change over time in pressure drop in a reactor in a fixed-bed flow reaction in which a one-phase fluid of gas or liquid, or a two-phase fluid of gas and liquid, is circulated through a reactor, a reaction method for controlling the pressure drop in the reactor, a pressure drop estimation device, and a pressure drop estimation program. [Means for solving the problem]

[0010] In order to solve the above problems, the present invention has the following aspects. [1] In a fixed-bed flow reaction in which a single-phase fluid (gas or liquid), or a two-phase fluid (gas and liquid) is circulated through a reactor packed with a solid catalyst, the reaction time t x A method for estimating a pressure drop in the reactor, comprising the steps of: The reaction time t x obtaining the viscosity μ of the fluid, the linear velocity u of the fluid, and the density ρ of the fluid at The reaction time t x Any other reaction time t before x-1 From the reaction time t x Between (t x -t x-1 ) the total amount of impurities in the fluid flowing into the reactor S IN , and the total amount of impurities S in the fluid discharged from the reactor OUT and obtaining Obtained S IN and S OUT Substituting into the following formula (1), the reaction time t x The porosity ε of the solid catalyst layer in the reactor x and deriving The obtained μ, u, ρ, and ε x The calculated pressure drop is calculated by substituting the above into the equation for calculating the pressure drop based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the void ratio of the solid catalyst layer in the reactor, and the calculated pressure drop is ΔP cal Derive The obtained ΔP cal Substituting into the following formula (2), the reaction time t xThe estimated pressure drop in the reactor at sim A method for estimating pressure drop in a reactor, comprising:

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[0020] The pressure loss estimation method according to the present invention can provide a method for accurately estimating a change in pressure loss over time in a reactor in a fixed-bed flow reaction in which a one-phase fluid of gas or liquid, or a two-phase fluid of gas and liquid, is circulated through the reactor, a reaction method for controlling the pressure loss in the reactor, a pressure loss estimation device, and a pressure loss estimation program. [Brief description of the drawings]

[0021] [Figure 1] FIG. 4 is a diagram showing a flow for obtaining an estimated value of pressure loss in a reactor according to one embodiment. [Diagram 2] FIG. 4 is a diagram showing a flow for obtaining an estimated value of pressure loss in a reactor according to one embodiment. [Diagram 3] 1 is a configuration block diagram of a pressure loss estimation derivation device according to an embodiment; [Figure 4] FIG. 2 is a diagram showing the change over time of the actual measured value of pressure drop in the hydrotreating reaction of heavy hydrocarbons and the change over time of the estimated value obtained by the pressure drop estimation method of one embodiment. [Diagram 5] FIG. 2 is a diagram showing the change over time of the actual measured value of pressure drop in the hydrotreating reaction of heavy hydrocarbons and the change over time of the estimated value obtained by the pressure drop estimation method of one embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] The following describes in detail the embodiments of the present invention. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to these contents and can be modified and implemented within the scope of its gist.

[0023] <Pressure loss estimation method> The method for estimating the pressure drop in this embodiment is a method for estimating the pressure drop at any reaction time t in a fixed bed flow reaction in which a one-phase fluid of gas or liquid, or a two-phase fluid of gas and liquid, is circulated through a reactor packed with a solid catalyst. x A method for estimating a pressure drop in the reactor, comprising: x A step of acquiring the viscosity μ of the fluid, the linear velocity u of the fluid, and the density ρ of the fluid at the reaction time t x Any other reaction time t before x-1 From the reaction time t x Between (t x -t x-1 ) the total amount of impurities in the fluid flowing into the reactor S IN , and the total amount of impurities S in the fluid discharged from the reactor OUT (S1B in Fig. 1) and the acquired S IN and S OUT Substituting into the following formula (1), the reaction time t x The porosity ε of the solid catalyst layer in the reactor x and deriving the obtained μ, u, ρ, and ε x The calculated pressure drop is calculated by substituting the above into the equation for calculating the pressure drop based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the void ratio of the solid catalyst layer in the reactor, and the calculated pressure drop is ΔP cal (S2 in Fig. 1) and the obtained ΔP cal Substituting into the following formula (2), the reaction time t x The estimated pressure drop in the reactor at sim The method is characterized by calculating (S3 in FIG. 1).

[0024]

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[0025] In the formula (1), ε x-1 is the reaction time t x-1 is the voidage of the solid catalyst layer in the reactor, and α is a tuning factor. The method for setting α will be described later.

[0026]

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[0027] In the above formula (2), σ is a tuning factor. The method for setting σ will be described later.

[0028] In a fixed-bed flow reaction, scale accumulates in the solid catalyst layer in the reactor as the reaction time progresses, and the porosity of the solid catalyst layer decreases. The main cause of scale formation is the accumulation of impurities, typically metal compounds, contained in the reactant-containing fluid on the solid catalyst layer. In the above formula (1), x-1 From the reaction time t x Between (t x -t x-1 ) the total amount of impurities in the fluid flowing into the reactor S IN , and the total amount of impurities S in the fluid discharged from the reactor OUT is the difference between (S IN -S OUT ) by calculating (S IN -S OUT It is believed that impurities in an amount of 100% or more are deposited on the solid catalyst layer, reducing the porosity of the solid catalyst layer in the reactor.

[0029] The above S IN is the reaction time t x-1 From the reaction time t x Between (t x -t x-1 ) can be obtained by measuring the impurity concentration (unit: ppm, for example) in the fluid before it flows into the reactor and calculating the product of that and the total amount (unit: kg, for example) of the fluid that flows into the reactor during that time. OUT is the reaction time t x-1From the reaction time t x Between (t x -t x-1 The impurity concentration in the fluid flowing into the reactor and the fluid flowing out from the reactor can be calculated by measuring the impurity concentration (for example, in ppm) in the fluid flowing out from the reactor during the reaction time t and multiplying it by the total amount (for example, in kg) of the fluid flowing out from the reactor during the reaction time t. x-1 From x Between (t x -t x-1 ) should be obtained at least once, and if obtained at least twice, the average value of the data can be used.

[0030] When multiple different solid catalyst layers are formed in the reactor, the reaction time t x The porosity ε of each solid catalyst layer in x(n) For example, it can be derived from the following formula (1-A) (ε x(n) Derivation method (1)).

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[0032] In the formula (1-A), n is an integer of 2 or more and represents the number of different solid catalyst layers. x(n) is the reaction time t x The porosity of the nth solid catalyst layer from the reactor inlet side is ε x-1(n) is the reaction time t x-1 The porosity of the nth solid catalyst layer from the reactor inlet side is α (n) is the tuning factor of the nth solid catalyst layer from the reactor inlet side, R (n) is the solid catalyst layer ratio of the nth solid catalyst layer from the reactor inlet side, and R (1) ~R (n) The sum of is 1. IN and S OUT is the same as above.

[0033] In the present invention, the solid catalyst layer ratio R (n)is the reaction time t x-1 From the reaction time t x Between (t x -t x-1 ) the total amount of impurities in the fluid flowing into the reactor S IN , and the total amount of impurities S in the fluid discharged from the reactor OUT is the difference between (S IN -S OUT ) is a coefficient for apportioning how much of the catalyst has been deposited on each of the plurality of different solid catalyst layers.

[0034] When multiple different solid catalyst layers are formed in the reactor, the reaction time t x The porosity ε of each solid catalyst layer in x(n) can also be derived, for example, by the following formula (1-B) (ε x(n) Derivation method (2)).

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[0035] In the formula (1-B), n is an integer of 2 or more and represents the number of different solid catalyst layers. x(n) is the reaction time t x The porosity of the nth solid catalyst layer from the reactor inlet side is ε x-1(n) is the reaction time t x-1 The porosity of the nth solid catalyst layer from the reactor inlet side is α const is the tuning factor, and S IN and S OUT is the same as above. ε x(n) In the derivation method (2), the same α const Since the solid catalyst layer ratio is not used, ε x(n) This method allows the pressure loss to be estimated more easily than derivation method (1).

[0036] In the present invention, when a plurality of different solid catalyst layers are formed in a reactor, the pressure drop can be more easily estimated by using the above ε x(n)It is preferable to adopt the derivation method (2).

[0037] In this specification, "impurities" means substances other than the reactants of the target chemical reaction at the reactor inlet, and substances originating from the "impurities" at the reactor inlet at the reactor outlet. In addition, there is no need to measure substances that are generally inactive in chemical reactions, such as nitrogen gas. It is sufficient to appropriately select impurities that accumulate on the solid catalyst layer according to the target chemical reaction, and measure only the above substances. The method for measuring the concentration of impurities in a fluid can be any method known in the art depending on the type of impurity and fluid, and examples of such methods include inductively coupled plasma mass spectrometer ICP-MS, ICP-OES, ICP-AES, various types of chromatography such as liquid chromatography and gas chromatography, and X-ray fluorescence analysis. In addition, the reaction time t x-1 From the reaction time t x Between (t x -t x-1 The total amount of fluid flowing into the reactor during the reaction time t and the total amount of fluid flowing out of the reactor during the reaction time t can be obtained by a flow meter, a change in the liquid level in the raw material tank and the product tank, etc. x-1 From the reaction time t x Between (t x -t x-1 The total amount of fluid flowing into the reactor and the total amount of fluid flowing out of the reactor can be controlled to the desired amount by using a mass flow controller, a control valve, a pump, a compressor, etc.

[0038] The reaction time t in the above formula (1) x-1 The porosity ε of the solid catalyst layer in the reactor x-1 For example, the reaction time t x-1 Any other reaction time t earlier than x-2 The porosity ε of the solid catalyst layer in the reactor x-2 , and the reaction time t x-2 From the reaction time t x-1 The total amount of impurities S in the fluid flowing into the reactor during IN, and the total amount of impurities S in the fluid discharged from the reactor OUT can be derived by measuring by the above-mentioned method and substituting it into the above-mentioned formula (1). That is, if ε0, which is the porosity of the solid catalyst layer in the reactor at the start of the reaction, is known, the change over time in the porosity ε of the solid catalyst layer in the reactor can be obtained by repeatedly applying the above-mentioned formula (1) thereafter.

[0039] The porosity ε0 of the solid catalyst layer in the reactor at the start of the reaction is, for example, the packing density BD of the solid catalyst layer (unit: kg / m 3 ), the true density of the packed solid catalyst, ρ cat (The unit is, for example, kg / m 3 ), and the pore volume PV (units are, for example, m 3 / kg), and ε0 = 1-(BD × (1 / ρ cat +PV) can be obtained by The packing density BD of the solid catalyst layer is the packing volume V of the solid catalyst layer. cat (For example, the unit is m 3 ), and the packed weight of the solid catalyst W cat (The unit is, for example, kg.) Then, BD=W cat / V cat It can be obtained by calculating Packing volume of solid catalyst layer V cat is the height of the solid catalyst layer (e.g., in m) and the cross-sectional area of ​​the reactor (e.g., cylindrical tubular reactor) (e.g., in m 2 The method for measuring the height of the solid catalyst layer will be described later. True density ρ of solid catalyst cat can be measured by a method known in the art, for example, by pycnometer measurement. The pycnometer method is a measurement method based on Archimedes' principle, and includes a liquid phase method and a gas phase method as a measurement means. The pore volume PV of a solid catalyst can be obtained by mercury porosimetry or gas (nitrogen gas, etc.) adsorption method.

