Information processing method, reaction temperature calculation device, reaction temperature calculation program, and non-temporarily readable recording medium for computers

Abstract

To provide an information processing method capable of estimating a reaction temperature required to achieve predetermined reaction conditions regarding a hydrotreating reaction of feedstock oil containing heavy coker cracked gas oil; a reaction temperature calculation device capable of estimating the reaction temperature; a reaction temperature calculation program for causing a computer to function as the reaction temperature calculation device; and a non-temporary readable recording medium for a computer that stores the program.SOLUTION: There is provided an information processing method, comprising: an information acquisition step of acquiring information on feedstock oil containing heavy coker cracked gas oil, information on produced oil, and information on operating conditions after a predetermined time is passed since a reaction is started; a deterioration degree calculation step of calculating a deterioration degree of a catalyst using a deterioration function based on the acquired information; and a reaction temperature calculation step of calculating information regarding the feedstock oil, information regarding the produced oil, and a reaction temperature required to satisfy the operating conditions, based on the deterioration degree of the catalyst.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an information processing method, a reaction temperature calculation device, a reaction temperature calculation program, and a non-temporarily readable recording medium for a computer. [Background technology]

[0002] The High Coker Gas Oil Section (HS) of the Coker Distillate HDS Unit (DHU) is a hydrogenation unit that primarily uses heavy coker cracked gas oil, which is the heavy oil fraction of coker cracked oil, as its feedstock. It is operated with the aim of reducing the sulfur content of the desulfurized heavy coker cracked gas oil, which is used as feedstock for the fluid catalytic cracking unit.

[0003] In the hydrogenation treatment of heavy coker-cracked diesel fuel, coke is produced as a by-product, and the accumulation of coke on the hydrogenation catalyst causes the activity of the hydrogenation catalyst to decrease over time. Furthermore, heavy coker-cracked diesel fuel contains silicon derived from the defoaming agent added to the coker upstream of the DHU-HS unit. The accumulation of these compounds on the hydrogenation catalyst also reduces the catalyst's activity over time. Therefore, to maintain the sulfur content in the resulting oil below a certain level and counteract the decrease in the hydrogenation catalyst's activity due to coke and silicon accumulation, the reaction temperature must be increased during operation.

[0004] In setting the reaction temperature, if the reaction temperature is too high, the catalyst activity will decrease, making it impossible to achieve the predetermined operating time (number of days) and reducing productivity. On the other hand, if the reaction temperature is too low, the decrease in catalyst activity will be mitigated, resulting in excess capacity before the predetermined operating time. If this excess capacity is not utilized, productivity will decrease. Therefore, a method for accurately estimating the predetermined reaction conditions (temperature, rate of reaction) is desired.

[0005] In the field of crude oil refining, various studies have been conducted on methods for accurately estimating the optimal reaction temperature. For example, Patent Document 1 discloses a method for estimating the reaction temperature required after switching to a feedstock oil containing atmospheric distilled diesel fuel in the hydrogenation treatment of feedstock oil containing atmospheric distilled diesel fuel with different properties, based on information regarding the properties and operating conditions of the atmospheric distilled diesel fuel before the switch, and information regarding the properties and operating conditions other than the reaction temperature of the atmospheric distilled diesel fuel after the switch. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 10-60455 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The method for estimating the reaction temperature described in Patent Document 1 focuses on the properties of the raw material oil and does not consider the decrease in the activity of the hydrogenation catalyst. Therefore, there is a need for a method to estimate the optimal reaction temperature while taking into account the decrease in the activity of the hydrogenation catalyst.

[0008] The present invention has been made in view of the above circumstances, and aims to provide an information processing method that can estimate the reaction temperature necessary to achieve predetermined reaction conditions in a hydrogenation reaction of feedstock oil containing heavy coker cracked light oil, a reaction temperature calculation device that can estimate the reaction temperature, a reaction temperature calculation program for causing a computer to function as the reaction temperature calculation device, and a non-temporarily readable recording medium for a computer storing the program. [Means for solving the problem]

[0009] To solve the above problems, the present invention has the following aspects. [1] An information processing method for a hydrogenation reaction of a feed oil containing heavy coker cracked light oil, comprising: an information acquisition step of acquiring information on the feed oil, the product oil, and the operating conditions after a predetermined time has elapsed since the start of the reaction; a degradation degree calculation step of calculating the degree of catalyst degradation using a degradation function based on the acquired information on the feed oil, the product oil, and the operating conditions; and a reaction temperature calculation step of calculating the reaction temperature necessary to satisfy the feed oil, the product oil, and the operating conditions based on the degree of catalyst degradation. [2] The information processing method according to [1], wherein the degradation function comprises a coke degradation function relating to the degradation of the catalyst due to coke deposition and a silicon degradation function relating to the degradation of the catalyst due to silicon deposition. [3] The information processing method according to [1] or [2], wherein the information relating to the raw material oil includes information relating to the sulfur concentration in the raw material oil, and the information relating to the produced oil includes information relating to the sulfur concentration in the produced oil. [4] The information processing method according to any one of [1] to [3], wherein the information relating to the operating conditions includes information relating to the partial pressure of hydrogen, information relating to the amount of catalyst charged, and information relating to the amount of feedstock supplied. [5] A reaction temperature calculation device comprising: an acquisition unit that acquires information on the raw material oil, information on the product oil, and information on the operating conditions after a predetermined time has elapsed since the start of the reaction, with respect to a hydrogenation reaction of a raw material oil containing heavy coker cracked light oil; an acquisition unit that calculates the degree of catalyst degradation using a degradation function based on the information on the raw material oil, the information on the product oil, and the information on the operating conditions acquired by the acquisition unit, and calculates the reaction temperature necessary to satisfy the information on the raw material oil, the information on the product oil, and the operating conditions based on the calculated degree of catalyst degradation. [6] The reaction temperature calculation apparatus according to [5], wherein the degradation function comprises a coke degradation function relating to the degradation of the catalyst due to coke deposition and a silicon degradation function relating to the degradation of the catalyst due to silicon deposition. [7] The reaction temperature calculation apparatus according to [5] or [6], wherein the information relating to the raw material oil includes information relating to the sulfur concentration in the raw material oil, and the information relating to the produced oil includes information relating to the sulfur concentration in the produced oil. [8] The reaction temperature calculation apparatus according to any one of [5] to [7], wherein the information relating to the operating conditions includes information relating to the partial pressure of hydrogen, information relating to the amount of catalyst filled, and information relating to the amount of feedstock supplied. [9] A reaction temperature calculation program for causing a computer to function as a reaction temperature calculation device as described in any one of items [5] to [8].

[10] [9] A non-temporary-readable recording medium of a computer storing the programs described therein. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide an information processing method that can estimate the reaction temperature necessary to achieve predetermined reaction conditions in a hydrogenation reaction of feedstock oil containing heavy coker cracked light oil, a reaction temperature calculation device that can estimate the reaction temperature, a reaction temperature calculation program for causing a computer to function as the reaction temperature calculation device, and a non-temporarily readable recording medium for a computer storing the program. [Brief explanation of the drawing]

[0011] [Figure 1] This is a flowchart of an information processing method according to one embodiment. [Figure 2] This is a flowchart of an information processing method according to one embodiment. [Figure 3] This is a flowchart of an information processing method according to one embodiment. [Figure 4] This is a block diagram of the configuration of a reaction temperature calculation device according to one embodiment. [Modes for carrying out the invention]

[0012] The embodiments of the present invention will be described in detail below, but the following description is merely one 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.

[0013] Information Processing Methods The information processing method of this embodiment includes an information acquisition step (S1 in Figure 1) for acquiring information about the feedstock oil, the product oil, and the operating conditions at a predetermined time after the start of the reaction with respect to the hydrogenation reaction of feedstock oil containing heavy coker cracked light oil; a degradation degree calculation step (S2 in Figure 1) for calculating the degree of catalyst degradation using a degradation function based on the acquired information about the feedstock oil, the product oil, and the operating conditions; and a reaction temperature calculation step (S3 in Figure 1) for calculating the reaction temperature necessary to satisfy the feedstock oil, the product oil, and the operating conditions based on the degree of catalyst degradation. Each step will be described below. Note that each of the steps shown below is performed by, for example, the reaction temperature calculation device 1 of this embodiment. For example, S1 is performed by the acquisition unit 11, and S2 and S3 are performed by the calculation unit 13 in the computer body 12.

[0014] ≪Information Acquisition Steps≫ The information acquisition step of this embodiment is to acquire information about the feedstock oil, the produced oil, and the operating conditions at a predetermined time after the start of the reaction. The predetermined time after the start of the reaction is, for example, any t days after the start of the reaction. t can be an integer or a decimal; for example, if t is 0.5, it means 12 hours after the start of the reaction. Furthermore, t days can be in the past, present, or future from the time the information processing method of this embodiment is implemented. For example, if the information processing method of this embodiment is implemented 2 days after the start of the reaction, and t is 4, then the reaction temperature 2 days later (in the future) will be estimated.

[0015] (Information regarding raw materials) Examples of information regarding the raw material oil include information regarding its composition. Examples of information regarding the raw material oil composition include information regarding the sulfur concentration and silicon concentration in the raw material oil.

[0016] Information regarding the sulfur concentration in the raw material oil can be obtained using sulfur concentration measurement methods known in this field, such as ultraviolet fluorescence spectroscopy or wavelength-dispersive X-ray fluorescence spectroscopy. Furthermore, the sulfur concentration in the raw material oil can be controlled by changing the raw material oil. It is preferable that the information regarding the sulfur concentration in the raw material oil be a set value; that is, the sulfur concentration of the raw material oil intended for use can be used.

[0017] Information regarding the silicon concentration in the raw material oil can be obtained using silicon concentration measurement methods known in this field, such as ICP-MS or X-ray fluorescence analysis. Furthermore, the silicon concentration in the raw material oil can be controlled by changing the raw material oil. It is preferable that the information regarding the silicon concentration in the raw material oil be a set value; that is, the silicon concentration of the raw material oil intended for use can be used.

[0018] (Information on refined oils) Examples of information regarding the generated oil include information about its composition. Examples of information regarding the generated oil's composition include information about its sulfur and silicon concentrations.

[0019] Information regarding the sulfur concentration in the generated oil can be obtained in the same way as in the case of the raw material oil described above. In this embodiment, it is preferable that the information regarding the sulfur concentration in the generated oil is a set value. That is, the sulfur concentration of the target generated oil can be used.

[0020] Information regarding the silicon concentration in the generated oil can be obtained in the same way as in the case of the raw material oil described above. In this embodiment, it is preferable that the information regarding the silicon concentration in the generated oil is a set value. That is, the silicon concentration of the target generated oil can be used. Note that if the sulfur concentration in the generated oil is kept constant, the silicon concentration in the generated oil will also be constant.