[0040] (Tuning factor α(α const ), σ setting method 1) When a single solid catalyst layer is formed in the reactor, the tuning factor α in the formula (1) and the tuning factor σ in the formula (2) can be set, for example, by the following method (method 1 for setting α and σ). Any reaction time t x Estimated pressure drop in the reactor at ΔP sim is derived from the above formula (1), the equation for calculating the pressure drop based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the void ratio of the solid catalyst layer in the reactor, and the above formula (2). At this time, since α and σ are not determined, ΔP sim is a function of α and σ. The reaction time t x The measured pressure loss ΔP and the above ΔP sim The relationship is ΔP=ΔP sim The values ​​of α and σ can be set so that

[0041] A plurality of different solid catalyst layers are formed in the reactor, and the porosity ε x(n) The above ε x(n) When derived by the derivation method (2), the tuning factor α in the above formula (1-B) const The tuning factor σ in the above formula (2) can be set, for example, by the following method (α const , σ setting method1). Any reaction time t x Calculated pressure drop ΔP for each solid catalyst layer in the reactor cal(n) is derived from the above formula (1-B), the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the formula for calculating the pressure drop from the void fraction of the solid catalyst layer in the reactor (n is an integer of 2 or more and represents the number of different solid catalyst layers. The same applies below). In this case, ΔP cal(n) is α const Next, the calculated pressure drop for each solid catalyst layer, ΔP cal(n) The calculated pressure drop in the solid catalyst layer is calculated by adding up the above values. cal α constThe calculated pressure drop in the solid catalyst layer is calculated as a function of ΔP cal Substituting this into equation (2), the estimated pressure drop in the all-solid catalyst layer ΔP sim In this case, α const , σ is not determined, so ΔP sim is α const and is a function of σ. The reaction time t x The measured pressure loss ΔP and the above ΔP sim The relationship is ΔP=ΔP sim So that α const , σ can be set.

[0042] The estimated pressure loss ΔP sim The comparison of the pressure loss ΔP with the actual pressure loss ΔP was performed over multiple reaction times, and the tuning factor α (α const ) and σ. For example, the ΔP sim and the ΔP are obtained at any 15 or more points during the reaction, and the average value of each is ΔP sim(ave) , ΔP (ave) Ratio ΔP (ave) / ΔP sim(ave) The value of α(α const ), σ can be set.

[0043] (Tuning factor α(α const ), σ setting method 2) When a single solid catalyst layer is formed in the reactor, the tuning factors α and σ may be set by the following method (method 2 for setting α and σ). Initial reaction time t int Estimated pressure drop in the reactor at ΔP sim is derived from the equation for calculating the pressure drop based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the void ratio of the solid catalyst layer in the reactor, and from the above-mentioned equation (2). In this case, the void ratio of the solid catalyst layer in the reactor at the start of the reaction, ε0, is used as the void ratio of the solid catalyst layer in the reactor. In this case, ΔP sim is a function of σ. The initial reaction time t intThe measured pressure loss ΔP and the above ΔP sim The relationship is ΔP=ΔP sim The value of σ can be set so that

[0044] The initial reaction time t int The void ratio of the solid catalyst layer in the reactor at the start of the reaction is ε0. int Any reaction time t after x Estimated pressure drop in the reactor at ΔP sim is derived from the above formula (1), the equation for calculating the pressure drop based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the void ratio of the solid catalyst layer in the reactor, and the above formula (2). At this time, since σ is already determined, ΔP sim is a function of α. The reaction time t x The measured pressure loss ΔP and the above ΔP sim The relationship is ΔP=ΔP sim The value of α can be set so that

[0045] A plurality of different solid catalyst layers are formed in the reactor, and the porosity ε x(n) The above ε x(n) When derived by the derivation method (2), the tuning factor α in the above formula (1-B) const The tuning factor σ in the above formula (2) may be set by the following method (α const , σ setting method2). Initial reaction time t int Calculated pressure drop ΔP for each solid catalyst layer in the reactor cal(n) is derived from a formula for calculating pressure drop based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the porosity of the solid catalyst layer in the reactor. In this case, the porosity of each solid catalyst layer in the reactor at the start of the reaction described above, ε 0(n) Next, the calculated pressure drop ΔP for each solid catalyst layer is used. cal(n) The calculated pressure drop in the solid catalyst layer is calculated by adding up the above values. cal The calculated pressure drop of the solid catalyst layer is calculated as ΔP calSubstituting this into equation (2), the estimated pressure drop in the all-solid catalyst layer ΔP sim In this case, ΔP sim is a function of σ. The initial reaction time t int The measured pressure loss ΔP and the above ΔP sim The relationship is ΔP=ΔP sim The value of σ can be set so that

[0046] The initial reaction time t int The porosity of each solid catalyst layer in the reactor at 0(n) As the reaction starts at the initial time t int Any reaction time t after x Calculated pressure drop ΔP for each solid catalyst layer in the reactor cal(n) is derived from the above formula (1-B), the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the formula for calculating the pressure drop based on the void fraction of the solid catalyst layer in the reactor. cal(n) is α const Next, the calculated pressure drop for each solid catalyst layer, ΔP cal(n) The calculated pressure drop in the solid catalyst layer is calculated by adding up the above values. cal α const The calculated pressure drop in the solid catalyst layer is calculated as a function of ΔP cal Substituting this into equation (2), the estimated pressure drop in the all-solid catalyst layer ΔP sim At this time, since σ has already been determined, ΔP sim is α const It is a function of . The reaction time t x The measured pressure loss ΔP and the above ΔP sim The relationship is ΔP=ΔP sim So that α const You can set the value of

[0047] In this specification, α (α const ), and the initial reaction period in σ setting method 2 refers to the total volume (V flow ) and the packed volume of the solid catalyst layer (V cat) is the ratio of V flow / V cat means the reaction progress when it becomes 100 or less. In the initial stage of the reaction start when the above relationship holds, since almost no impurities are deposited on the solid catalyst layer, by approximately using ε0 as the porosity of the solid catalyst layer in the reactor, σ and α (α const ) can be determined step by step and uniquely.

[0048] When performing the reaction in a multitubular reactor equipped with a plurality of reactors, it is preferable to set the tuning factors α (α const ) and σ for each reactor.

[0049] <Equation for calculating pressure loss based on fluid viscosity, fluid linear velocity, fluid density, and porosity of solid catalyst layer in reactor> As the equation for calculating the pressure loss based on the fluid viscosity, fluid linear velocity, fluid density, and porosity of the solid catalyst layer in the reactor, a known equation in the art can be used. Examples of the equation for calculating the pressure loss in the reactor when the fluid is a single phase of gas or liquid include the Ergun equation, Blake·Kozeny equation, Burke·Plummer equation, Kozeny·Carman equation, Fanning equation, etc. Examples of the equation for calculating the pressure loss in the reactor when the fluid is a two-phase of gas and liquid include the Ergun·Larkins equation, Lockhart·Martinelli equation, etc., but are not limited thereto. Hereinafter, the Ergun equation will be described as the equation for calculating the pressure loss in the reactor when the fluid is a single phase of gas or liquid, and the Ergun·Larkins equation will be described as the equation for calculating the pressure loss in the reactor when the fluid is a two-phase of gas and liquid. However, the present invention is not limited to these equations.

[0050] <Ergun equation> In a fixed-bed flow-through reaction, the calculated value of the pressure loss in the reactor when the fluid is a single phase of gas or liquid can be derived by the Ergun equation represented by the following equation (7). In this embodiment, the calculated value of the pressure loss in the reactor obtained by the Ergun equation is ΔP1 calLet us assume that.

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[0052] In the above formula (7), a, b, and m are constants in the Ergun formula, ε is the void ratio of the solid catalyst layer in the reactor, μ is the viscosity of the fluid [kg / ms], u is the linear velocity of the fluid [m / s], and ρ is the density of the fluid [kg / m 3 ], dp is the spherical diameter [m] if the solid catalyst is assumed to be a sphere, and H is the bed height of the solid catalyst [m].

[0053] In the formula (7), a, b, and m are constants and are empirically determined values. For example, when the solid catalyst is spherical, a = 150, b = 1.75, and m = 3.0 can be used. For example, when the solid catalyst is not spherical, a = 180, b = 1.80, and m = 3.6 can be used.

[0054] In this embodiment, ε in the formula (7) is ε derived from the formula (1) or the formula (1-1) described below. x is used. μ is the viscosity of the fluid at the reaction temperature [kg / ms]. If the fluid is gas, it can be calculated by inputting the composition analysis results obtained by, for example, gas chromatography into a process simulator, and the result can be obtained by temperature conversion by multiplying the result obtained from JIS K 2283 "Crude oil and petroleum products - Test method for kinetic viscosity and calculation method for viscosity index" by the density converted to 15°C obtained from JIS K2249 "Crude oil and petroleum products - Test method for density and density, mass, and volume conversion table" for example. At the reaction temperature of a general fixed-bed flow reaction, the viscosity of the fluid, both gas and liquid, does not change enough to affect the pressure loss in the reactor, so the value obtained once can be used continuously as a fixed value. ρ is the density of the fluid at the reaction temperature [kg / m 3], and when the fluid is a gas, for example, the composition analysis results obtained by gas chromatography are input into a process simulator, and the calculation results are calculated by assuming the composition to be constant and correcting the density corresponding to said composition for temperature and pressure. When the fluid is a liquid, it can be obtained by correcting the density converted to 15°C obtained by, for example, JIS K2249 "Crude oil and petroleum products - Density test method and density, mass and volume conversion table" by temperature. u is the linear velocity of the fluid at the reaction temperature [m / s], and the flow rate of the fluid [m 3 / s] is the cross-sectional area [m 2 The flow rate of the fluid can be obtained by dividing by S IN and S OUT The step of acquiring the information can be performed in the same manner as described above.

[0055] dp is the spherical diameter [m] when the solid catalyst is assumed to be a sphere. The shape of the solid catalyst used in fixed bed flow reactions is selected according to the application, but ring-shaped, cylindrical, tablet-shaped, honeycomb-shaped, three-leaf-shaped, four-leaf-shaped, and even spherical catalyst shapes are commonly used. In this embodiment, if the packed solid catalyst is spherical, its spherical diameter can be taken as dp. On the other hand, if the solid catalyst is not spherical, the spherical diameter can be calculated assuming that the solid catalyst is a sphere, and this diameter can be taken as dp. As described in a known document (Ind. Eng. Chem. Des. Dev. 1986, 25, 1034-1036), for example, if it is a cylinder, it can be calculated by formula (8-1), if it is a three-leaf clover, it can be calculated by formula (8-2), and if it is a four-leaf clover, it can be calculated by formula (8-3).