[0021] (Information regarding driving conditions) Examples of information regarding operating conditions include information on hydrogen partial pressure, catalyst charge amount, feed oil supply amount, and hydrogen supply amount. For example, information regarding operating conditions may include at least one of the following: information on hydrogen partial pressure, catalyst charge amount, feed oil supply amount, and hydrogen supply amount. In particular, it is preferable that information regarding operating conditions includes information on hydrogen partial pressure, catalyst charge amount, and feed oil supply amount, and more preferably that it includes all of the following: information on hydrogen partial pressure, catalyst charge amount, feed oil supply amount, and hydrogen supply amount. It is also preferable that the operating conditions include information on time, such as the time elapsed after any number of days since the start of the reaction. Furthermore, it is preferable that the operating conditions include information on the measured value of the reaction temperature.

[0022] Information regarding hydrogen partial pressure, catalyst loading amount, feedstock supply amount, and hydrogen supply amount can be determined by methods known in this art. Information regarding hydrogen partial pressure, catalyst loading amount, feedstock supply amount, and hydrogen supply amount can be controlled in the hydrogenation reaction of feedstock oil containing heavy coker cracked diesel fuel. Information regarding operating conditions is preferably set values; that is, planned operating conditions are used.

[0023] ≪Steps for calculating the degree of deterioration≫ The degradation degree calculation step of this embodiment is a step of calculating the degradation degree of the catalyst using a degradation function based on the acquired information regarding the raw material oil, the generated oil, and the operating conditions.

[0024] <Degree of deterioration> The degree of deterioration is expressed by the following formula 1. Φ=k t / k0 expression 1 In the above equation 1, k0 is the reaction rate constant of the catalyst at 0 days after the reaction (i.e., at the start of the reaction), and k t is the reaction rate constant of the catalyst after t days of any given reaction. Note that k0 and k t The temperature T will be described later. SOR This is the reaction rate constant in [the context].

[0025] In this embodiment, the degree of catalyst degradation can be calculated using a degradation function based on the acquired information regarding the raw material oil, the generated oil, and the operating conditions.

[0026] <Degradation function> The degradation function is a function used to calculate the degree of catalyst degradation. In this embodiment, it is preferable that the degradation function consists of a coke degradation function related to the degradation of the catalyst due to coke deposition and a silicon degradation function related to the degradation of the catalyst due to silicon deposition. While there are no particular limitations on such a degradation function, for example, the degradation function represented by Equation 2 below can be given as an example.

[0027] Φ = Φ C Φ Si formula 2 In the above formula 2, Φ C Φ is the Coke degradation function, Si This is the silicon degradation function.

[0028] The following explains the Coke degradation function and the silicon degradation function.

[0029] <Coke Degradation Function 1> The coke deterioration function is not particularly limited as long as it is a function capable of calculating the degree of deterioration related to the coke deterioration of the catalyst. For example, the coke deterioration function 1 represented by the following formula 3 can be cited as an example.

[0030] Φ C = exp(−Dt) Formula 3 In the above formula 3, D is the deterioration coefficient due to coke of the active species of the catalyst, and t is the number of days elapsed since the start of the reaction (days).

[0031] D can be obtained by the following formula (4). Formula (4) is a formula capable of calculating the deterioration coefficient due to coke of the active species of the catalyst by specific parameters, and is a formula first discovered by the inventors of the present application based on the operation results of actual machines and the like.

[0032]

Number

[0033] In this specification, the "required temperature" means the reaction temperature required to achieve predetermined reaction conditions. That is, the required temperature on the 0th day means the reaction temperature required to achieve the reaction conditions of the above S F , S P , LHSV, and P at the start of the reaction.

[0034] In this specification, "reference hydrogen partial pressure" refers to the standard pressure under the actual reaction conditions. It is determined as the average value of the reaction pressure used when determining the hydrogen partial pressure coefficient a, as described later.

[0035] In this specification, "reference reaction temperature" refers to the T obtained within the range of typical operating conditions that may actually be used. SOR It represents the average value.

[0036] In the above formula 4, T SOR α represents the initial activity of the catalyst, and α represents the degradation rate of the catalyst. That is, T SOR A larger value for α indicates greater catalyst degradation, and this degradation behavior is reflected in the value of D.

[0037] In the above equation 4, (1 / S P n-1 -1 / S F n-1 The term represented by LHSV is the desulfurization reaction rate constant, and as mentioned above, S P S F When LHSV is set as the value and the system is operated under certain conditions, it becomes a constant. In the above equation 4, (P B / P) a The term represented by is a term that shows the dependence on the hydrogen partial pressure, and as mentioned above, when P is set as the value and the operation is performed under constant conditions, it becomes a constant. In equation 4 above, exp[Ec / R(1 / T B -1 / T SOR The term represented by ) is a term that shows temperature dependence and is a constant.

[0038] In the above formula 4, S F S P LHSV and P are values ​​substituted based on the information regarding the feed oil, the produced oil, and the operating conditions obtained in the information acquisition step described above. LHSV can be determined by dividing the feed oil supply rate (volume / hour) by the catalyst filling rate (volume).

[0039] As mentioned above, S F LHSV and P are parameters that can be controlled. Also, S P is the sulfur concentration of the target product oil. That is, according to formula 4 above, S F S P The degradation coefficient of the catalyst's active species due to coke can be calculated under the reaction conditions of LHSV and P. The method for determining n, which is the reaction order of the hydrogenation reaction of feedstock oil containing heavy coker cracked diesel fuel, will be described later.

[0040] (How to determine the basic degradation parameters of Coke) In the above formula 4, α, P B a, Ec, T B , T SORis a constant. Hereinafter, these parameters will be collectively referred to as "Basic Coke Degradation Parameter 1". Basic Coke Degradation Parameter 1 is a parameter determined according to the catalyst used, and may be determined while performing the reaction in the actual machine, or may be determined in advance on a bench scale based on the actual machine operating conditions. In this embodiment, it is preferable to determine it in advance on a bench scale based on the actual machine operating conditions. When using a feedstock oil containing heavy coker cracked light oil as the feedstock oil when determining the basic coke degradation parameter, the decrease in activity due to silicon deposition will be reflected in addition to the decrease in activity due to coke deposition. Therefore, it is preferable to use a feedstock oil that is substantially free of silicon when determining the basic coke degradation parameter. Substantially free of silicon means that the silicon concentration in the feedstock oil is less than 0.3 ppm by weight. The inventors of this application have found that the degradation of the catalyst due to coke deposition in the hydrogenation reaction of a feedstock oil containing heavy coker cracked light oil is almost the same as the degradation of the catalyst due to coke deposition in the hydrogenation reaction (indirect desulfurization reaction) of a feedstock oil containing vacuum distilled light oil obtained by vacuum distillation of atmospheric distillation residue. In other words, vacuum-distilled diesel fuel can be used as the raw material to determine the basic degradation parameters of coke. Hereafter, when "assumed actual operating conditions" are used to determine the parameters of the coke degradation function, the assumed actual operating conditions are those other than the silicon concentration, and the silicon concentration in the raw material is less than 0.3 ppm. The following are the basic degradation parameters P for Coke. B a, Ec, T B An example of how to determine this is shown below. The example shown below is a method (P) that is determined from the catalyst degradation behavior (change in reaction rate constant) analyzed from data obtained from the reaction in the actual machine described above, or from a bench-scale reaction based on the actual machine operating conditions. B a, Ec, T B This is how to determine it. Also, the basic degradation parameters of Coke, α, T SORTwo examples of how to determine these are shown, but the present invention is not limited to these. The first example is a method of determining (α and T) from the catalyst degradation behavior (change in reaction rate constant) analyzed from data obtained from the reaction in the actual machine described above, or from a bench-scale reaction based on the actual machine operating conditions. SOR Method 1) for determining the first example is a method (α and T) that is determined from the reaction temperature profile analyzed from data obtained from the reaction in the actual machine or from a bench-scale reaction based on the actual machine operating conditions described above. SOR Method 2) for finding it.

[0041] (P B a, Ec, T B How to find it) The method for determining the basic degradation parameters of coke in this embodiment is based on the catalyst degradation behavior analyzed from data obtained from the reaction in the actual machine described above, or from a bench-scale reaction based on the actual machine operating conditions. This catalyst degradation behavior (degree of degradation) follows the same concept as in Equation 1 above and can be expressed by Equation 5 below. Φ'=k t ' / k0' expression 5 In the above equation 5, k0' is the reaction rate constant of the catalyst at 0 days after the reaction (i.e., at the start of the reaction), and k t ' represents the reaction rate constant of the catalyst after t days of any reaction. Note that k0' and k t ' is the temperature T described later. SOR This is the reaction rate constant in '.

[0042] Equation 5, like Equation 1, is a degradation function based on the reaction rate constant. The reaction rate constant is expressed by the Arrhenius equation in Equation 6 below.

[0043]

number

[0044] Temperature T at the start of reaction SORThe reaction rate constant k0 in ' is k after t days of reaction. t The reaction rate constant k0 decreases to '. To obtain an activity equivalent to the reaction rate constant k0' after t days of reaction, the reaction temperature should be set to T t Assuming that this must be the case, equation 7 below can be derived from equations 5 and 6. Note that the reaction in this embodiment is a hydrogenation reaction of feed oil containing heavy coker cracked light oil, so the activation energy E is set to the desulfurization activation energy Ea (kJ / mol).

[0045]

number

[0046] (Ec and T B How to find it) Under constant conditions for LHSV, hydrogen partial pressure, hydrogen / raw oil ratio, and sulfur concentration in the raw oil, the sulfur concentration in the produced oil is set to a constant value S. Pn The reaction is carried out for a certain period of time to achieve the desired result. Since the catalyst degrades during the reaction, the sulfur concentration in the resulting oil is adjusted to S Pn To achieve this, the reaction is carried out while increasing the reaction temperature. If the reaction time is plotted on the x-axis and the measured reaction temperature on the y-axis, and a regression line is drawn, then y=a n x+b n (0 n The straight line represented by ) is obtained. n and b n This value reflects the degradation behavior of the catalyst. b in this straight line n T in equation 7 SOR '. In the above equation 7, T SOR ' to b n Substitute T t Substituting the measured reaction temperature into ', the degree of degradation Φ' at any given reaction t days can be obtained. The activation energy Ea for desulfurization can be the value obtained by the method described later. Plotting reaction time on the x-axis and the logarithm of Φ' on the y-axis, and drawing a regression line, we get y = -a n ’ x(|-a​n ’ | = a n ’ is obtained. A straight line represented by a is obtained. a n ’ represents the deterioration rate of the catalyst.

[0047] n types of sulfur concentrations S Pn Perform the same reaction for each, and in the same way, n a's n , b n are obtained, and in the same manner as above, n a's n ’ are obtained. n is an integer of 3 or more. The larger the number of n, the higher the accuracy of Ec that can be obtained. On the other hand, if the number of n is too large, it takes time to obtain Ec and it is not efficient. In this embodiment, n is preferably 3 to 20, and more preferably 3 to 10. The n a's obtained in this way n ’ and b n are respectively substituted into the following formula 8. The following formula 8 is an equation capable of calculating the activation energy of coke and the reference reaction temperature, and is an equation first found by the inventors of the present application based on the operation results of actual machines and the like.