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[0057] In the above formulas (8-1) to (8-3), L is the average major diameter [m] of the solid catalyst, and D is the average minor diameter [m] of the solid catalyst. The average major diameter and average minor diameter of the solid catalyst can be measured, for example, for the major diameters and minor diameters of 50 or more solid catalysts, and the average value thereof can be adopted. In the present invention, dp of the solid catalyst is measured before the start of the reaction, and it is assumed that the value of dp does not change during the reaction.

[0058] H is the bed height [m] of the solid catalyst. The bed height of the solid catalyst can be measured by a method known in the art when the solid catalyst is filled before the start of the reaction. The bed height of the solid catalyst can be measured, for example, by gauging at the time of catalyst filling. In the present invention, it is assumed that the value of the bed height of the solid catalyst does not change during the reaction.

[0059] Substitute the above parameters into the formula (7) to derive ΔP1 cal And the obtained ΔP1 cal is substituted into ΔP in the formula (2) cal to obtain an estimated value ΔP x of the pressure loss in the reactor at the reaction time t sim (hereinafter, the estimated value of the pressure loss in the reactor when the fluid is a single phase of gas or liquid may be denoted as ΔP1 sim ) can be obtained.

[0060] <Ergun·Larkins formula> In a fixed-bed flow reactor, when the fluid is a two-phase of gas and liquid, the calculated value of the pressure loss in the reactor can be derived by the Ergun·Larkins formula composed of the following formulas (9) to (14). In the present embodiment, the calculated value of the pressure loss in the reactor obtained by the Ergun·Larkins formula is denoted as ΔP2 cal .

[0061]

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[0062] In the formula (9), δ Lis the ΔP of the liquid cal / H, δ G is the ΔP of the gas cal / H, δ LG is the ΔP of the gas / liquid cal / H, and χ=(δ L / δ G ) 1 / 2 , where 0.05<χ<30.)

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[0064] In the formula (10), R L is the liquid holdup.

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[0066] In the above formula (11), ρ m is the average gas-liquid density, ρ L is the liquid density, ρ G is the density of the gas, R L is the same as above.

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[0068] Calculated pressure drop in the reactor using the Ergun·Larkins equation ΔP2 cal The derivation of is explained below. First, δ L and δ G is derived as follows using the Ergun formula (formula (13) and formula (14) below).

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[0070] In the above formula (13), a, b, and m are constants in the Ergun formula, ε is the void ratio of the solid catalyst layer in the reactor, μ L is the viscosity of the liquid [kg / ms], u L is the linear velocity of the liquid [m / s], ρ L is the density of the liquid [kg / m 3 ], dp is the spherical diameter [m] when the solid catalyst is assumed to be a sphere, and H is the catalyst bed height [m]. The method for calculating these values ​​is as explained in the Ergun formula. In this embodiment, ε in the formula (13) is ε derived from the formula (1) or the formula (1-1) described below. x Use.

[0071]

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[0072] In the above formula (14), a, b, and m are constants in the Ergun formula, ε is the void ratio of the solid catalyst layer in the reactor, μ G is the viscosity of the gas [kg / ms], u G is the linear velocity of the gas [m / s], ρ G is the density of the gas [kg / m 3 ], dp is the spherical diameter [m] when the solid catalyst is assumed to be a sphere, and H is the catalyst bed height [m]. The method for calculating these values ​​is as explained in the Ergun formula. In this embodiment, ε in the formula (14) is ε derived from the formula (1) or the formula (1-1) described below. x Use.

[0073] The obtained δ L and δ G Therefore, χ = (δ L / δ G ) 1 / 2 Next, δ L , δ G , χ is used to obtain δ from the above formula (9). LG From the above formula (10), L Next, the obtained R L Using the above formula (11), ρ m The obtained δLG and ρ m Using the above formula (12), ΔP2 cal Then, the obtained ΔP2 cal ΔP in the above formula (2) cal By substituting the above, the reaction time t x The estimated pressure drop in the reactor at sim (Hereafter, the estimated pressure drop in the reactor when the fluid is two-phase, gas and liquid, is ΔP2 sim (sometimes written as

[0074] In the method for estimating pressure drop according to the present invention, when a plurality of different solid catalyst layers are formed in a reactor, the calculated pressure drop ΔP in each solid catalyst layer is calculated. cal(n) The pressure loss in the solid catalyst layer is calculated by integrating the above values. cal Then, the obtained ΔP cal By substituting into the above formula (2), the estimated pressure drop ΔP in the reactor when multiple different solid catalyst layers are formed in the reactor is obtained. sim can be sought.

[0075] ΔP obtained by the method for estimating pressure drop in a reactor of the present invention sim is ΔP / ΔP, where ΔP is the actual pressure drop in the reactor. sim is preferably 0.50 or more and 1.50 or less on average, and more preferably 0.80 or more and 1.20 or less. sim For example, the average of 15 or more points is ΔP / ΔP sim can be obtained by measuring

[0076] ΔP / ΔP for a given period sim When the average value of ΔP / ΔP falls outside the above range, it is preferable to reset the tuning factor α. simIf the average value of is outside the above range, it suggests that the increase in pressure drop is caused not only by the accumulation of impurities in the fluid on the solid catalyst layer but also by other factors.

[0077] When a single solid catalyst layer is formed in the reactor, ΔP / ΔP sim When the average value of falls outside the above range, it is preferable to reset the tuning factor α as follows. ΔP / ΔP for a given period sim At any reaction time t after the average value of x Estimated pressure drop in the reactor at ΔP sim is derived from the above formula (1), a formula for calculating the pressure drop based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the void ratio of the solid catalyst layer in the reactor, and the above formula (2). x The measured pressure loss ΔP and the above ΔP sim The relationship is ΔP=ΔP sim The value of α can be reset so that

[0078] A plurality of different solid catalyst layers are formed in the reactor, and the porosity ε x(n) The above ε x(n) When derived using method (2), ΔP / ΔP for a given period sim When the average value of is outside the above range, the tuning factor α const It is preferable to reset the following: ΔP / ΔP for a given period sim At any reaction time t after the average value of x Calculated pressure drop ΔP for each solid catalyst layer in the reactor cal(n) is derived from the above formula (1-B), the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the pressure drop calculation formula based on the void ratio of the solid catalyst layer in the reactor. Next, the calculated pressure drop ΔP cal(n) The calculated pressure drop in the solid catalyst layer is calculated by adding up the above values. cal The calculated pressure drop of the solid catalyst layer is calculated as ΔPcal Substituting this into equation (2), the estimated pressure drop in the all-solid catalyst layer ΔP sim At this time, the reaction time t x The measured pressure loss ΔP and the above ΔP sim The relationship is ΔP=ΔP sim So that α const You can simply reset the value of

[0079] ΔP / ΔP for a given period sim The estimated pressure loss ΔP after the average value of sim The comparison of the pressure loss ΔP with the actual pressure loss ΔP was performed over multiple reaction times, and the tuning factor α (α const For example, it is preferable to determine again ΔP / ΔP sim After the average value of ΔP falls outside the range sim and the ΔP are obtained at any 15 or more points during the reaction, and the average value of each is ΔP sim(ave) , ΔP (ave) Ratio ΔP (ave) / ΔP sim(ave) The value of α(α const ) can be reconfigured.

[0080] ΔP / ΔP during the above-mentioned predetermined period sim The fact that the average value of falls outside the above range suggests that the porosity of the solid catalyst layer is reduced due to other factors in addition to the deposition of impurities contained in the fluid containing reactants such as metal compounds on the solid catalyst layer. For example, when the fluid contains a compound containing carbon element, coke is generated in the reactor and the coke is deposited on the solid catalyst layer, which may reduce the porosity of the solid catalyst layer.

[0081] Based on the above-mentioned method for estimating the pressure drop in the reactor, the inventors of the present application further x Reaction temperature T t(x) (S1C in FIG. 2), t(x) and the coking threshold T B The relationship betweent(x) >T B When the above condition is satisfied, the porosity ε of the solid catalyst layer in the reactor is x In the step of deriving the above formula (1), the above S is added to the following formula (1-1) instead of the above formula (1). IN , the above S OUT , said T B , and the T t(x) Substituting the above reaction time t x The porosity ε of the solid catalyst layer in the reactor x (S1BC in Figure 2), we have found a new method to estimate the change in the porosity of the solid catalyst layer over time and the pressure drop in the reactor due to the change in the porosity over time, taking into account the deposition of coke in the solid catalyst layer in addition to the deposition of impurities in the solid catalyst layer.

[0082]

number

[0083] Reaction time t x Reaction temperature T t(x) Examples of the temperature that can be used include the maximum temperature of the solid catalyst layer (hot spot temperature), the weight average temperature (WABT) of the solid catalyst layer, the inlet temperature of the reactor, the outlet temperature of the reactor, and the average temperature of the inlet temperature and the outlet temperature of the reactor. Among these, it is preferable to use the maximum temperature of the solid catalyst layer. The above-mentioned temperatures can be obtained, for example, by a thermometer in the reactor.

[0084] In the above formula (1-1), the threshold value T B is the temperature at which coke is generated and begins to deposit on the solid catalyst bed. The coking threshold is uniquely determined when a combination of the type of solid catalyst, the type of fluid containing reactants, and the liquid hourly space velocity (LHSV) and / or gas hourly space velocity (GHSV) of the fluid relative to the solid catalyst is determined. In other words, when the above combination is determined, T B is a constant value. The coking threshold T BA method for obtaining T will be described, but this method is merely an example. B The method of obtaining the above is not limited to this.

[0085] (Coking threshold T B How to get 1) As mentioned above, the coking threshold T B is the temperature at which coke is generated and begins to accumulate on the solid catalyst layer. Therefore, in the case of a reaction in which the solid catalyst can be extracted over time, the extracted solid catalyst is analyzed by elemental analysis, etc., and the reaction temperature at which the carbon concentration in the solid catalyst reaches a certain value or more is defined as T B The certain value may be, for example, 0.05% by mass or more. The extraction and elemental analysis of the solid catalyst are preferably performed at intervals of 5 to 20°C, more preferably at intervals of 5 to 10°C, of ​​the reaction temperature. The reaction temperature is as described above, and it is preferable to adopt the maximum temperature of the solid catalyst layer. In this method, the coking threshold T B may be obtained while carrying out the reaction in an actual machine, or may be obtained in advance in a laboratory or bench scale that is smaller than the actual machine. B In order to obtain the above, as described above, the type of solid catalyst, the type of fluid containing the reactants, and the LHSV and / or GHSV of the fluid relative to the solid catalyst may be set to be the same as the reaction conditions in the actual equipment. In actual plants, it is often difficult to remove the catalyst over time, so the coking threshold T B In the first method, the threshold value of coking T is obtained in advance on a laboratory or bench scale. B It is preferable to obtain

[0086] (Coking threshold T B How to get 2) As described above, when coke starts to be generated, the coke begins to deposit on the solid catalyst layer, the voids in the solid catalyst layer are gradually blocked, and the pressure loss increases. Further, in a fixed-bed flow reaction, since the activity of the solid catalyst decreases with time due to various factors, the reaction is carried out while increasing the reaction temperature with time in order to keep the activity of the entire reactor constant. When the inventors of the present application examined the relationship between the reaction temperature and the measured value of the pressure loss in the reactor using the hydrotreating reaction of heavy hydrocarbon oil as a model, it was found that when the measured value of the pressure loss in the reactor was plotted against the reaction temperature at the initial stage of the reaction when coke was not deposited on the solid catalyst layer, a linear relationship (straight line 1) represented by y = a1x + b1 was obtained. In the straight line 1, y is the measured value of the pressure loss in the reactor, x is the reaction temperature, a1 is the slope, and b1 is the intercept. The reaction temperature is as described above, and it is preferable to adopt the maximum temperature of the solid catalyst layer, and the same applies hereinafter.

[0087] When the inventors of the present application further investigated, it was found that after coke started to deposit on the solid catalyst layer, when the measured value of the pressure loss in the reactor was plotted against the reaction temperature, the plot deviated significantly upward from the straight line 1. And it was found that after coke started to deposit on the solid catalyst layer, when the measured value of the pressure loss in the reactor was plotted against the reaction temperature, a new linear relationship (straight line 2) represented by y = a2x + b2 was obtained. In the straight line 2, y is the measured value of the pressure loss in the reactor, x is the reaction temperature, a2 is the slope and satisfies a2 > a1, and b2 is the intercept and satisfies b2 < b1. That is, when the inventors of the present application plotted the measured value of the pressure loss in the reactor against the reaction temperature, the plot shifted from the straight line 1 to the straight line 2 before and after the start of deposition of coke on the solid catalyst layer, and the reaction temperature at the intersection of the straight line 1 and the straight line 2 (the inflection point from the straight line 1 to the straight line 2) is T B was found to be obtainable.

[0088] The method for measuring the inflection point will now be described in detail. From the start of the reaction, the actual pressure drop measurements in the reactor and the reaction temperature are obtained over time, plotted, and line 1 is obtained using Excel or the like. For example, the above plot is performed at M points from the start of the reaction, and line 1 expressed as y=a1x+b1 is obtained. M is a positive integer, for example, 5 to 350. Next, the reaction temperature at the M+1th point is substituted for x in the equation for line 1, and y is calculated. (M+1) The obtained y (M+1) and the measured pressure drop in the reactor at the M+1 point ΔP (M+1) ΔP (M+1) / y (M+1) Calculate. Said ΔP (M+1) / y (M+1) When is 0.8 to 1.2, it is judged as a plot on the line 1, and the plot is also included to recalculate a1 and b1 of line 1. From the (M+2)th point onwards, the calculation of the ratio between the calculated value and the pressure drop in the reactor is repeated in the same manner, and when the ratio is within the range of 0.8 to 1.2, the same process as for the (M+1)th point is carried out.

[0089] When the ratio exceeds 1.2, it can be determined that coke is generated, the coke starts to accumulate on the solid catalyst layer, and the plot of the measured value of pressure drop in the reactor against the reaction temperature shifts from the line 1 to the line 2. At N points after the point at which the ratio exceeds 1.2, the measured value of pressure drop in the reactor and the reaction temperature are obtained over time and plotted, and line 2 expressed by y=a2x+b2 is obtained using Excel or the like. N is a positive integer, for example, 5 to 350. Then, the intersection point of the line 1 and the line 2 is obtained, and the threshold value T of coking is calculated as x at the intersection point. B can be obtained. In this method, the coking threshold T B may be obtained while carrying out the reaction in an actual machine, or may be obtained in advance in a laboratory or bench scale that is smaller than the actual machine. BIn order to obtain the above, as described above, the type of solid catalyst, the type of fluid containing the reactants, and the LHSV and / or GHSV of the fluid relative to the solid catalyst may be set to be the same as the reaction conditions in the actual equipment.

[0090] Coking threshold T B The second method does not require the removal of the solid catalyst, and does not require the reaction to be stopped. B This is preferable to acquisition method 1.

[0091] The tuning factor α is calculated by the above method. t(x) ≦T B The value set in T t(x) >T B It can still be used after that. The tuning factors β and γ can be set, for example, by the following method.

[0092] (Method 1 for setting tuning factors β and γ) Reaction temperature T t(x) and the coking threshold T B The relationship between t(x) >T B Any reaction time t when x Estimated pressure drop in the reactor at ΔP sim is derived from the above formula (1-1), the equation for calculating the pressure drop based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the void ratio of the solid catalyst layer in the reactor, and the above formula (2). At this time, since β and γ are not determined, ΔP sim is a function of β and γ. The reaction time t x The measured pressure loss ΔP and the above ΔP sim The relationship is ΔP=ΔP sim The values ​​of β and γ can be set so that

[0093] The estimated pressure loss ΔP sim The comparison of the pressure drop ΔP with the reaction temperature T t(x) and the coking threshold T B The relationship betweent(x) >T B When any reaction time t is met for the first time x It is preferable to carry out the above-mentioned steps at several subsequent reaction times to determine the tuning factors β and γ. For example, sim and the ΔP are obtained at any 15 or more points during the reaction, and the average value of each is ΔP sim(ave) , ΔP (ave) Ratio ΔP (ave) / ΔP sim(ave) β and γ can be set so that the value of is closest to 1.

[0094] (Method 2 for setting tuning factors β and γ) Reaction temperature T t(x) and the coking threshold T B The relationship between t(x) >T B Any reaction time t when x Estimated pressure drop in the reactor at ΔP sim is derived from the above formula (1-1), a formula for calculating the pressure drop based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the porosity of the solid catalyst layer in the reactor, and the above formula (2). At this time, a provisional value is set as β. The provisional value of β may be, for example, greater than 0 and equal to or less than 10, and may be 1. By using a tentative value for β, the ΔP derived by the above method sim is a function of γ. The reaction time t x The measured pressure loss ΔP and the above ΔP sim The relationship is ΔP=ΔP sim The value of γ can be set so that

[0095] Using the thus obtained β and γ, x Any other reaction time t later x+1 Estimated pressure drop in the reactor at ΔP sim is derived from the above formula (1-1), a formula for calculating pressure drop based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the void fraction of the solid catalyst layer in the reactor, and the above formula (2).

[0096] The reaction time t x+1 The measured pressure loss ΔP and the above ΔP sim ΔP / ΔP sim If is outside the range of 0.5 to 1.5, change the tentative value of β and repeat the above procedure (reaction time t x The measured pressure loss ΔP and the above ΔP sim The relationship is ΔP=ΔP sim Set the value of γ so that On the other hand, ΔP / ΔP sim When is within the range of 0.5 to 1.5, the β and γ are used, and the reaction time t x+1 Any other reaction time t later x+2 Estimated pressure drop in the reactor at ΔP sim is derived in the same manner as above. The reaction time t x+2 The measured pressure loss ΔP and the above ΔP sim ΔP / ΔP sim If it is out of the range of 0.5 to 1.5, the provisional value of β is changed in the same manner as above, and the value of γ is set again by the above method. On the other hand, ΔP / ΔP sim When is within the range of 0.5 to 1.5, the β and γ are used, and the reaction time t x+2 Any other reaction time t later x+3 Estimated pressure drop in the reactor at ΔP sim is derived in the same manner as above, and the above operations are repeated.

[0097] The above-mentioned operation is repeated, and the reaction time t x ΔP / ΔP for all 15 points below sim When is within the range of 0.5 to 1.5, β and γ can be determined.

[0098] <Application example of the pressure loss estimation method of the present invention> A suitable application example of the method for estimating pressure drop in the case where the fluid is a two-phase gas and liquid fluid of the present invention is the hydrotreating reaction of heavy hydrocarbon oil. The method for estimating pressure drop in the hydrotreating reaction of heavy hydrocarbon oil will be described below.

[0099] (Hydrotreatment of heavy hydrocarbon oil) The hydrotreating reaction of heavy hydrocarbon oil is a two-phase fixed bed flow reaction in which liquid heavy hydrocarbon oil and gaseous hydrogen are circulated through a reactor to carry out the reaction. Heavy hydrocarbon oil contains metal impurities, and these metal impurities accumulate on the solid catalyst layer, causing the pressure loss to increase over time. Representative examples of metal elements contained in metal impurities contained in heavy hydrocarbon oil include Ni, V, Fe, Na, Zn, Al, Ba, Ca, Mg, P, Pb, Mo, Cr, Cd, As, Se, and Si. In addition, in the hydrotreating reaction of heavy hydrocarbon oil, it is necessary to increase the reaction temperature over time as the activity of the solid catalyst decreases, and it is known that when the reaction temperature exceeds a certain value, coke is generated, and the coke begins to accumulate on the solid catalyst layer and blocks the voids in the fixed catalyst layer.

[0100] First, at any reaction time t x Any other reaction time t before x-1 From the reaction time t x Between (t x -t x-1 ) the total amount of metal impurities in the heavy hydrocarbon oil flowing into the reactor IN , and the total amount of metal impurities S in the heavy hydrocarbon oil discharged from the reactor OUT Obtain the above S IN is the reaction time t x-1 From the reaction time t x Between (t x -t x-1 The metal impurity concentration (unit: ppm, for example) in the heavy hydrocarbon oil before it flows into the reactor during the above process can be measured, and the product of this and the amount (unit: kg, for example) of the heavy hydrocarbon oil that flows into the reactor during the above process can be calculated. OUT is the reaction time tx-1 From the reaction time t x Between (t x -t x-1 The metal impurity concentration (unit: ppm, for example) in the heavy hydrocarbon oil after it flows out of the reactor during the reaction can be measured, and the product of this and the amount of heavy hydrocarbon oil (unit: kg, for example) that flows out of the reactor during that time can be calculated.

[0101] A method for measuring the concentration of metal impurities includes, for example, ICP-MS. The amount of the heavy hydrocarbon oil flowing into the reactor and the amount of the heavy hydrocarbon oil flowing out from the reactor can be obtained, for example, by a flow meter.

[0102] In addition, the hydrogen used in the hydrotreating reaction of heavy hydrocarbon oil does not usually contain impurities that accumulate on the solid catalyst layer. IN and the above S OUT There is no need to measure the impurity concentration in hydrogen to derive

[0103] The obtained S IN and S OUT Substituting into the above formula (1), the reaction time t x The porosity ε of the solid catalyst layer in the reactor x The porosity ε0 of the solid catalyst layer in the reactor at the start of the reaction can be obtained by the above-mentioned method, and ε x-1 can be obtained by repeatedly applying the above formula (1) starting from ε0.