[0048] ln(a n ’ ) = ln(A) - (Ec / Rb n ) Equation 8 In the above formula 8, A is the frequency factor, Ec is the activation energy of coke deterioration (kJ / mol), and R is the gas constant: 0.00831 (kJ / (mol·K)).

[0049] For the combination of n a's n <00​​​​​​​​​​ Also, by averaging n b n , T B can be obtained.

[0051] Ec and T B In determining LHSV, hydrogen partial pressure, hydrogen / feedstock oil ratio, and sulfur concentration in the feedstock oil, it is preferable to set conditions in accordance with actual operating conditions. Such LHSV is, for example, 0.5 to 2.0 h -1 , the hydrogen partial pressure is, for example, 14 to 17 MPa, the hydrogen / feedstock oil ratio is, for example, 500 to 1300 [Nm 3 / kL], and the sulfur concentration in the feedstock oil is, for example, 3 to 5 mass%. n types of sulfur concentration S Pn is also preferably set to conditions in accordance with actual operating conditions. Such S Pn is, for example, 0.1 mass% or less. The reaction period is, for example, 300 to 2500 days.

[0052] (Method for obtaining P B and a) Set LHSV, hydrogen / feedstock oil ratio, sulfur concentration in the feedstock oil, silicon concentration, and sulfur concentration in the product oil to certain conditions, and conduct the reaction for a certain period under the condition of hydrogen partial pressure P m . Since the catalyst deteriorates due to the reaction, in order to make the sulfur concentration in the product oil a constant value, the operation is carried out while increasing the reaction temperature. Plot the reaction time on the horizontal axis and the measured reaction temperature on the vertical axis, and draw a regression line, then y = a m x + b m (0 < a m ). A straight line represented by this is obtained. b m in this straight line becomes T SOR ’ in the above formula 7. In the above formula 7, substitute b SOR into T m ’ and substitute the measured reaction temperature into T t ’, then the degree of deterioration Φ’ at an arbitrary reaction time of t days can be obtained. Plot the reaction time on the horizontal axis and the logarithm of Φ’ on the vertical axis, and draw a regression line, then y = -a m ’x(|―a m ’ |=a m ’ The straight line represented by ) is obtained. m ’ This represents the rate of catalyst degradation.

[0053] m types of hydrogen partial pressure P m A similar reaction is performed on m a m , b m We find m a using the same method as above. m ’ The result is obtained. m is an integer greater than or equal to 3. A larger number of m allows for a more accurate result of a. On the other hand, if the number of m is too large, it takes too long to obtain a, making it inefficient. In this embodiment, m is preferably between 3 and 20, and more preferably between 3 and 10. mseta obtained in this way m 'and P m Substitute the values ​​into equation 9 below. Equation 9 is a formula that can calculate the hydrogen partial pressure coefficient and the reference hydrogen partial pressure, and is the first formula discovered by the inventors of this application based on the operating results of the actual machine.

[0054] ln(a m ’ )=-aln(P m )+B1 Equation 9 In the above formula 9, B1 can be set to 0.

[0055] mCOa m 'and P m Regarding the combination, ln(a m ’ ) on the vertical axis, ln(P m Plot the values ​​on the x-axis, draw a regression line, and find its slope. This slope is the hydrogen partial pressure coefficient a.

[0056] Furthermore, the above m hydrogen partial pressures P m By averaging P B It is possible to find this.

[0057] a and P BWhen determining the LHSV, hydrogen / raw oil ratio, sulfur concentration in the feed oil, and sulfur concentration in the produced oil, it is preferable to use conditions that are consistent with actual operating conditions. For example, LHSV (Low-Hour High-Speed ​​Variable) durations are 0.5 to 2.0 hours. -1 Therefore, the hydrogen / raw material ratio is, for example, 500-1300 [Nm³]. 3 The ratio is [ / kL], and the sulfur concentration in the raw material oil is, for example, 3-5% by mass, while the sulfur concentration in the produced oil is, for example, 0.1% by mass or less. m types of hydrogen partial pressure P m Similarly, it is preferable to set the conditions to be in line with the actual operating conditions. m For example, the pressure is 14-17 MPa. The reaction period is, for example, 300-2500 days.

[0058] (α and T SOR How to find it 1) The reaction is carried out for a certain period of time in an actual machine or on a bench scale, so that the LHSV, hydrogen partial pressure, hydrogen / raw oil ratio, sulfur concentration in the feed oil, and sulfur concentration in the product oil are as assumed to be the actual operating conditions. Since the catalyst deteriorates during the reaction, the reaction temperature is increased during operation. The assumed actual operating conditions are (Ec and T B (How to find P) B The operating conditions described in (and how to find a) are given as an example. If we plot the reaction time on the x-axis and the measured reaction temperature on the y-axis and draw a regression line, we get y=a α x+b α A straight line is obtained that can be represented by this line a α b is a value correlated with α in the above equation 4, and α is T in the above equation 4. SOR This is the result. In the above equation 7, T SOR ' to b α Substitute T t Substituting the measured reaction temperature into ', we obtain the degree of deterioration Φ' at any given reaction time t days. Plotting the reaction time on the x-axis and the logarithm of Φ' on the y-axis, and drawing a regression line, we get y = -a α ’ x(|-a α ’ |=a α ’Let's assume that a straight line represented by ) is obtained. α ’ This represents the rate of catalyst degradation.

[0059] Driving condition S P S F , LHSV, P, and P obtained by the method described above B a, Ec, T B、 T SOR (that is, b α Substitute ) into equation 4 above to find D. Substitute the found D into equation 3 above to get Φ C This is obtained. In this case, Φ C is a function of α. In equation 2 above, Φ Si If we set = 1, then Φ = Φ C Thus, Φ becomes a function of α. If we plot reaction time on the x-axis and the logarithm of Φ on the y-axis, and draw a regression line by changing α so that 0 < α, we get y = -a α ” x(|-a α ” |=a α ” Multiple lines represented by ) are obtained for each value of α. α ” And, as mentioned above, a α ’ The value of α when these two values ​​are equal can be defined as α in equation 4.

[0060] (α and T SOR Method 2 for finding it) (α and T SOR Perform the same reaction as in method 1) to find y=a α x+b α We obtain a straight line represented by b α T in the above equation 4 SOR Let's assume that the operating condition is S. P S F , LHSV, P, and P obtained by the method described above B a, Ec, T B、 T SOR (that is, b α Substitute ) into equation 4 above to find D. Substitute the found D into equation 3 above to get Φ CThis is obtained. In this case, Φ C is a function of α. In equation 2 above, Φ Si If we set = 1, then Φ = Φ C Thus, Φ becomes a function of α. Substitute the obtained Φ with Φ' in equation 7 above, T SOR (that is, b α ) to T in the above formula 7 SOR ’ Substitute into T t To summarize, T t ' is a function of α. The measured reaction temperature T obs T for t ' ratio (T t ' / T obs The value of α when ) becomes 1 can be taken as α in the above equation 4. Similarly, for N reaction temperatures T obs T for t ' ratio (T t ' / T obs It is preferable to calculate the values ​​of these values ​​and set the value of α in equation 4 to the value of α when the average of these values ​​is closest to 1. N is an integer of 10 or more, preferably between 10 and 500, and more preferably between 50 and 200.

[0061] (A variation of the Coke degradation function 1) A variation of the Cork degradation function 1 is described below. The Cork degradation function 1-1, represented by equation 10 below, may also be used as the Cork degradation function 1.

[0062] Φ C =exp(-D't) Equation 10 In equation 10 above, D' is the degradation coefficient of the active species of the catalyst, and t is the number of days elapsed in the reaction.

[0063] D' can be found using equation 11 below.

[0064]

number

[0065] S in the above formula 11 F S P LHSV and P are as described in the explanation for Equation 4 above. In Equation 11 above, G is a value substituted based on the information on the feed oil and the information on the operating conditions obtained in the information acquisition step described above. Specifically, G is the hydrogen supply amount (Nm³ 3 It can be calculated by dividing the supply rate of raw material oil (kL / hour) by the supply rate of raw material oil (kL / hour).

[0066] In this specification, "reference hydrogen / raw material ratio" refers to the standard hydrogen / raw material ratio under actual reaction conditions. It is determined as the average value of the hydrogen / raw material ratio used when determining the hydrogen / raw material ratio coefficient b, which will be described later.

[0067] In the above formula 11, (G B / G) b The term represented by is a term that indicates the dependence on the hydrogen / raw material ratio, and as mentioned above, when G is set to a specific value and the operation is performed under constant conditions, it becomes a constant.

[0068] P B a, Ec, T B , T SORThis can be calculated using the same method as described in Equation 4 above. Hereafter, G B I will explain how to find b and α'.

[0069] G B , b is P B a, Ec, T B , T SOR Similarly, this parameter is determined according to the catalyst used, and may be determined while performing the reaction in the actual machine, or it may be determined in advance on a bench scale based on the actual machine operating conditions. In this embodiment, it is preferable to determine it in advance on a bench scale based on the actual machine operating conditions. Hereinafter, G B Next, I will explain how to find b.

[0070] (G B (How to find b) The method for determining the basic degradation parameters in this embodiment is based on the catalyst degradation behavior analyzed from data obtained from the reaction in the actual machine described above, or from a bench-scale reaction based on the actual machine operating conditions.

[0071] Under constant conditions for LHSV, hydrogen partial pressure, sulfur concentration in the feed oil, and sulfur concentration in the produced oil, the hydrogen / feed oil ratio G h The reaction is carried out for a certain period of time under these conditions. Since the catalyst degrades during the reaction, the reaction temperature is increased during operation to maintain a constant sulfur concentration in the resulting oil. When the reaction time is plotted on the x-axis and the measured reaction temperature on the y-axis, and a regression line is drawn, y=a h x+b h (0 h This is the case. A straight line is obtained that is represented by ). In this straight line, b h T in equation 7 SOR '. In the above equation 7, T SOR ' to b h Substitute T t ’ Substituting the measured reaction temperature into the equation yields the degree of deterioration Φ' at any given reaction time t. Plotting the reaction time on the x-axis and the logarithm of Φ' on the y-axis, and drawing a regression line, we get y = -a h ’ x(|―a h ’ ​|=a h ’ Thus, a straight line represented by ) is obtained. a h ’ represents the deterioration rate of the catalyst.