[0104] In this embodiment, the reaction time t x Reaction temperature T t(x) obtaining the T t(x) and the coking threshold T B The relationship between t(x) >T B When the above condition is satisfied, the porosity ε of the solid catalyst layer in the reactor is x In the step of deriving the above formula (1), the above S is added to the following formula (1-1) instead of the above formula (1). IN , the above S OUT , said T B, and the T t(x) Substituting the above reaction time t x The porosity ε of the solid catalyst layer in the reactor x It is preferable to obtain In this embodiment, the reaction time t x Reaction temperature T t(x) is as described above, and it is preferable to adopt the maximum temperature of the catalyst layer. The reaction temperature can be obtained, for example, by a thermometer in the reactor.

[0105] Heavy hydrocarbon oil δ L is derived by the above formula (13). In this case, the porosity ε of the solid catalyst layer in the reactor is determined by the above formula (1) or the above formula (1-1). x The viscosity μ of the heavy hydrocarbon oil at the reaction temperature is used. L [kg / ms] can be obtained by multiplying the result obtained from JIS K 2283 "Crude oil and petroleum products - Kinematic viscosity test method and viscosity index calculation method" by the density converted to 15°C obtained from JIS K2249 "Crude oil and petroleum products - Density test method and density, mass, and volume conversion table" and converting it to temperature. The density ρ of heavy hydrocarbon oil at the reaction temperature is L [kg / m 3 ] can be obtained by correcting the density at 15°C obtained by, for example, JIS K2249 "Crude oil and petroleum products - Density test method and density, mass and volume conversion table" with temperature. L [m / s] is the flow rate of heavy hydrocarbon oil [m 3 / s] is the cross-sectional area [m 2 The flow rate of the heavy hydrocarbon oil can be obtained, for example, by a flow meter.

[0106] δ of hydrogen G is derived by the above formula (14). In this case, the solid catalyst void ratio ε in the reactor is determined by the above formula (1) or the above formula (1-1). x The viscosity of hydrogen at the reaction temperature μ G[kg / ms] can be obtained by inputting the composition analysis results obtained by gas chromatography into a process simulator and calculating the density of hydrogen at the reaction temperature ρ G [kg / m 3 ] can be obtained by correcting the density corresponding to the composition obtained by composition analysis using gas chromatography, for example, with temperature. G [m / s] is the flow rate of hydrogen [m 3 / s] is the cross-sectional area [m 2 The flow rate of hydrogen can be obtained, for example, by a gas meter.

[0107] The obtained δ L and δ G Therefore, χ = (δ L / δ G ) 1 / 2 Next, δ L , δ G , χ is used to obtain δ from the above formula (9). LG From the above formula (10), L Next, the obtained R L Using the above formula (11), ρ m Then, the obtained δ LG and ρ m Using the above formula (12), ΔP2 cal Then, the obtained ΔP2 cal ΔP in the above formula (2) cal By substituting the above, the reaction time t x The estimated pressure drop in the reactor ΔP sim (ΔP2 sim ) can be obtained.

[0108] The conditions for the hydrotreating reaction of heavy hydrocarbon oil are generally a reaction temperature of 300 to 450°C, preferably 350 to 410°C, a hydrogen partial pressure of 4 to 20 MPa, preferably 8 to 15 MPa, and a liquid hourly space velocity of the reactor of 0.05 to 5 h -1 , preferably 0.1 to 2 hours -1The hydrogen / oil ratio is 400 to 3,000 (L / L), and preferably 500 to 1,400 (L / L).

[0109] The catalyst used in the hydrotreating reaction of heavy hydrocarbon oil is not particularly limited, and any hydrotreating catalyst known in the art can be used.Various catalyst supports can be used, such as silica, alumina, boria, magnesia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-boria, alumina-zirconia, alumina-titania, alumina-boria, alumina-chromia, titania-zirconia, silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, and the like, or mixtures of two or more of these.Of these inorganic oxides, preferred ones include alumina, silica-alumina, alumina-titania, alumina-boria, and alumina-zirconia, and particularly preferred ones include alumina, and among aluminas, γ-alumina is particularly preferred. These inorganic oxides may be used alone or in combination of two or more.

[0110] The metal contained in the carrier as an active component includes at least one metal selected from the group 6 metals and the group 8-10 metals of the periodic table, and is preferably molybdenum, tungsten, cobalt, and nickel metals and compounds containing them. These metal components are effective in any form of metal, metal oxide, or metal sulfide, and may be present in a form in which the metal component is bonded to the catalyst carrier by ion exchange or the like. The content of this metal component is usually within the range of about 10-25 mass% based on the catalyst and calculated as an oxide. If the metal content is less than 10 mass%, the absolute amount of the metal acting as an active site is small, so that hydrotreating activity including desulfurization activity (hereinafter simply referred to as hydrotreating activity) is not expressed, and conversely, if the content of the supported metal is too much than 25 mass%, the metal will aggregate and the number of active sites will decrease, resulting in a decrease in hydrotreating activity. Furthermore, in addition to the active metals consisting of metals in Groups 6 and 8 of the Periodic Table, phosphorus, boron, zinc, zirconia, etc. may be contained, if necessary.

[0111] Although the hydrotreating reaction of heavy hydrocarbon oil has been given as an example of a fixed-bed flow reaction in which a two-phase fluid of gas and liquid flows through a reactor packed with a solid catalyst, the present invention is not limited thereto. In other words, the pressure drop estimation method of the present invention can be applied to any reaction in which impurities in the fluid can be measured and coke is produced. An example of such a reaction is the hydrotreating method of light hydrocarbons.

[0112] <How to use the pressure loss estimation method of the present invention> Examples of applications of the pressure loss estimation method of the present invention include: (1) confirmation of an abnormal increase in pressure loss during a reaction operation; (2) estimation of when to terminate a reaction; (3) estimation of the progress of pressure loss until the end of an operation period based on an operation plan; (4) estimation of operating conditions that result in an allowable pressure loss or less for the operation period; and (5) selection of a crude oil type that results in an impurity content below an upper limit.

[0113] (Confirmation of abnormal increase in pressure loss during reaction operation) The porosity ε of the solid catalyst layer derived by the above formula (1) of the present invention x Using the above, the estimated pressure loss ΔP obtained by the pressure loss estimation method sim When the actual measured value ΔP is significantly different from the actual measured value ΔP (especially ΔP / ΔP sim >1.5), it is suggested that the increase in pressure drop is not only due to the accumulation of impurities in the fluid on the solid catalyst layer, but also due to other factors. For example, pressure drop may increase when coke is generated and begins to accumulate on the solid catalyst layer, gradually blocking the pores in the solid catalyst layer. In this case, the change in pressure drop over time can be estimated again by resetting the tuning factor α. The method for resetting the tuning factor α is as described above. In addition, the porosity ε of the solid catalyst layer derived from the above formula (1-1) x Using the above method, the estimated pressure loss ΔP sim The method using the above formula (1-1) is preferable to the above method of resetting the tuning factor α because it is not necessary to change the tuning factor α.

[0114] (Estimation of when the reaction should end) The estimated pressure loss values ​​obtained by the pressure loss estimation method of the present invention are plotted against the reaction time, and an estimated pressure loss curve is created by connecting these plots, thereby estimating the reaction time at which the allowable pressure loss set in the reactor is reached, and the time at which the reaction should be terminated can be determined with reference to the estimated time. In addition, the reaction time at which the allowable pressure loss set in the reactor is reached can also be estimated by plotting the estimated future pressure loss values ​​against the reaction time by substituting the predicted values ​​of the expected future operating conditions, the amount of impurities deposited, etc. into the above formula, and the time at which the reaction should be terminated can also be estimated with reference to the estimated time.

[0115] (Estimation of pressure loss trends until the end of the operation period based on the operation plan) The pressure loss until the end of operation can be estimated from the estimated pressure loss value obtained by the pressure loss estimation method of the present invention and future operating conditions, and it can be confirmed that the pressure loss will be below the allowable pressure loss under these operating conditions.

[0116] (Estimation of operating conditions that will keep pressure loss below allowable level for the operating period) The estimated pressure loss obtained by the method for estimating pressure loss of the present invention can be used to estimate operating conditions (mainly flow rate) that will keep the pressure loss below the allowable pressure loss until the end of the operating period. Details will be described later.

[0117] (Selection of crude oil type with impurity content below the upper limit) From the estimated pressure drop value obtained by the pressure drop estimation method of the present invention, it is possible to estimate the impurity content that will keep the pressure drop below the allowable pressure drop until the end of the operating period, and to select crude oil containing impurities at or below the estimated value.

[0118] <Reaction method for controlling pressure loss> Another embodiment of the present invention is a fixed bed flow reaction in which a one-phase fluid of gas or liquid, or a two-phase fluid of gas and liquid, is flowed through a reactor packed with a solid catalyst, and the reaction time t x A reaction method for controlling a pressure drop in the reactor, comprising: x Any other reaction time t before x-1 From the reaction time t x Between (t x -t x-1 ) the total amount of impurities in the fluid flowing into the reactor S IN , and the total amount of impurities S in the fluid discharged from the reactor OUT A step of acquiring S IN and S OUT Substituting into the following formula (3), the reaction time t x The porosity ε of the solid catalyst layer in the reactor x and deriving a desired pressure drop ΔP in the reactor. x Substituting into the following equation (4), ΔP cal The obtained ΔP cal and the εx into an equation for calculating the pressure drop based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the porosity of the solid catalyst layer in the reactor, and the reaction is carried out by adjusting the viscosity μ of the fluid, the linear velocity u of the fluid, and the density ρ of the fluid so that the equation for calculating the pressure drop is valid.

[0119]

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[0120]

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[0121] In the method of estimating pressure loss already described, parameters such as the viscosity μ of the fluid, the linear velocity u of the fluid, and the density ρ of the fluid are substituted into a predetermined formula to obtain an estimated pressure loss value ΔP sim However, in this embodiment, the desired pressure loss ΔP x Set the ΔP x is substituted into a prescribed formula, and the reaction is carried out by adjusting the fluid viscosity μ, the fluid linear velocity u, and the fluid density ρ so that the prescribed formula holds. The conditions of the fluid viscosity μ, the fluid linear velocity u, and the fluid density ρ required for control to achieve a desired pressure loss are obtained, and the reaction is carried out under those conditions.

[0122] Any reaction time t x ε in x The void ratio ε0 of the solid catalyst layer in the reactor at the start of the reaction can be calculated by the above formula (3) in the same manner as described in the above-mentioned method for estimating pressure drop. The tuning factors α and σ can be calculated in the same manner as described in the above-mentioned method for estimating pressure drop.

[0123] In this embodiment, the reaction time t x Reaction temperature T t(x) obtaining the T t(x) and the coking threshold T B The relationship between t(x) >T B When ε satisfies x is preferably calculated by the following formula (3-1) in the same manner as in the above-described method for estimating pressure loss. B and the tuning factors β and γ can be obtained in the same manner as described above in the method for estimating pressure loss.