[0072] h types of hydrogen / feedstock oil ratios G h Perform the same reaction for, and in the same way, h a's h , b h are obtained, and by the same method as above, h a's h ’ are obtained. h is an integer of 3 or more. The larger the number of h, the more accurate b can be obtained. On the other hand, if the number of h is too large, it takes time to obtain b and it is not efficient. In the present embodiment, h is preferably 3 to 20, and more preferably 3 to 10. The h a's obtained in this way h ’ and G h [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​When determining the LHSV, hydrogen partial pressure, sulfur concentration in the feed oil, and sulfur concentration in the produced oil, it is preferable to use conditions that are consistent with actual operating conditions. For example, LHSV (Low-Hour High-Speed ​​Variable) durations are 0.5 to 2.0 hours. -1 The hydrogen partial pressure is, for example, 14-17 MPa, the sulfur concentration in the raw oil is, for example, 3-5% by mass, and the sulfur concentration in the produced oil is, for example, 0.1% by mass or less. h-type hydrogen / raw oil ratio G h Similarly, it is preferable to set conditions that are in line with actual operating conditions. h For example, 500~1300 [Nm 3 The concentration is [ / kL]. The reaction period is, for example, 300 to 2500 days.

[0077] Furthermore, α' is obtained using the same method as described in Coke Degradation Function 1, except that Equation 11 is used instead of Equation 4. ((α and T SOR Method 1) and (α and T) to find the answer SOR It can be found using the same method as method 2)).

[0078] <Coke Degradation Function 2> In this embodiment, the coke degradation function relating to the degradation of the catalyst due to coke deposition is preferably the coke degradation function 2 represented by the following equation 13, which consists of an easily deactivating active species degradation function relating to the degradation of easily deactivating active species of the catalyst and a difficult-to-deactivate active species degradation function relating to the degradation of difficult-to-deactivate active species of the catalyst.

[0079] Φ C =k1×exp(-D1t)+k2×exp(-D2t) Equation 13 In equation 13 above, k1 is the activity site coefficient of the easily deactivating active species of the catalyst, and k2 is the activity site coefficient of the difficult-to-deactivate active species of the catalyst. The activity site coefficients represent the relative reaction rate constants of both active species. D1 is the degradation coefficient of the easily deactivating active species of the catalyst due to coke, D2 is the degradation coefficient of the difficult-to-deactivate active species of the catalyst due to coke, t is the number of days elapsed in the reaction, and k1 + k2 = 1.

[0080] In the hydrotreating reaction of heavy coker cracked naphtha, as described above, since the catalyst deteriorates due to coke deposition, in order to keep the sulfur content in the produced oil below a certain level, it is necessary to increase the reaction temperature for operation. In the hydrotreating reaction of heavy coker cracked naphtha, at the initial stage of the reaction start, the reaction temperature rises rapidly. This rapid rise in the reaction temperature means a rapid deterioration of the catalyst at the initial stage of the reaction start. On the other hand, after the middle stage of the reaction, the reaction temperature rises gently. This gentle rise in the reaction temperature means a gentle deterioration of the catalyst after the middle stage of the reaction.

[0081] That is, in the hydrotreating reaction of heavy coker cracked naphtha, it is suggested from the profile of the reaction temperature with respect to the reaction time that rapid deterioration of the catalyst occurs at the initial stage of the reaction start and gentle deterioration of the catalyst occurs after the middle stage of the reaction.

[0082] Based on the profile of the reaction temperature with respect to the above reaction time, the inventors of the present application assumed that there are easily deactivated active species that are deactivated by coke at the initial stage of the reaction start and difficult-to-deactivate active species that are deactivated by coke after the middle stage of the reaction in the catalyst, and further improved the coke deterioration function 1 and found the coke deterioration function 2. As a result, according to the coke deterioration function 2, it was found that the degree of deterioration of the catalyst due to coke can be calculated more accurately than the coke deterioration function 1. The easily deactivated active species are mainly the active species whose activity is lost at the initial stage of the reaction, and the difficult-to-deactivate active species mean the active species whose activity is lost after the middle stage of the reaction.

[0083] In the above formula 13, k1 represents the active site coefficient of the easily deactivated active species of the catalyst, and k2 represents the active site coefficient of the difficult-to-deactivate active species of the catalyst. k1 and k2 are constants specific to the catalyst, and the method for obtaining them will be described later.

[0084] D1 can be obtained by the following formula 14, and D2 can be obtained by the following formula 15.

[0085]

Equation

[0086]

Number

[0087] In the above formula 14 and the above formula 15, S F is the sulfur concentration (mass %) in the feedstock oil at the end of any reaction day t, and S P is the sulfur concentration (mass %) in the product oil at the end of any reaction day t. n is the reaction order of the hydrotreating reaction of the feedstock oil containing heavy coker cracked light oil. LHSV is the liquid hourly space velocity (per hour -1 ) at the end of any reaction day t. P B is the reference hydrogen partial pressure (MPa), and P is the hydrogen partial pressure (MPa) at the end of any reaction day t. a is the hydrogen partial pressure coefficient. Ec is the activation energy (kJ / mol) of coke deterioration. R is the gas constant: 0.00831 (kJ / (mol·K)). T B is the reference reaction temperature (K), and T SOR is the required temperature (K) on day 0. In the above formula 14, α1 is the catalyst constant of the easily deactivated active site (a constant representing the deterioration rate of the catalyst by coke). In the above formula 15, α2 is the catalyst constant of the hardly deactivated active site (a constant representing the deterioration rate of the catalyst by coke).

[0088] In the above formula 14 and the above formula 15, S F , S P , LHSV, and P are values substituted based on the information on the feedstock oil, the information on the product oil, and the information on the operating conditions obtained in the above-described information acquisition step, in the same manner as the description of the above formula 4. Note that LHSV can be obtained by dividing the supply amount of the feedstock oil (volume / hour) by the catalyst filling amount (volume).

[0089] As described above, S F , LHSV, and P are parameters that can be controlled. Also, S P is the sulfur concentration of the target product oil. That is, according to the above formula 14 and the above formula 15, the above S F , S PThe degradation coefficients due to coke for readily deactivating active species of the catalyst and for less deactivating active species of the catalyst can be calculated under the reaction conditions of LHSV and P. The method for determining n, which is the reaction order of the hydrogenation reaction of feedstock oil containing heavy coker cracked diesel fuel, will be described later.

[0090] (How to determine the basic degradation parameters of Coke) In formulas 14 and 15, α1, α2, P B a, Ec, T B , T SOR Similar to equation 4 above, P is a constant, and these parameters are collectively referred to as the "basic coke degradation parameters 2". The basic coke degradation parameters 2 are parameters determined according to the catalyst used, and may be determined while performing the reaction in the actual machine, or may be determined in advance on a bench scale based on the actual machine operating conditions. In this embodiment, it is preferable to determine them in advance on a bench scale based on the actual machine operating conditions. In equations 14 and 15 above, P B a, Ec, T B This can be determined by the same method as in equation 4 above. On the other hand, α1, α2, T SOR This can be determined, for example, by the following two methods. In addition, the activity point coefficient k1 of the easily deactivating active species of the catalyst and the activity point coefficient k2 of the difficult-to-deactivate active species of the catalyst in equation 13 can also be determined simultaneously as follows.

[0091] (α1, α 2、 T SOR How to find k1 and k2 1) In a real-world or bench-scale environment, the reaction is carried out for a certain period of time under conditions that match the assumed real-world operating conditions: LHSV, hydrogen partial pressure, hydrogen / raw oil ratio, sulfur concentration in the feed oil, and sulfur concentration in the product oil. Since the catalyst degrades during the reaction, the reaction temperature is increased during operation. The reaction time is plotted on the x-axis and the reaction temperature on the y-axis. When drawing a regression line for these plots, as described above, the initial reaction period (x1~x n ) A straight line represented by y=a1x+b1 correlates with the rapid increase in reaction temperature, and (x) n+1 ~xm Two straight lines represented by y = a2x + b2 are obtained that correlate with the gradual increase in reaction temperature. In the above equation, a1 > a2 > 0, and b1 <b2であり、x1<x n <x n+1 <x m x n , x m This represents the reaction time correlated with the nth (m)th plot from the start of the reaction.

[0092] The above a1 is a value correlated with α1, and b1 is a value correlated with k1+k2, T SOR Furthermore, a2 is a value correlated with α2, and b2 is a value correlated with k2. Next, the intersection point of y=a1x+b1 and y=a2x+b2 is (x ip , y ip ) calculates this intersection point. This intersection point represents the inflection point of y=a1x+b1 and y=a2x+b2. That is, (x ip , y ip Up to (x ip , y ip From this, we assume that there are two active species: an easily deactivating active species of the catalyst and a difficult-to-deactivate active species of the catalyst.

[0093] In the above formula 7, T SOR Substitute b1 into ', T t Substituting the reaction temperature into ', we obtain the degree of deterioration Φ' after any given reaction t days. Plot the reaction time on the x-axis and the logarithm of Φ' on the y-axis, and x1~x ip If we draw the regression line up to y=-a1 ’ x(|-a1 ’ |=a1 ’ This is the result. A straight line represented by ) is obtained. Also, x ip ~x m If we draw the regression line up to y=-a2 ’ x-b2 ’ (|-a2 ’ |=a2 ’ And |-b2 ’ |=b2 ’ The straight line represented by ) is obtained. a1 ’ This is a value correlated with α1, and a2’ This is a value correlated with α2, and b2 ’ This is a value correlated with k2.

[0094] k2 is the value of b2 obtained from the regression line described above. ’ This can be found by substituting into equation 16 below. Since k1 is k1 + k2 = 1, k1 can be found from k1 = 1 - k2. k2 = exp(-b2) ’ ) Equation 16

[0095] Driving condition S P S F , LHSV, P, and P obtained by the method described above B a, Ec, T B , T SOR Substitute (b1) into equations 14 and 15 to obtain D1 and D2. Substitute the obtained D1, D2, k1, and k2 into equation 13 to obtain Φ C This is obtained. In this case, Φ C is a function of α1 and α2. In equation 2 above, Φ Si If we set = 1, then Φ = Φ C Thus, Φ becomes a function of α1 and α2. Plot the reaction time on the x-axis and the logarithm of Φ on the y-axis, and change α1 such that 0 < α1 by setting α2 = 0, and then x1 ~ x ip If we draw the regression line up to y=-a α1 ” x(|-a α1 " |=a α1 ” Multiple lines represented by ) are obtained for each value of α1. a α1 ” And, as mentioned above, a1 ’ The value of α1 when these two values ​​are equal can be taken as α1 in equation 14. Next, the function Φ of α1 and α2 obtained by the method described above is C Substitute the obtained α1 into (Φ), and change α2 so that 0 < α2 to x ip ~x m If we draw the regression line up to y=-a α2 ” xb α2 "(|-a α2 ” |=a α2 " Multiple lines represented by ) are obtained for each value of α². α2 And, as mentioned above, a2 ’ The value of α2 when the two equations are equal can be considered as α2 in equation 15.

[0096] (α1, α 2、 T SOR Method for determining k1 and k2 (2) (α1, α 2、 T SOR The same reaction as in method 1) for determining k1 and k2 is performed, and T SOR (b1) is obtained. The operating condition is S P S F , LHSV, P, and P obtained by the method described above B a, Ec, T B , T SOR Substitute (b1) into equations 14 and 15 to obtain D1 and D2. Substitute the obtained D1 and D2 into equation 13 to get Φ C This is obtained. In this case, Φ C is a function of α1, α2, k1, and k2. In equation 2 above, Φ Si If we set = 1, then Φ = Φ C Thus, Φ becomes a function of α1, α2, k1, and k2. Substitute the obtained Φ into Φ' in equation 7 above, T SOR (i.e., b1) is T in the above formula 7. SOR ’ Substitute into T t To summarize, T t ' is a function of α1, α2, k1, and k2. If we set α2 to 0 and k2 = 1 - k1, then T t ' is a function of α1 and k1. x1~x ip The measured reaction temperature T obs T for t ' ratio (T t ' / T obs The combination of α1 and k1 when ) is 1 can be found, and this α1 can be used as α1 in equation 14 above. Note that k1 at this time is a provisional value. Similarly, the M reaction temperatures T obs T fort ' ratio (T t ' / T obs It is preferable to calculate the values ​​of these and set the value of α1 in equation 14 to the value of α1 when the average of these values ​​is closest to 1. M is an integer of 10 or more, preferably between 10 and 500, and more preferably between 50 and 200. Using the obtained α1, if we set k1 = 1 - k2, then T t ' becomes a function of α² and k². ip ~x m The measured reaction temperature T obs T for t ' ratio (T t ' / T obs The combination of α2 and k2 when ) is 1 can be found, and these α2 and k2 can be used as α2 and k2 in equation 15. By substituting the obtained k2 into k1 = 1 - k2, k1 can be found, and this k1 can be used as k1 in equation 14. Similarly, L reaction temperatures T obs T for t ' ratio (T t ' / T obs It is preferable to calculate the values ​​of α2 and k2 in equation 15 such that the average of these values ​​approaches 1. It is also preferable to use the value of k1 obtained from the resulting k2 as the value of k1 in equation 14. L is an integer of 10 or more, preferably between 10 and 500, and more preferably between 50 and 200.

[0097] Thus, α1, α 2、 T SOR To find k1 and k2, we need to obtain y = a1x + b1 and y = a2x + b2. These can be found, for example, as follows.

[0098] Using the above method, plot the reaction time on the horizontal axis and the reaction temperature on the vertical axis. When a regression line is drawn from the start to the end of the reaction, a straight line represented by y = a’x + b’ is obtained. This straight line does not take into account the inflection point. Starting from the end of the reaction, delete the plots in order, and adjust the y = a’x + b’ so that the correlation coefficient approaches 1 to obtain y = a1’x + b1’. Similarly, starting from the start of the reaction, delete the plots in order, and adjust the y = a’x + b’ so that the correlation coefficient approaches 1 to obtain y = a2’x + b2’. When the average of the correlation coefficients of y = a1’x + b1’ and y = a2’x + b2’ is closest to 1, the respective straight lines become y = a1x + b1 and y = a2x + b2. Note that all plots should belong to either y = a1x + b1 or y = a2x + b2.

[0099] The reaction time required to obtain y = a1x + b1 and y = a2x + b2 is usually 100 days or more. Also, generally, it is sufficient to carry out the reaction until the correlation function of y = a’x + b’ as described above becomes 0.5 or more.

[0100] (Modified Example of Coke Deterioration Function 2) A modified example of the coke deterioration function 2 will be described below. As the coke deterioration function 2, the coke deterioration function 2-1 represented by the following formula 17 may be used.

[0101] Φ C = k1×exp(-D1’t) + k2×exp(-D2’t) Formula 17 In the above formula 17, k1, k2, and t are the same as in the above formula 13, D1’ is the deterioration coefficient of coke of the easily deactivated active species of the catalyst, and D2’ is the deterioration coefficient of coke of the difficult-to-deactivate active species of the catalyst.

[0102] D1’ can be obtained by the following formula 18, and D2’ can be obtained by the following formula 19.

[0103]

Number

[0104]

Number

[0105] In formulas 18 and 19, S F S P ,n,LHSV,P B P, a, Ec, R, T B , T SOR This is the same as formulas 14 and 15 above, and G B , G and b are the same as in equation 11, and in equation 18, α1' is the catalytic constant for the easily deactivating active site (a constant representing the rate of degradation of the catalyst due to coke), and in equation 19, α2' is the catalytic constant for the difficult-to-deactivate active site (a constant representing the rate of degradation of the catalyst due to coke).

[0106] P B a, Ec, T B , T SOR G can be obtained by the same method as described in equations 14 and 15 above, B b can be determined using the same method as described in equation 11 above.

[0107] Furthermore, α1' and α2' can be determined using the same method as described for determining α1 and α2 in the degradation function 2, except that equation 17 is used instead of equation 13, equation 18 is used instead of equation 14, and equation 19 is used instead of equation 15.

[0108] <Silicon Degradation Function> The silicon degradation function is not particularly limited as long as it is a function that can calculate the degree of degradation related to the silicon degradation of the catalyst, but for example, the degradation function represented by equation 20 below can be given as an example. The degradation function represented by equation 20 below is a function that the inventors of the present invention first discovered by applying the metal degradation in the diffusive degradation model of heavy oil described in non-patent literature (Journal of Chemical Engineering, Vol. 24, No. 4 (1998), p. 656) to silicon degradation.

[0109]

number

[0110] In equation 20, η represents the diffusion of reactants, i.e., sulfur compounds, within the pores of the catalyst. Equation 20 is a silicon degradation function in which the catalyst degradation behavior due to pore blockage caused by silicon deposition is expressed by the catalyst efficiency coefficient η. When η = 1, it indicates that there is no diffusion inhibition and the reaction is effectively utilized even inside the pores, while a smaller value indicates that the reaction occurs near the outer surface of the catalyst. The value of SiOC in equation 20 can be determined by the following equation 21. η, SiOC ∞ The method for calculating this will be explained later.

[0111]

number

[0112] In the above formula 21, WHSV, Si f Si pThis value is substituted based on the information regarding the raw material oil, the produced oil, and the operating conditions obtained in the information acquisition step described above. WHSV can be calculated by dividing the raw material oil supply rate (weight / hour) by the catalyst filling rate (weight).

[0113] As mentioned above, WHSV, Si f This is a controllable parameter. Also, Si p is the silicon concentration of the target generated oil. That is, according to formulas 20 and 21 above, WHSV, Si f Si p The silicon degradation function can be calculated under these reaction conditions.

[0114] In the hydrogenation reaction of feedstock oils, including heavy coker cracked diesel fuel, catalyst degradation occurs due to silicon deposition, as described above. Therefore, it is necessary to operate the reaction at a higher temperature to maintain the sulfur content in the resulting oil below a certain level. This degradation of the catalyst due to silicon deposition can be explained by a decrease in the diffusion rate of the feedstock oil into the catalyst pores. In other words, in the hydrogenation reaction of heavy coker cracked diesel fuel, the feedstock oil needs to diffuse into the catalyst pores and access the active sites. When the diffusion rate is sufficiently greater than the reaction rate, the feedstock oil can access all the active sites. However, when the diffusion rate is small relative to the reaction rate, the feedstock oil cannot access all the active sites, and none of the active sites function effectively. The diffusion rate decreases over time as the catalyst pores become blocked due to silicon deposition.

[0115] The extent to which active sites within catalyst pores are effectively utilized is determined by the relationship between the reaction rate and the diffusion rate. This relationship can be theoretically expressed by the catalytic efficiency coefficient η. When there is no diffusion inhibition and virtually all active sites within the catalyst pores are utilized, η is 1. On the other hand, when virtually all active sites within the catalyst pores are not utilized, η becomes less than 1. Furthermore, when only active sites near the outer surface of the catalyst are utilized, η approaches 0.

[0116] As described above, the inventors of this application have found a coke degradation function based on the assumption that there are easily deactivated active species that are deactivated by coke in the early stages of the reaction and difficult-to-deactivate active species that are deactivated by coke from the middle stages of the reaction onward. Here, it is also considered that a decrease in activity due to silicon deposition occurs throughout the entire reaction period. The inventors of this application have found that by combining the coke degradation function and the silicon degradation function, it is possible to calculate the degree of catalyst degradation with greater accuracy.

[0117] In the above formula 20, η, SiOC ∞ is a constant. Hereinafter, these parameters will be collectively referred to as "basic silicon degradation parameters." Basic silicon degradation parameters are parameters determined according to the catalyst used, and may be determined while performing the reaction in the actual machine, or may be determined in advance on a bench scale based on the actual machine operating conditions. In this embodiment, it is preferable to determine them in advance on a bench scale based on the actual machine operating conditions. The following are the basic degradation parameters η and SiOC. ∞ Examples of how to determine this will be explained, but the present invention is not limited to these examples.

[0118] (SiOC ∞ How to find it) SiOC ∞ This is a catalyst-specific value and can be determined using methods known in this field. SiOC ∞ An example of how to determine this is to carry out the reaction for a certain period of time in an actual machine or on a bench scale, so that the LHSV, hydrogen partial pressure, hydrogen / raw material ratio, sulfur concentration in the feed material, silicon concentration, sulfur concentration in the produced oil, and silicon concentration in the produced oil are as assumed to be the actual operating conditions. Since the catalyst deteriorates during the reaction, the operation is carried out while increasing the reaction temperature. Actual operating conditions include, as an example, the reaction conditions for obtaining a deteriorated catalyst as described in (Method 1 for determining η) below. If the reaction is continued for a long time, even if the reaction temperature is set to the maximum operating temperature of the equipment (for example, BASE (the total reaction period is t total When (day) is set, the reaction starts ~0.34 × t totalAt the average reaction temperature (in Japan) + 90°C, the silicon concentration in the produced oil no longer reaches the predetermined value. The reaction is continued until the silicon concentration in the feedstock oil equals the silicon concentration in the produced oil, at which point the reaction is stopped and the catalyst is extracted. The silicon concentration of the extracted catalyst is measured, and the obtained value is called the SiOC. ∞ It can be done this way.

[0119] (Method 1 for finding η) On a bench scale, a reaction is carried out for a certain period of time using a new catalyst and a corresponding degraded catalyst, so that the LHSV, hydrogen partial pressure, hydrogen / raw material ratio, sulfur concentration in the feed material, silicon concentration, sulfur concentration in the produced oil, and silicon concentration in the produced oil are all within the assumed operating conditions of the actual machine. For example, the degraded catalyst is LHSV 0.5 to 2 hours. -1 Hydrogen partial pressure 11-17 MPa, hydrogen / raw material ratio 500-1300 [Nm] 3 A catalyst can be used that has been reacted for 100 days or more with a sulfur concentration of 3-5% by mass and a silicon concentration of 0.3-7 ppm by weight in the feedstock oil, and a sulfur concentration of less than 0.1% by mass and a silicon concentration of less than 0.3 ppm by weight in the produced oil. The reaction may be carried out on a full-scale or bench-scale system. For several days during which the sulfur concentration of the produced oil is stable, the desulfurization reaction rate constants of the degraded catalyst and the new catalyst are determined based on Equation 24 described below. The desulfurization reaction rate constant of the degraded catalyst is corrected by the catalyst weight-average temperature (reaction temperature) of the new catalyst to calculate the desulfurization reaction rate constant. Specifically, it is calculated as k1 in Equation A below. Equation A below is based on the Arrhenius equation represented by Equation 6 above.