[0124]

number

[0125] (When the fluid is one phase of gas or liquid) Regarding the reaction method for controlling the pressure drop when the fluid is one phase of gas or liquid, we will explain the case where the Ergun formula is used to calculate the pressure drop based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the void ratio of the solid catalyst layer in the reactor. First, the desired pressure drop ΔP1 x Set the ΔP1 x ΔP in the above formula (4) x Substituting into, ΔP cal (Hereafter, the calculated pressure drop in the reactor when the fluid is one phase of gas or liquid is ΔP1 cal Next, we derive the above ΔP1 cal ε derived from the above formula (3) or the above formula (3-1) x , the height H of the solid catalyst layer, and the spherical diameter dp when the solid catalyst is assumed to be a sphere are substituted. The bed height H of the solid catalyst and the spherical diameter dp when the solid catalyst is assumed to be a sphere are as explained in the above-mentioned method for estimating pressure loss.

[0126] By substituting the above parameters, the variables in the Ergun formula are the viscosity μ of the fluid, the linear velocity u of the fluid, and the density ρ of the fluid. By selecting a combination of μ, u, and ρ that satisfies the Ergun formula and carrying out a reaction under those conditions, the desired pressure drop ΔP1 x can be achieved.

[0127] In chemical reactions, it is often difficult to significantly change the viscosity μ and density ρ of the fluid containing the reactants. In such cases, the desired pressure loss ΔP1 can be achieved by selecting u so that the Ergun equation holds true. x can be achieved.

[0128] (When the fluid is two-phase, gas and liquid) Regarding the reaction method for controlling the pressure drop when the fluid is two-phase gas and liquid, we will explain the case where the Ergun-Larkins equation is used to calculate the pressure drop based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the void ratio of the solid catalyst layer in the reactor. First, the desired pressure drop ΔP2 x Set the ΔP2 x ΔP in the above formula (4) x Substituting into, ΔP cal (Hereafter, the calculated pressure drop in the reactor when the fluid is two-phase, gas and liquid, is ΔP2 cal Next, we derive the above ΔP2 cal ε derived from the above formula (3) or the above formula (3-1) x , the height H of the solid catalyst layer, and the spherical diameter dp when the solid catalyst is assumed to be a sphere are substituted. The bed height H of the solid catalyst and the spherical diameter dp when the solid catalyst is assumed to be a sphere are as explained in the above-mentioned method for estimating pressure loss.

[0129] Specifically, the ΔP2 cal , Substituting H into the formula (12), x , and substitute dp into the above formulas (13) and (14). From the above formulas (9), (13), and (14), δ LG Let μ be the viscosity of the liquid.L , the linear velocity of the liquid, u L , density of the liquid ρ L , the viscosity of the gas μ G , the linear velocity of the gas, u G , the density of the gas ρ G From the above equations (10), (11), (13), and (14), ρ m , μ L , u L , ρ L , μ G , u G , ρ G From these equations and the above equation (12), ΔP2 cal μ L , u L , ρ L , μ G , u G , ρ G Let μ be an equation that satisfies the above equation. L , u L , ρ L , μ G , u G , ρ G By selecting a combination of these and carrying out the reaction under these conditions, the desired pressure drop ΔP2 x can be achieved.

[0130] As mentioned above, in chemical reactions, it is often difficult to significantly change the viscosity μ and density ρ of the fluid containing the reactants. In such cases, the linear velocity u of the liquid that satisfies the above formula is L , the linear velocity of the gas, u G By selecting and carrying out the reaction, the desired pressure drop ΔP2 x can be achieved.

[0131] <Pressure loss estimation device, pressure loss estimation program> Another embodiment of the present invention is a fixed bed flow reaction in which a one-phase fluid of gas or liquid, or a two-phase fluid of gas and liquid, is flowed through a reactor packed with a solid catalyst, and the reaction time t x The pressure drop estimation deriving device in the reactor, xa fluid information acquisition unit for acquiring a viscosity μ of the fluid, a linear velocity u of the fluid, and a density ρ of the fluid at the reaction time t x Any other reaction time t before x-1 From the reaction time t x Between (t x -t x-1 ) the total amount of impurities in the fluid flowing into the reactor S IN , and the total amount of impurities S in the fluid discharged from the reactor OUT An impurity information acquisition unit that acquires the impurity information and the acquired S IN and S OUT Substituting into the above formula (5), the reaction time t x The porosity ε of the solid catalyst layer in the reactor x and a porosity derivation unit for deriving the obtained μ, u, ρ, and ε x The calculated pressure drop is calculated by substituting the above into the equation for calculating the pressure drop based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the void ratio of the solid catalyst layer in the reactor, and the calculated pressure drop is ΔP cal Derive ΔP cal The derived part and the obtained ΔP cal Substituting into the above formula (6), the reaction time t x The estimated pressure drop in the reactor at sim A pressure loss estimate deriving unit for deriving the pressure loss estimate ΔP sim and an output unit that outputs the signal.

[0132] The pressure loss estimation derivation device of this embodiment further calculates the reaction time t x Reaction temperature T t(x) A temperature information acquisition unit acquires the temperature information, t(x) and the coking threshold T B The relationship between t(x) >T B When the above condition is satisfied, the porosity ε of the solid catalyst layer in the reactor is x In the void ratio derivation part for deriving the above, the above S is added to the above formula (5-1) instead of the above formula (5). IN , the above S OUT , said T B , and T t(x) Substituting the above reaction time t xThe porosity ε of the solid catalyst layer in the reactor x It is preferable to derive

[0133] Specifically, as shown in FIG. 3, the pressure loss estimation derivation device 10 of this embodiment has an acquisition unit 11, a computer main body 14 that processes information from the acquisition unit 11, and an output unit 20 that outputs information processed in the computer main body 14 (an estimated value of the pressure loss in the reactor) to the outside.

[0134] The acquisition unit 11 receives predetermined information input by a reaction operator and transmits the information acquired by this input to the computer 14. The acquisition unit 11 of this embodiment acquires a time t x a fluid information acquiring unit 12 for acquiring a viscosity μ of the fluid, a linear velocity u of the fluid, and a density ρ of the fluid at the reaction time t x Any other reaction time t before x-1 From the reaction time t x Between (t x -t x-1 ) the total amount of impurities in the fluid flowing into the reactor S IN , and the total amount of impurities S in the fluid discharged from the reactor OUT The impurity information acquisition unit 13 further acquires the reaction time t x Reaction temperature T t(x) It is preferable to provide a temperature information acquisition unit 19 that acquires temperature information.

[0135] Specifically, the fluid information acquisition unit 12 acquires the reaction time t x Viscosity μ of the fluid at (μ if the fluid is two-phase gas and liquid) L and μ G ), the linear velocity of the fluid u (if the fluid is gas and liquid, u L and u G ), and the density of the fluid, ρ (if the fluid is gas and liquid, ρ L and ρ G ) is obtained by the reaction operator entering it, and is transmitted to the computer main body 14. Specifically, the impurity information acquisition unit 13 acquires the reaction time t x Any other reaction time t before x-1 From the reaction time t x Between (t x -t x-1 ) the total amount of impurities in the fluid flowing into the reactor S IN , and the total amount of impurities S in the fluid discharged from the reactor OUT is obtained by the reaction operator entering it, and is transmitted to the computer main body 14. Specifically, the temperature information acquisition unit 19 acquires the reaction time t x Reaction temperature T t(x) is obtained by the reaction operator entering it, and is transmitted to the computer main body 14.

[0136] In this embodiment, the fluid information acquisition unit 12, the impurity information acquisition unit 13, and the temperature information acquisition unit 19 are configured by a common keyboard. The specific configurations of the fluid information acquisition unit 12, the impurity information acquisition unit 13, and the temperature information acquisition unit 19 are not limited, and although they are keyboards in this embodiment, they may be touch panels or the like. The fluid information acquisition unit 12, the impurity information acquisition unit 13, and the temperature information acquisition unit 19 may be configured separately and each may be independently connected to the computer main body 14. In addition, the fluid information acquisition unit 12, the impurity information acquisition unit 13, and the temperature information acquisition unit 19 may be configured to directly acquire each of the above information from a computer, an analysis device, or the like used for controlling the reactor, by wire or wirelessly.

[0137] The computer main body 14 is a so-called computer capable of processing various information. A predetermined program is installed in the computer main body 14, and the operation unit 15 is functionally configured by executing the program. Specifically, the operation unit 15 is functionally configured by executing the program to include a porosity derivation unit 16 and a ΔP cal A derivation section 17 and a pressure loss estimated value derivation section 18 are configured.

[0138] When the above information is input from the acquisition unit 11 to the computer main body 14, the porosity derivation unit 16 calculates the T t(x) and the coking threshold T B The relationship between t(x) ≦T B When the above formula (5) is satisfied, the above T t(x) and the coking threshold T B The relationship between t(x) >T B When the above formula (5-1) is satisfied, the porosity ε of the solid catalyst layer in the reactor is x Calculate ΔP cal When the above information is input from the acquisition unit 11 to the computer main body 14, the derivation unit 17 calculates ΔP from a formula for calculating pressure loss based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the void ratio of the solid catalyst layer in the reactor. cal Derive ΔP cal In the outlet 17, when the fluid is one phase of gas or liquid, ΔP cal (ΔP1 cal ) can be derived. Also, ΔP cal In the outlet 17, when the fluid is two-phase, that is, gas and liquid, ΔP cal (ΔP2 cal The pressure loss estimate deriving unit 18 can derive the ΔP cal ΔP derived by the derivation unit 17 cal From the above formula (6), the reaction time t x Estimated pressure loss ΔP sim Derive.

[0139] In addition, the porosity derivation section 16, ΔP cal It is preferable that the derivation unit 17 and the pressure loss estimated value derivation unit 18 cooperate to have a function of deriving the tuning parameter α in the formula (5), the tuning factors β and γ in the formula (5-1), and the tuning factor σ in the formula (6) by the method already explained in the section on the pressure loss estimation method.

[0140] The calculation unit 15 outputs the calculation result obtained as described above based on the information input by the reaction operator to the output unit 20 as an estimated value of pressure loss.

[0141] The output unit 20 receives the calculation results (estimated values ​​of pressure loss in the reactor) output by the computer main body 14 (more specifically, the calculation unit 15) and outputs them to the outside. The output unit 20 in this embodiment is configured by a display unit such as a CRT display, a liquid crystal display, or a PDP, but is not limited to this and may be configured to output to a printing unit such as a printer, or other devices (for example, a computer used for controlling the hydrotreating reaction of heavy hydrocarbon oil, etc.). The output unit 20 may also be a combination of these.

[0142] The pressure loss estimation deriving device 10 of this embodiment may be a device that derives only an estimated value of the pressure loss in the reactor when the fluid is a single phase of gas or liquid, or may be a device that derives only an estimated value of the pressure loss in the reactor when the fluid is a two-phase fluid of gas and liquid, or may be a device that derives both an estimated value of the pressure loss in the reactor when the fluid is one phase and an estimated value of the pressure loss in the reactor when the fluid is two phases.

[0143] In the case of an apparatus that derives both an estimated value of the pressure drop in the reactor when the fluid is one phase and an estimated value of the pressure drop in the reactor when the fluid is two phases, it is preferable that the apparatus is provided with a fluid phase number information acquisition unit (not shown) that acquires information on the number of phases of a fluid by having a reaction operator input whether the fluid is one phase or two phases in acquisition unit 11.

[0144] The fluid phase number information is transmitted to the computer body 14, whereby ΔP cal An equation for calculating the pressure drop used in the outlet 17 is appropriately selected depending on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the void fraction of the solid catalyst layer in the reactor.

[0145] Each component of the pressure loss estimation deriving device 10 may be configured by hardware logic, or may be realized by software using a CPU as follows.

[0146] That is, the pressure loss estimation derivation device 10 includes a CPU (central processing unit) that executes instructions of a control program that realizes each function, a ROM (read only memory) that stores the program, a RAM (random access memory) that expands the program, and a storage device (recording medium) such as a memory that stores the program and various data. The object of the present invention can also be achieved by supplying a recording medium on which a program code (executable program, intermediate code program, source program) of the control program of the pressure loss estimation derivation device 10, which is software that realizes the above-mentioned functions, is recorded in a computer-readable manner to the pressure loss estimation derivation device 10, and having the computer (or CPU or MPU) read and execute the program code recorded in the recording medium.

[0147] Examples of the recording medium that can be used include tape systems such as magnetic tape and cassette tape, disk systems including magnetic disks such as flexible disks and hard disks and optical disks such as CD-ROM / MO / MD / DVD / CD-R, card systems such as IC cards (including memory cards) / optical cards, and semiconductor memory systems such as mask ROM / EPROM / EEPROM / flash ROM.

[0148] The pressure loss estimation derivation device 10 may be configured to be connectable to a communication network, and the program code may be supplied via the communication network. The communication network is not particularly limited, and may be, for example, the Internet, an intranet, an extranet, a LAN, ISDN, VAN, a CATV communication network, a virtual private network, a telephone line network, a mobile communication network, a satellite communication network, or the like. The transmission medium constituting the communication network is not particularly limited, and may be, for example, a wired medium such as IEEE1394, USB, power line carrier, cable TV line, telephone line, or ADSL line, or may be a wireless medium such as infrared light such as IrDA or a remote control, Bluetooth (registered trademark), 802.11 wireless, HDR, a mobile phone network, a satellite line, or a terrestrial digital network. The present invention may also be realized in the form of a carrier wave or a data signal string in which the program code is embodied by electronic transmission. EXAMPLES

[0149] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0150] [Measurement of metal impurity concentrations in heavy hydrocarbon oils] The metal impurity concentrations in the heavy hydrocarbon oil were measured by ICP-OES. Specifically, the metal-equivalent concentrations of Ni, V, and Fe in the heavy hydrocarbon oil before it flowed into the reactor, and the metal-equivalent concentrations of Ni, V, and Fe in the heavy hydrocarbon oil after it flowed out of the reactor were measured by ICP-OES.

[0151] [Measurement of density and viscosity of heavy hydrocarbon oil] The density of the heavy hydrocarbon oil was obtained by correcting the density converted to 15°C measured in accordance with JIS K2249 "Crude oil and petroleum products - Density test method and density, mass and volume conversion table" by the reaction temperature. The viscosity of heavy hydrocarbon oil was obtained by multiplying the result obtained in accordance with JIS K 2283 "Crude oil and petroleum products - Test method for kinematic viscosity and calculation method for viscosity index" by the density converted to 15°C measured in accordance with JIS K2249 "Crude oil and petroleum products - Test method for density and density, mass and volume conversion table", and then converting it into temperature.

[0152] [Measurement of density and viscosity of hydrogen] The density of hydrogen was obtained by correcting the density corresponding to the composition obtained by composition analysis using gas chromatography for temperature and pressure. The viscosity of hydrogen was obtained by inputting the composition analysis results obtained by gas chromatography into a process simulator and calculating it.

[0153] The reaction temperature was measured by a thermometer in the reactor, and the maximum temperature was adopted.

[0154] [Example 1] Four different types of heavy hydrocarbon oil hydrotreating catalysts A to D (molybdenum-nickel catalysts in which molybdenum and nickel are supported on γ-alumina, shape: four-leaf clover) were packed into a reactor to form four solid catalyst layers. At this time, the bed height H (m) of each solid catalyst layer was measured using a scale. The bed height H of each solid catalyst layer and the cross-sectional area (m) of the reactor (cylindrical tubular reactor) were 2 ) to obtain the packed volume V of each solid catalyst layer. cat (m 3 ) was calculated. In addition, the packed volume V cat and filling weight W cat (kg), BD=W cat / V cat Calculate the packing density BD (kg / m 3 The packing density BD of each solid catalyst layer and the true density ρ cat (kg / m 3 ), and the pore volume PV (m 3 / kg, ε0=1-(BD×(1 / ρ cat+PV) was calculated, and ε0 of each solid catalyst layer was calculated. The true density of the solid catalyst was determined by the pycnometer method (liquid phase method). The pore volume of the solid catalyst was measured by mercury intrusion porosimeter (MICROMERITICS AUTO-PORE 9200: manufactured by Shimadzu Corporation) as the mercury intrusion device.

[0155] From the average major axis and the average minor axis of each solid catalyst, the spherical diameter dp was calculated by the above formula (8-3) assuming that each solid catalyst was a sphere. Table 1 shows dp, H, ε0 and layer structures of hydrotreating catalysts A to D. In Table 1, zone 1 is the reactor inlet side, and zone 4 is the reactor outlet side.

[0156] [Table 1]

[0157] Heavy hydrocarbon oil heated to the reaction temperature and hydrogen were introduced from the top of the reactor, and hydrotreating was carried out under the following conditions.

[0158] Reaction conditions: Reaction temperature: 377°C Pressure (hydrogen partial pressure): 10.3MPa Liquid space velocity ;0.2h -1 Linear speed (oil); 0.0043m / s Linear speed (hydrogen): 0.067 m / s Hydrogen / oil ratio: 860m 3 / m 3 Sulfur content in produced oil: 0.30 mass%

[0159] Feedstock properties: Oil type: Middle Eastern crude oil atmospheric distillation residue Density (15℃); 0.9616g / cm 3 Sulfur component: 2.97% by mass Vanadium: 15 ppm Nickel: 31 ppm Iron: 18 ppm Kinematic viscosity; 369mm 3 / s(50℃) Produced oil properties: Vanadium; 6 ppm Nickel; 9 ppm Iron: 13 ppm The sulfur content was measured in accordance with JIS K2541 "Crude petroleum and petroleum products - Determination of sulfur content." The above reaction conditions are average values ​​over the entire reaction period.

[0160] After 24 hours from the start of the reaction, the concentration of metal impurities in the heavy hydrocarbon oil before it flowed into the reactor was measured, and the product of this and the total amount of heavy hydrocarbon oil that flowed into the reactor during the 24 hours was calculated to obtain the total amount of impurities S in the heavy hydrocarbon oil that flowed into the reactor during the 24 hours from the start of the reaction. IN The total amount of impurities in the heavy hydrocarbon oil that flowed out of the reactor during the 24-h period from the start of the reaction, S, was obtained by measuring the concentration of metal impurities in the heavy hydrocarbon oil that flowed out of the reactor 24 hours after the start of the reaction and calculating the product of this and the total amount of heavy hydrocarbon oil that flowed out of the reactor during the 24-h period. OUT (kg / 24h) was obtained. In the above formula (1-B), ε0 and S of the solid catalyst layer in each zone are IN , S OUT and the ε 24h α const The above ε 24h The density, linear velocity, and viscosity of the heavy hydrocarbons after 24 hours, the density, linear velocity, and viscosity of hydrogen, and the dp and H of the catalyst are substituted into the above equations (9) to (14) to calculate the pressure loss ΔP after 24 hours in the solid catalyst layer in each zone. cal(n) (ΔP2 cal(n) ) to α const The pressure drop of the solid catalyst layer in the first to fourth zones was calculated as a function of ΔP cal (ΔP2 cal ) to α const The calculated pressure drop of the solid catalyst layer was calculated as a function of ΔPcal (ΔP2 cal ) into the above formula (2) to obtain the estimated pressure drop ΔP sim (ΔP2 sim ) to α const and as a function of σ. After that, the above pressure loss estimation work was performed every 24 hours, and the estimated pressure loss value ΔP sim (ΔP2 sim ) to α const The actual pressure drop ΔP and the estimated pressure drop ΔP at 15 points in the reaction from the start of the reaction were obtained as a function of σ. sim ΔP (ave) , ΔP sim(ave) Ratio ΔP (ave) / ΔP sim(ave) so that the value of α approaches 1. const , σ was adjusted, and α const It was found that when = 0.0065 and σ = -0.19, the measured values ​​and estimated values ​​matched well.

[0161] α const The above pressure drop estimation work was carried out every 24 hours with σ = 0.0065 and σ = -0.19. Figure 4 shows a graph of the actual measured values ​​(actual values) and estimated values ​​of pressure drop against the reaction time.

[0162] As shown in 4, up until 269 days, α const , the value of σ was not changed, but ΔP / ΔP sim The average value of was 1.06, and the pressure loss was estimated with a very high degree of accuracy. sim The value of gradually increased (after 264 days: 1.09, after 265 days: 1.16, after 266 days: 1.20, after 267 days: 1.24, after 268 days: 1.28, after 269 days: 1.30), and α const The value of was changed to 0.03 (σ was unchanged), and the reaction was carried out for a total of approximately 300 days. The measured and estimated values ​​of pressure drop during the entire reaction period were in good agreement. sim The mean (estimated value) was 1.06.