[0120]

number

[0121] Desulfurization reaction rate constant of the new catalyst (k fresh The desulfurization reaction rate constant (k) of the corrected degraded catalyst for ) used ) is the relative activity (k used / k fresh ) k fresh / k fresh and k used / k fresh The difference includes not only silicon deposition but also the decrease in activity due to coke deposition, so that decrease is k used / k fresh It is necessary to correct (add) to this. The inventors' investigation revealed that, as described above, the degradation of the catalyst due to coke deposition in the hydrogenation reaction of feedstock oil containing heavy coker cracked diesel fuel is almost the same as the degradation due to coke deposition in the catalyst in the hydrogenation reaction (indirect desulfurization reaction) of feedstock oil containing vacuum distilled diesel fuel obtained by vacuum distillation of atmospheric distillation residue, and that the degradation behavior is linear with respect to the amount of carbon deposition. That is, (k fresh / k fresh -k used / k fresh The decrease in activity due to coke deposition in the mixture can be determined by the hydrogenation reaction of the feedstock oil, including silicon-free vacuum-distilled diesel fuel.

[0122] Using the new catalyst, a hydrogenation reaction is carried out on feed oil containing vacuum-distilled diesel fuel to produce an indirect desulfurization degradation catalyst. The indirect desulfurization degradation catalyst is used, for example, for LHSV 0.5 to 2.5 hours. -1 Hydrogen partial pressure 3-7 MPa, hydrogen / raw material ratio 100-400 [Nm] 3A catalyst can be used that has been reacted for 100 days or more at a sulfur concentration of 0.5 to 3% by mass in the feed oil, a silicon concentration of less than 0.3 ppm by weight, a sulfur concentration of less than 0.3% by mass in the produced oil, and a silicon concentration of less than 0.3 ppm by weight. The reaction time is preferably similar to that of the above-mentioned desulfurized catalyst. The reaction may be carried out on a full-scale or bench-scale. Using the obtained indirect desulfurization desulfurization catalyst, the desulfurization reaction rate constant (k) in the hydrogenation reaction of feed oil containing heavy coker cracked light oil can be determined in the manner described above. used(coke) ) The horizontal axis represents the amount of coke deposit, and the amount of activity reduction from the new catalyst due to coke deposit (k fresh / k fresh (=1)-k used(coke) / k fresh The carbon content is plotted on the vertical axis, and the amount of activity reduction per 1% by mass of carbon deposit is calculated from the slope of the line connecting the plotted points to the origin. Examples of degraded catalysts with different carbon content include those extracted from the upper and lower parts of the same reaction tower, or catalysts operated at different times. This is because even catalysts of the same brand will have different carbon content depending on the packing location in the reaction tower, the operating period, and the properties of the feedstock oil. The amount of activity reduction due to carbon deposits on the degraded catalyst is calculated by multiplying the calculated amount of activity reduction per 1% by mass of carbon deposit by the amount of carbon deposited on the degraded catalyst. The calculated decrease in activity due to deposited carbon is added to the relative activity of the original degraded catalyst to calculate the relative activity of the catalyst degraded solely by silicon deposition. Using the same new catalyst (SiOC / SiOC ∞ For multiple degradation catalysts with different SiOCs (i.e., different SiOCs), the relative activity of the degradation catalysts due to silicon deposition alone is calculated using the method described above. As multiple degradation catalysts with different SiOCs, for example, catalysts extracted from the upper and lower parts of the same reaction column, or catalysts operated at different times, can be used. This is because even catalysts of the same brand will have different silicon content depending on the packing location in the reaction column, the operating period, and the properties of the feedstock oil. The horizontal axis represents the silicon allowable ratio (SiOC / SiOC) of the degradation catalyst relative to its silicon allowable capacity. ∞), the vertical axis represents the relative activity due to silicon deposition alone, with the activity of the new catalyst set to 1 (Φ Si The points are plotted, and the value of η used in the silicon degradation function represented by equation 20 that best approximates these points is determined. Number of plots (SiOC / SiOC) ∞ The number of different degradation catalysts is preferably 2 to 5.

[0123] The above explains how to determine the coke degradation function, the silicon degradation function, and the parameters used in these functions (basic degradation parameters for coke, basic degradation parameters for silicon, activity point coefficient k1 for easily deactivating active species, activity point coefficient k2 for difficult-to-deactivate active species of catalyst, etc.). In the above explanation, the parameters used in the coke degradation function and the parameters used in the silicon degradation function were determined separately, but they may also be determined simultaneously by fitting. Specifically, the reaction is carried out on an actual machine or bench scale under assumed actual operating conditions, and data on the change in reaction temperature over time is obtained. For example, when using coke degradation function 1, equations 23, 2, 3, 4, and 20 described later are used. The reaction conditions are substituted into equations 4 and 20. Then, the T of equation 23 described later is t However, the basic degradation parameters for coke degradation in Equation 4 and the basic degradation parameters for silicon in Equation 20, which match the measured reaction temperature, may be determined by fitting.

[0124] <<Steps for calculating reaction temperature>> The reaction temperature calculation step in this embodiment is a step of calculating information regarding the feedstock oil, information regarding the product oil, and the reaction temperature necessary to satisfy the operating conditions, based on the degree of catalyst degradation. Preferably, the reaction temperature is calculated using a degradation rate equation based on the Arrhenius equation.

[0125] <Deterioration rate formula> The degradation rate equation is based on the Arrhenius equation represented by equation 6. Similar to the calculation method for equation 7, equation 22 below can be derived from equations 1 and 6.

[0126]

number

[0127]

number

[0128] In equation 23 above, the T obtained by the method described above is SOR By substituting Φ, we can determine the time of any reaction after t days. t (K) can be obtained. The activation energy of the desulfurization reaction in the above equation 23 can be determined as follows.

[0129] (How to determine the activation energy of the desulfurization reaction) The activation energy of the desulfurization reaction can be determined by methods known in this art, based on the Arrhenius equation represented by Equation 6 above. An example is described below.

[0130] First, we determine the reaction order of the desulfurization reaction of feed oil containing heavy coker cracked diesel fuel. The reaction is carried out under constant conditions of LHSV(x) with constant reaction temperature, hydrogen partial pressure, hydrogen / feed oil ratio, and sulfur concentration in the feed oil, and the sulfur concentration in the resulting oil is measured. The S in the desulfurization reaction rate equation, represented by Equation 24 below, is used. F The sulfur concentration in the raw material oil is S P Substitute LHSV(x) into LHSV to obtain the sulfur concentration in the resulting oil. Plot the result on the left side on the vertical axis and 1 / LHSV on the horizontal axis. In this case, the vertical axis is a function of n.

[0131]

number

[0132] Perform the same reaction for x types of LHSV(x) and obtain x of the above plots. Draw a regression line passing through the origin based on the obtained plots and obtain a line represented by y=cx. y is (1 / n-1)((1 / S P n-1 )-(1 / S F n-1 )) where x is 1 / LHSV and c is k. Calculate the correlation function using Excel or similar software, and find the n that brings the correlation coefficient closest to 1. The resulting n is the reaction order. Note that n should be calculated to the order of one decimal place.

[0133] The above x is an integer greater than or equal to 3. A larger number of x values ​​allows for obtaining a more accurate n. On the other hand, if the number of x values ​​is too large, it takes too long to obtain n, making it inefficient. In this embodiment, x is preferably between 3 and 20, and more preferably between 3 and 10.

[0134] When determining n, it is preferable that the reaction temperature, hydrogen partial pressure, hydrogen / raw material oil ratio, and sulfur concentration in the raw material oil be conditions that are in line with actual operating conditions. Such reaction temperatures are, for example, 330-410°C, with a hydrogen partial pressure of 14-17 MPa and a hydrogen / raw material ratio of 500-1300 Nm³. 3 The ratio is [ / kL], and the sulfur concentration in the raw material oil is 3-5% by mass. Similarly, it is preferable that the x types of LHSV(x) also be under conditions that are consistent with actual operating conditions. Such LHSV(x) should be 0.5 to 2.0 hours. -1 That is the case.

[0135] If we let the activation energy E in the Arrhenius equation represented by equation 6 above be the activation energy Ea for desulfurization, and take the natural logarithm of both sides, we obtain the equation shown in equation 25 below.

number

[0136] The hydrogen partial pressure, hydrogen / raw oil ratio, LHSV, and sulfur concentration in the raw oil are kept constant, and the reaction is carried out at a reaction temperature T(y), and the sulfur concentration in the produced oil is measured. S in the desulfurization reaction rate equation represented by Equation 24 above F The sulfur concentration in the raw material oil is S P The sulfur concentration in the resulting oil is used to determine the reaction rate constant k by substituting LHSV for LHSV and the obtained n above. The obtained reaction rate constant is substituted into equation 25, and the result on the left side (lnk) is plotted on the vertical axis, and 1 / T(1 / T(y)) is plotted on the horizontal axis.

[0137] The same reaction is carried out for y types of reactions at reaction temperature T(y), and y plots are obtained. A regression line is drawn from the obtained plots, and its slope is determined. Since this slope is Ea / R, the activation energy Ea of desulfurization can be obtained by subtracting R from the slope.

[0138] The above y is an integer greater than or equal to 3. A larger number of y values ​​allows for a more accurate Ea. On the other hand, if the number of y values ​​is too large, it takes a long time to obtain Ea, making it inefficient. In this embodiment, y is preferably between 3 and 20, and more preferably between 3 and 10.

[0139] When determining Ea, it is preferable that the hydrogen partial pressure, hydrogen / raw material ratio, LHSV, and sulfur concentration in the feed material are conditions that are consistent with actual operating conditions. Such a hydrogen partial pressure would be, for example, 14-17 MPa, and the hydrogen / raw oil ratio would be 500-1300 [Nm³]. 3 [ / kL], and LHSV is 0.5-2.0 hours. -1 The sulfur concentration in the raw material oil is 3-5% by mass. Similarly, it is preferable that the reaction temperature T(y) for type y be a condition that matches the actual operating conditions. Such a T(y) is 330 to 410°C.

[0140] By substituting the parameters obtained in this way into equation 23, the reaction temperature T required to achieve the predetermined reaction conditions can be calculated. t It is possible to find this.

[0141] Measured reaction temperature T obs The reaction temperature T obtained by the information processing method of this embodiment is determined for the given condition. t T is the proportion t / T obs The temperature is preferably 0.97 to 1.03 in °C, and more preferably 0.985 to 1.015. t / T obs If the value falls within the aforementioned range, it can be determined that the reaction temperature has been estimated with good accuracy.

[0142] ≪Information Output Step≫ The system may further include an information output step (S4 in Figure 1) in which information indicating the reaction temperature obtained in this manner is output. For example, S4 is performed by the output unit 14.