[0163] [Example 2] At the actual scale, the coking threshold T B According to the acquisition method 2, B When we searched for T B The coking threshold T B In acquisition method 2, line 1 was y=0.0002x+0.0372, and line 2 was y=0.0163x-5.9256. Therefore, the reaction temperature T t Until the temperature exceeds 370°C, the estimated pressure loss ε calculated by the above formula (1) in the method of Example 1 is x The estimated pressure loss was calculated using the following formula (α=0.0065, σ=-0.19, as in Example 1). After 101 days, the reaction temperature T t becomes 371℃, T B The temperature exceeded 370°C. The metal impurity concentration in the heavy hydrocarbon oil before it flows into the reactor after 101 days is measured, and the product of this and the total amount of heavy hydrocarbon oil that flows into the reactor between 100 days and 101 days is calculated to obtain the total amount of impurities S in the heavy hydrocarbon oil that flows into the reactor between 100 days and 101 days. IN The total amount of impurities in the heavy hydrocarbon oil that flowed out of the reactor between 100 days and 101 days was calculated by measuring the concentration of metal impurities in the heavy hydrocarbon oil that flowed out of the reactor between 100 days and 101 days, and calculating the product of this concentration and the total amount of heavy hydrocarbon oil that flowed out of the reactor between 100 days and 101 days. OUT (kg / 24h) was obtained. In the above formula (1-1), ε of the solid catalyst layer of each zone is 100日 , and S IN , S OUT ,R,T B , T t(x) and the ε 101日 were obtained as functions of β and γ. Here, in accordance with the above-mentioned setting method 2 of tuning factors β and γ, β=1 was substituted as a temporary value, and the above ε 101日 was obtained as a function of γ. 101日The density, linear velocity, and viscosity of the heavy hydrocarbons, the density, linear velocity, and viscosity of hydrogen, and the dp and H of the catalyst after 101 days are substituted into the above equations (9) to (14) to calculate the pressure loss ΔP after 101 days in the solid catalyst layer of each zone. cal(n) was obtained as a function of γ. Next, the calculated pressure drop of the solid catalyst layer in zones 1 to 4 was summed up to obtain the calculated pressure drop of the entire solid catalyst layer, ΔP cal was obtained as a function of γ. The calculated pressure drop of the all-solid catalyst layer, ΔP cal Substituting this into equation (2), the estimated pressure drop in the all-solid catalyst layer ΔP sim was obtained as a function of γ. The actual pressure loss ΔP after 101 days and the above ΔP sim ΔP=ΔP sim When calculated, γ was 340. After that, the above pressure loss estimation work was performed every 24 hours, and ΔP / ΔP was calculated at 15 points. sim Since the values ​​fell within the range of 0.5 to 1.5, we set β = 1 and γ = 340 and continued the pressure estimation work. Figure 5 shows a graph of the measured and estimated pressure drop versus reaction time.

[0164] As shown in FIG. 5, the measured and estimated values ​​of pressure drop during the entire reaction period were in good agreement. In addition, there was no need to change the tuning parameter α, as in Example 1. During this period, ΔP (measured value) / ΔP sim The mean (estimated value) was 1.01. [Explanation of symbols]

[0165] 10... Pressure loss estimation derivation device, 11... Acquisition section, 12... Fluid information acquisition section, 13... Impurity information acquisition section, 14... Calculator, 15... Calculation section, 16... Porosity derivation section, 17... ΔP cal Derivation section, 18...pressure loss estimated value derivation section, 19...temperature information acquisition section, 20...output section

Claims

1. In a fixed bed flow reaction in which a gas or liquid one-phase fluid, or a gas and liquid two-phase fluid, is passed through a reactor packed with a solid catalyst, any reaction time t ｘ A method for estimating a pressure drop in the reactor, comprising the steps of: The reaction time t ｘ obtaining the viscosity μ of the fluid, the linear velocity u of the fluid, and the density ρ of the fluid at The reaction time t ｘ Any other reaction time t before ｘ－１ From the reaction time t ｘ Between (t ｘ -t ｘ－１ ) the total amount of impurities in the fluid flowing into the reactor S ＩＮ , and the total amount of impurities S in the fluid flowing out of the reactor ＯＵＴ and obtaining Acquired S ＩＮ and S ＯＵＴ Substituting into the following formula (1), the reaction time t ｘ The porosity ε of the solid catalyst layer in the reactor ｘ and deriving The obtained μ, u, ρ, and ε ｘ is substituted into the equation for calculating pressure drop based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the porosity of the solid catalyst layer in the reactor, and the calculated pressure drop value ΔP ｃａｌ Derive The obtained ΔP ｃａｌ is substituted into the following formula (2), and the reaction time t ｘ The estimated pressure drop ΔP in the reactor ｓｉｍ A method for estimating a pressure drop in a reactor, comprising: The method for estimating pressure drop in a reactor, wherein a formula for calculating the pressure drop based on the void ratio of the solid catalyst layer in the reactor is the Ergun formula, the Blake-Kozeny formula, the Burke-Plummer formula, the Kozeny-Carman formula, or the Fanning formula when the fluid is a single phase of gas or liquid, and is the Ergun-Larkins formula when the fluid is a two-phase of gas and liquid. [0010] (In formula (1), ε ｘ－１ is the reaction time t ｘ－１ is the void ratio of the solid catalyst layer in the reactor, and α is the tuning factor.) [0025] (In formula (2), σ is a tuning factor.)

2. Furthermore, the reaction time t ｘ Reaction temperature T ｔ（ｘ） obtaining a Said T ｔ（ｘ） and the coking threshold T, which is the temperature at which coke forms and begins to deposit on the solid catalyst layer. Ｂ The relationship between ｔ（ｘ） >T Ｂ When the above condition is satisfied, the porosity ε of the solid catalyst layer in the reactor is ｘ In the step of deriving the formula (1), the following formula (1-1) is used instead of the formula (1): ＩＮ , the S ＯＵＴ , said T Ｂ and the T ｔ（ｘ） Substituting the above, the reaction time t ｘ The porosity ε of the solid catalyst layer in the reactor ｘ The method for estimating pressure drop in a reactor according to claim 1, further comprising deriving: [0030] (In formula (1-1), R is a gas constant, and β and γ are tuning factors.)

3. In a fixed bed flow reaction in which a gas or liquid one-phase fluid, or a gas and liquid two-phase fluid, is passed through a reactor packed with a solid catalyst, any reaction time t ｘ A reaction method for controlling a pressure drop in the reactor, comprising: The reaction time t ｘ Any other reaction time t before ｘ－１ From the reaction time t ｘ Between (t ｘ -t ｘ－１ ) the total amount of impurities in the fluid flowing into the reactor S ＩＮ , and the total amount of impurities S in the fluid flowing out of the reactor ＯＵＴ and obtaining Acquired S ＩＮ and S ＯＵＴ Substituting into the following formula (3), the reaction time t ｘ The porosity ε of the solid catalyst layer in the reactor ｘ and deriving The desired pressure loss ΔP in the reactor ｘ Substituting into the following formula (4), ΔP ｃａｌ Derive The obtained ΔP ｃａｌ and the ε ｘ Substituting the above into the equation for calculating the pressure drop based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the void fraction of the solid catalyst layer in the reactor, A reaction method for controlling a pressure drop in a reactor, comprising: adjusting a viscosity μ of a fluid, a linear velocity u of the fluid, and a density ρ of the fluid so that the equation for calculating the pressure drop is satisfied; A reaction method for controlling pressure drop in a reactor, wherein a formula for calculating the pressure drop based on the void ratio of the solid catalyst layer in the reactor is the Ergun formula, the Blake-Kozeny formula, the Burke-Plummer formula, the Kozeny-Carman formula, or the Fanning formula when the fluid is a single phase of gas or liquid, and is the Ergun-Larkins formula when the fluid is a two-phase of gas and liquid. [0045] (In formula (3), ε ｘ－１ is the reaction time t ｘ－１ is the void ratio of the solid catalyst layer in the reactor, and α is the tuning factor.) [0050] (In equation (4), σ is a tuning factor.)

4. Furthermore, the reaction time t ｘ Reaction temperature T ｔ（ｘ） obtaining a Said T ｔ（ｘ） and the coking threshold T Ｂ The relationship between ｔ（ｘ） >T Ｂ When the above condition is satisfied, the porosity ε of the solid catalyst layer in the reactor is ｘ In the step of deriving, instead of the formula (3), the following formula (3-1) is used to calculate the S ＩＮ , the S ＯＵＴ , said T Ｂ and the T ｔ（ｘ） Substituting the above, the reaction time t ｘ The porosity ε of the solid catalyst layer in the reactor ｘ The reaction method for controlling pressure drop in a reactor according to claim 3, wherein [006] (In formula (3-1), R is a gas constant, and β and γ are tuning factors.)

5. In a fixed bed flow reaction in which a gas or liquid one-phase fluid, or a gas and liquid two-phase fluid, is passed through a reactor packed with a solid catalyst, any reaction time t ｘ The pressure loss estimation deriving device in the reactor, The reaction time t ｘ a fluid information acquiring unit that acquires a viscosity μ of the fluid, a linear velocity u of the fluid, and a density ρ of the fluid; The reaction time t ｘ Any other reaction time t before ｘ－１ From the reaction time t ｘ Between (t ｘ -t ｘ－１ ) the total amount of impurities in the fluid flowing into the reactor S ＩＮ , and the total amount of impurities S in the fluid flowing out of the reactor ＯＵＴ An impurity information acquisition unit that acquires Acquired S ＩＮ and S ＯＵＴ Substituting into the following formula (5), the reaction time t ｘ The porosity ε of the solid catalyst layer in the reactor ｘ A porosity derivation unit that derives The obtained μ, u, ρ, and ε ｘ is substituted into the equation for calculating pressure drop based on the viscosity of the fluid, the linear velocity of the fluid, the density of the fluid, and the porosity of the solid catalyst layer in the reactor, and the calculated pressure drop value ΔP ｃａｌ Derive ΔP ｃａｌ A derivation portion; The obtained ΔP ｃａｌ is substituted into the following formula (6), and the reaction time t ｘ The estimated pressure drop ΔP in the reactor ｓｉｍ A pressure loss estimate deriving unit that derives The estimated pressure loss ΔP ｓｉｍ an output unit that outputs A pressure loss estimation device comprising: The pressure loss estimation deriving device, wherein an equation for calculating the pressure loss based on the porosity of the solid catalyst layer in the reactor is the Ergun equation, the Blake-Kozeny equation, the Burke-Plummer equation, the Kozeny-Carman equation, or the Fanning equation when the fluid is a single phase of gas or liquid, and is the Ergun-Larkins equation when the fluid is a two-phase of gas and liquid. [0070] (In formula (5), ε ｘ－１ is the reaction time t ｘ－１ is the void ratio of the solid catalyst layer in the reactor, and α is the tuning factor.) [0080] (In equation (6), σ is a tuning factor.)

6. Furthermore, the reaction time t ｘ Reaction temperature T ｔ（ｘ） A temperature information acquisition unit that acquires Said T ｔ（ｘ） and the coking threshold T, which is the temperature at which coke forms and begins to deposit on the solid catalyst layer. Ｂ The relationship between ｔ（ｘ） >T Ｂ When the above condition is satisfied, the porosity ε of the solid catalyst layer in the reactor is ｘ In the porosity derivation part for deriving the above formula (5), the following formula (5-1) is used to calculate the above S ＩＮ , the S ＯＵＴ , said T Ｂ , and T ｔ（ｘ） Substituting the above, the reaction time t ｘ The porosity ε of the solid catalyst layer in the reactor ｘ The pressure loss estimation deriving device according to claim 5, wherein the pressure loss estimation deriving device derives the following: [0090] (In formula (5-1), R is a gas constant, and β and γ are tuning factors.)

7. A pressure loss estimation program for causing a computer to function as a fluid information acquisition means in the fluid information acquisition unit, an impurity information acquisition means in the impurity information acquisition unit, a porosity derivation means in the porosity derivation unit, a ΔP cal derivation means in the ΔP cal derivation unit, a pressure loss estimate derivation means in the pressure loss estimate derivation unit, and an output means in the output unit of the pressure loss estimation derivation device of claim 5 or 6.

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