[0143] Hydrogenation reaction of feedstock oil containing heavy coker cracked diesel fuel This document outlines the hydrogenation reaction of feedstock oils, including heavy coker cracked diesel fuel. Heavy coker-cracked diesel fuel is a fraction obtained by distilling coker-cracked oil, with a boiling point range of approximately 350-520°C at atmospheric pressure. The density of heavy coker-cracked diesel fuel is 0.96-1.00 g / mL. The content of heavy coker-cracked diesel fuel in the feedstock oil may be, for example, 50% by volume or more, or 70% by volume or more. In addition to heavy coker-cracked diesel fuel, other types of oil included in the feedstock include heavy cycle oil obtained from a fluid catalytic cracking unit. The content of heavy cycle oil in the feedstock can range from 0 to 50% by volume.

[0144] The hydrogenation reaction of feedstock oil containing heavy coker cracked diesel fuel can be carried out by contacting the feedstock oil containing heavy coker cracked diesel fuel with a hydrogenation catalyst in the presence of hydrogen. The hydrogenation catalyst is not particularly limited, and any hydrogenation catalyst known in this art can be used. Various materials can be used as catalyst supports, such as silica, alumina, boria, magnesia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titania, silica-boria, alumina-zirconia, alumina-titania, alumina-boria, alumina-chromia, titania-zirconia, silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, or mixtures of two or more of these. Among these inorganic oxides, preferred ones include alumina, silica-alumina, alumina-titania, alumina-boria, and alumina-zirconia, with alumina being particularly preferred, and γ-alumina being particularly preferred among aluminas. These inorganic oxides may be used individually or in combination of two or more.

[0145] The metal to be included as an active component in the support is at least one metal selected from Group 6 and Groups 8-10 of the periodic table, preferably molybdenum, tungsten, cobalt, and nickel. These metals are effective in metallic form, metal oxide, or metal sulfide, and may also exist in a form where the metal is bonded to the catalyst support by ion exchange or the like. The content of this metal component is usually in the range of about 1 to 25 mass%, based on the catalyst and in terms of oxides. If the metal content is less than 1 mass%, the absolute amount of metal acting as active sites is small, and hydrogenation activity, including desulfurization activity (hereinafter simply referred to as hydrogenation activity), will not be exhibited. Conversely, if the content of the supported metal is too much more than 25 mass%, metal aggregation occurs, reducing the number of active sites, and as a result, the hydrogenation activity actually decreases. Furthermore, if necessary, in addition to the active metals consisting of Group 6 and Group 8 of the periodic table, phosphorus, boron, zinc, zirconia, etc. can be included. When applying the method of the present invention, there are no restrictions on the form of the catalyst layer, and it can be applied to reactors with catalyst layers such as fixed beds, moving beds, and fluidized beds.

[0146] The conditions for the hydrogenation reaction of feedstock oil containing heavy coker cracked diesel are generally a reaction temperature of 330-410°C, preferably 360-400°C, a hydrogen partial pressure of 10-20 MPa, preferably 14-17 MPa, and an LHSV of 0.1-2.0 hr. -1 Preferably 0.5 to 1.2 hours -1 The hydrogen / raw material ratio is 170-1400 [Nm³]. 3 [kL], preferably 500-1300 [Nm 3 It is [ / kL].

[0147] The sulfur concentration in the feedstock oil containing heavy coker cracked diesel is typically 3-5% by mass. The sulfur concentration in the resulting oil is typically 0.1% by mass or less. The silicon concentration in the feedstock oil containing heavy coker cracked diesel is typically 0.3 ppm by weight to 7 ppm by weight. The silicon concentration in the resulting oil is typically less than 0.3 ppm by weight.

[0148] <<Reaction Temperature Calculation Device>> The reaction temperature calculation device of this embodiment includes an acquisition unit that acquires information on the raw material oil, the product oil, and the operating conditions at a predetermined time after the start of a hydrogenation reaction of a raw material oil containing heavy coker cracked light oil; and a calculation unit that calculates the degree of catalyst degradation using a degradation function based on the information on the raw material oil, the product oil, and the operating conditions acquired by the acquisition unit, and calculates the reaction temperature necessary to satisfy the information on the raw material oil, the product oil, and the operating conditions based on the calculated degree of catalyst degradation. The reaction temperature calculation device of this embodiment may also have an output unit that outputs information indicating the calculated reaction temperature.

[0149] The reaction temperature calculation device 1 of this embodiment is configured using an information processing device such as a personal computer, a server device, or a dedicated device. The reaction temperature calculation device 1 may be configured using one or more information processing devices. For example, the reaction temperature calculation device 1 may be constructed as a cluster machine, as a cloud, or in any other manner. The reaction temperature calculation device 1 has, for example, an acquisition unit 11 and a computer main unit 12 that processes information from the acquisition unit, as shown in Figure 4. The reaction temperature calculation device 1 may also have an output unit 14 that outputs the information processed by the computer main unit 12 to the outside. These components are realized, for example, by a hardware processor such as a CPU (Central Processing Unit) executing a program (software). Furthermore, some or all of these components may be realized by hardware (including circuitry) such as an LSI (Large Scale Integrated Circuit), ASIC (Application Specific Integrated Circuit), FPGA (Field-Programmable Gate Array), or GPU (Graphics Processing Unit), or by the cooperation of software and hardware. The program may be stored in advance on a storage device such as an HDD (Hard Disk Drive) or flash memory (a storage device equipped with a non-transient storage medium), or it may be stored on a removable storage medium such as a DVD or CD-ROM (a non-transient storage medium) and installed on the storage device when the storage medium is inserted into the drive device. The storage device consists of, for example, an HDD, flash memory, EEPROM (Electrically Erasable Programmable Read Only Memory), ROM (Read Only Memory), or RAM (Random Access Memory).

[0150] The acquisition unit 11 receives predetermined information from the reaction operator and transmits the acquired information to the computer unit 12. The information acquired by the acquisition unit 11 in this embodiment is information about the feedstock oil, the product oil, and the operating conditions at a predetermined time after the start of the reaction, relating to the hydrogenation reaction of feedstock oil containing heavy coker cracked light oil. The information about the feedstock oil, the product oil, and the operating conditions at a predetermined time after the start of the reaction is as described above. For example, the acquisition unit 11 performs the information acquisition step described above. The acquisition unit 11 only needs to acquire information about the feedstock oil, the product oil, and the operating conditions at a predetermined time after the start of the reaction, and there are no particular limitations on the method of acquisition.

[0151] In this embodiment, the acquisition unit 11 is configured as a single keyboard. The specific configuration of the acquisition unit 11 is not limited; in this embodiment, it is a keyboard, but it may also be a touch panel or the like. Furthermore, acquisition units for acquiring various types of information may be configured separately and each may be independently connected to the computer main unit 12. Also, the acquisition unit 11 may be configured to directly acquire the aforementioned information via wired or wireless connection from a computer used for controlling reactors, etc.

[0152] The main unit of the computer 12 is, for example, a so-called computer capable of processing various kinds of information. The main unit of the computer 12 includes an arithmetic unit 13. For example, a predetermined program is incorporated into the main unit of the computer 12, and the arithmetic unit 13 is functionally configured by the execution of this program. Specifically, the arithmetic unit 13 calculates the degree of catalyst degradation using a degradation function based on information about the feedstock oil, information about the produced oil, and information about the operating conditions obtained by the acquisition unit 11 after a predetermined time has elapsed since the start of the reaction. Based on the degree of catalyst degradation, it calculates the information about the feedstock oil, information about the produced oil, and the reaction temperature required to satisfy the operating conditions. The degradation function is as described above. As described above, the reaction temperature can be determined, for example, from a degradation rate formula. For example, the arithmetic unit 13 executes the degradation degree calculation step and the reaction temperature calculation step described above. The arithmetic unit 13 may include, for example, a processor such as a CPU (Central Processing Unit) or MPU (Micro Processing Unit) and non-volatile or volatile semiconductor memory (e.g., RAM (Random Access Memory), ROM (Read Only Memory), flash memory, EPROM (Erasable Programmable Read Only Memory), EEPROM (Electrically Erasable Programmable Read Only Memory)). For example, the arithmetic unit 13 may be a microcontroller such as an MCU.

[0153] The calculation unit 13 may output to the output unit 14 information regarding the raw material oil obtained as described above, information regarding the produced oil, and information indicating the reaction temperature necessary to satisfy the operating conditions.

[0154] The output unit 14 receives the calculation result (reaction temperature) output by the computer main unit 12 (specifically, the calculation unit 13) and outputs the received calculation result to an external device. In this embodiment, the output unit 14 is composed of a display unit such as a CRT display, liquid crystal display, or PDP, but is not limited to these, and may be configured to output to a printing unit such as a printer, or to other devices (for example, a computer used for controlling the hydrogenation reaction of feedstock oil containing heavy coker cracked diesel fuel). The output unit 14 may also be a combination of these. For example, the output unit 14 performs the information output step described above.

[0155] Furthermore, this embodiment provides a reaction temperature calculation program for enabling a computer to function as a reaction temperature calculation device, and a non-temporarily readable recording medium for the computer that stores the program. Examples of non-temporarily readable recording media for the computer include magnetic tape (such as digital data storage (DSS)), magnetic disks (such as hard disk drives (HDD) and flexible disks (FD)), optical disks (such as compact discs (CD), digital versatile discs (DVD), and Blu-ray discs (BD)), magneto-optical disks (MO), and flash memory (such as SSDs (Solid State Drives), memory cards, and USB memory).

[0156] <Information Processing Method and Method for Utilizing Reaction Temperature Calculation Device> According to the information processing method and reaction temperature calculation device of this embodiment, it is possible to estimate the reaction temperature necessary to achieve predetermined reaction conditions in the hydrogenation reaction of feedstock oil containing heavy coker cracked light oil. According to the information processing method and reaction temperature calculation device of this embodiment, it is possible to obtain a time-series plot of the estimated reaction temperature. The following applications can be considered from the relationship between the plot and the maximum operating temperature of the equipment, etc.

[0157] The first application is to estimate the operating time (in days) required to replace the catalyst under predetermined reaction conditions. That is, the plot allows for the estimation of the time at which the maximum operating temperature of the equipment is reached, and from this time, the operating time (in days) required to replace the catalyst can be estimated. Furthermore, if the estimated reaction temperature is not below the equipment's set temperature, the information processing method shown in S4-1 to S4-3 of Figure 2 may be performed. The information processing method shown in S4-1 to S4-3 of Figure 2 includes an information acquisition step (S4-1 in Figure 2) to acquire information regarding the target reaction temperature, a degradation degree calculation step (S4-2 in Figure 2) to calculate the degree of catalyst degradation using a degradation function based on the acquired target reaction temperature, and a reaction condition calculation step (S4-3 in Figure 2) to calculate information regarding the feedstock oil, the product oil, and the operating conditions necessary to satisfy the target reaction temperature based on the degree of degradation. The method may further include an information output step (S4-4 in Figure 2) to output the information regarding the feedstock oil, the product oil, and the operating conditions obtained in this way. Specifically, for example, when using the Coke degradation function 1 and the silicon degradation function, the T in equation 23 above... t Substitute the desired reaction temperature into the equation and find Φ. Substitute the obtained Φ into equation 2 above and find Φ C , Φ Si We find the value of Φ obtained. C Substitute the above equation 3 to find D. Substitute the obtained D into the above equation 4 to find S such that the equation in the above equation 4 holds true. P S F We just need to find the combinations of LHSV and P. Also, in the above combinations, for example S P S F P and LHSV may be calculated using the following set values. Furthermore, any of the following Coke degradation functions may be used: Coke degradation function 1, Coke degradation function 1-1, Coke degradation function 2, or Coke degradation function 2-1. Also, the above is Φ Si The explanation was given on the premise that no changes would be made, C Without changing Φ Si You may change this. Specifically, in the silicon degradation function, Si f Si pThe conditions for WHSV may be changed. Note that each of the above steps is performed, for example, by the reaction temperature calculation device 1 of this embodiment. For example, S4-1 is performed by the acquisition unit 11, S4-2 and S4-3 are performed by the calculation unit 13 in the computer body 12, and S4-4 is performed by the output unit 14. Note that the target temperature may be stored in advance in the calculation unit 13 in the computer body 12.

[0158] A second application is to estimate the reaction conditions (processing rate (LHSV), etc.) required to achieve a predetermined operating time. Such an information processing method is represented by steps S1A to S3A in Figure 3. The information processing method shown in steps 1A to 3A in Figure 3 includes an information acquisition step (S1A in Figure 3) to acquire information regarding the target reaction temperature at a predetermined operating time, a degradation degree calculation step (S2A in Figure 3) to calculate the degree of catalyst degradation using a degradation function based on the acquired target reaction temperature, and a reaction condition calculation step (S3A in Figure 3) to calculate information regarding the feedstock oil, the product oil, and the operating conditions necessary to satisfy the target reaction temperature based on the degree of degradation. It may further include an information output step (S4A in Figure 3) to output the information regarding the feedstock oil, the product oil, and the operating conditions obtained in this way. Specifically, for example, when using the coke degradation function 1 and the silicon degradation function, the T in equation 23 t Substitute the desired reaction temperature into the equation and find Φ. Substitute the obtained Φ into equation 2 above and find Φ C , Φ Si We find the value of Φ obtained. C Substitute the above equation 3 to find D. Substitute the obtained D into the above equation 4 to find S such that the equation in the above equation 4 holds true. P S F We just need to find the combinations of LHSV and P. Also, in the above combinations, for example S P S F P and LHSV may be calculated using the following set values. Furthermore, any of the following Coke degradation functions may be used: Coke degradation function 1, Coke degradation function 1-1, Coke degradation function 2, or Coke degradation function 2-1. Also, the above is Φ SiThe explanation was given on the premise that no changes would be made, C Without changing Φ Si You may change this. Specifically, in the silicon degradation function, Si f Si p The conditions for WHSV may be changed. Note that each of the above steps is performed, for example, by the reaction temperature calculation device 1 of this embodiment. For example, S1A is performed by the acquisition unit 11, S2A and S3A are performed by the calculation unit 13 in the computer body 12, and S4A is performed by the output unit 14. Note that the target temperature may be stored in advance in the calculation unit 13 in the computer body 12. [Examples]

[0159] 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.

[0160] [Examples] A hydrogenation reaction was carried out on a bench scale by contacting a feed oil containing 100% by volume of heavy coker-cracked diesel fuel with a hydrogenation catalyst. Based on the obtained results, the degradation function was calculated. In this example, the coke degradation function 1-1 represented by equation 10 was used. The parameters in equations 11 and 20 were determined by the method described above, and were found to be α' = 0.0135, P B =15.9(MPa), a=0.6, Ec=156(kJ / mol), T B =643.15(K), T SOR =628.95(K), G B = 550 (Nm) 3 ( / kL), b=0.2, n=1.5, η=0.6, SiOC ∞ It was 9.0 (by weight).

[0161] The reaction was carried out in a real-world facility using the same feedstock oil and hydrogenation catalyst as in the hydrogenation reaction performed on a bench scale. The operating conditions in Equations 11 and 21 were as follows: F =3.54 (mass%), Si f =1.5(weight ppm), P=15.6(MPa), G=614(Nm 3 / kL), LHSV=0.787(hour -1 ), S P =0.1(mass%), Si p = 0 (weight ppm). Furthermore, when the activation energy for desulfurization was determined in advance using the method described above, it was found to be Ea = 120 (kJ / mol).

[0162] These basic degradation parameters and reaction conditions were substituted into Equation 11 to obtain D' at an arbitrary reaction time t days. The obtained D' and the number of reaction days t were substituted into Equation 10 to obtain Φ C We obtained Si f Si p Substitute the reaction elapsed days t, LHSV, crude oil flow rate, and catalyst filling amount into Equation 21 to obtain WHSV, and the obtained η and SiOC. ∞ Substitute Φ into the above equation 20. Si We obtained Φ. C and Φ Si Φ was determined from the above equation 2. The Φ, Ea, and T obtained in this way SOR Substitute this into equation 23 above to obtain the required temperature T after any reaction t days. t The following was determined. Table 1 shows the measured reaction temperatures for t=513 days, 1008 days, 2002 days, and 2474 days (however, S P The reaction temperature after correcting it to 0.1 (mass%), and the required temperature T determined by the above method. t , and the required temperature T t This shows the percentage of measured reaction temperatures.

[0163] [Table 1]

[0164] As shown in Table 1, the required temperature T obtained by the present invention t It was found that this value was almost equivalent to the measured reaction temperature. [Explanation of symbols]

[0165] 1. Reaction temperature calculation device 11...Acquisition part 12···Computer Body 13···Calculation Department 14···Output Department

Claims

1. Regarding the hydrogenation reaction of feedstock oil containing heavy coker cracked diesel fuel, an information acquisition step is performed to obtain information about the feedstock oil, information about the produced oil, and information about the operating conditions after a predetermined time has elapsed since the start of the reaction. A degradation degree calculation step in which the degree of catalyst degradation is calculated using a degradation function based on the acquired information on the raw material oil, the information on the produced oil, and the information on the operating conditions, An information processing method comprising: a step of calculating a reaction temperature based on the degree of deterioration of the catalyst, which calculates information regarding the feedstock oil, information regarding the produced oil, and the reaction temperature necessary to satisfy the operating conditions, The information relating to the feedstock oil includes information relating to the sulfur concentration and silicon concentration in the feedstock oil, the information relating to the produced oil includes information relating to the sulfur concentration and silicon concentration in the produced oil, and the information relating to the operating conditions includes information relating to the hydrogen partial pressure, information relating to the catalyst charge amount, and information relating to the feedstock oil supply amount. The aforementioned degradation function is a function represented by equation 2 below, in this information processing method. Φ = Φ Ｃ Φ Ｓｉ Formula 2 In the above formula 2, Φ is the degree of catalyst degradation, Ｃ Φ is the Coke degradation function represented by equation 3 below, Ｓｉ This is the silicon degradation function represented by equation 20 below. Φ Ｃ =exp(-Dt) Equation 3 In equation 3 above, D is the degradation coefficient of the active species of the catalyst due to coke, which is calculated from equation 4 below, and t is the number of days elapsed in the reaction. [Math 1] In the formula (4), α is a catalyst constant (a constant representing the rate of deterioration of the catalyst due to coke), and S Ｆ is the sulfur concentration (mass%) in the feedstock oil at the end of an arbitrary reaction day t, and S Ｐ is the sulfur concentration (mass%) in the product oil at the end of an arbitrary reaction day t. n is the reaction order of the hydrotreating reaction of the feedstock oil containing heavy coker cracked gas oil. LHSV is the liquid hourly space velocity (h －１ ) at the end of an arbitrary reaction day t, P Ｂ is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) at the end of an arbitrary reaction day t, a is the hydrogen partial pressure coefficient, Ec is the activation energy of coke deterioration (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol·K)), T Ｂ is the reference reaction temperature (K), T ＳＯＲ is the required temperature (K) on the 0th day. α, P Ｂ , a, Ec, T Ｂ , T ＳＯＲ are constants determined according to the catalyst used. These constants are determined while performing the reaction in a full-scale unit or are determined in advance on a bench scale based on full-scale operating conditions. [Math 2] In the above formula 20, Φ Ｓｉ is the degree of degradation, η is the catalyst effectiveness coefficient, SiOC is the amount of silicon deposited on the catalyst from the start of the reaction to a given reaction day t (unit: weight %), and SiOC ∞ is the maximum silicon deposition amount of the catalyst (unit: weight %). η is a catalyst-specific constant, greater than 0 and less than 1. Note that if SiOC = 0, Φ Ｓｉ = 1. η and SiOC ∞ η and SiOC are constants determined according to the catalyst used. ∞ This is determined by performing the reaction in the actual machine, or by determining it in advance on a bench scale based on the actual machine's operating conditions.

2. Regarding the hydrogenation reaction of feedstock oil containing heavy coker cracked diesel fuel, an information acquisition step is performed to obtain information about the feedstock oil, information about the produced oil, and information about the operating conditions after a predetermined time has elapsed since the start of the reaction. A degradation degree calculation step in which the degree of catalyst degradation is calculated using a degradation function based on the acquired information on the raw material oil, the information on the produced oil, and the information on the operating conditions, An information processing method comprising: a step of calculating a reaction temperature based on the degree of deterioration of the catalyst, which calculates information regarding the feedstock oil, information regarding the produced oil, and the reaction temperature necessary to satisfy the operating conditions, The information relating to the feed oil includes information relating to the sulfur concentration and silicon concentration in the feed oil, the information relating to the produced oil includes information relating to the sulfur concentration and silicon concentration in the produced oil, and the information relating to the operating conditions includes information relating to the partial pressure of hydrogen, information relating to the amount of catalyst charged, information relating to the amount of feed oil supplied, and information relating to the amount of hydrogen supplied. The aforementioned degradation function is a function represented by equation 2 below, in this information processing method. Φ = Φ Ｃ Φ Ｓｉ Formula 2 In the above formula 2, Φ is the degree of catalyst degradation, Ｃ Φ is the Coke degradation function represented by the following equation 10, Ｓｉ This is the silicon degradation function represented by equation 20 below. Φ Ｃ =exp(-D't) Equation 10 In the above equation 10, D' is the degradation coefficient of the active species of the catalyst due to coke, which is calculated from the following equation 11, and t is the number of days elapsed in the reaction. [Math 3] In the above equation 11, α' is the catalyst constant (a constant representing the degradation rate of the catalyst coke), and S Ｆ is the sulfur concentration (mass%) in the raw material oil after t days of any reaction, and S Ｐ is the sulfur concentration (mass%) in the produced oil after t days of any reaction, n is the reaction order of the hydrogenation reaction of the feedstock oil containing heavy coker cracked light oil, and LHSV is the liquid space velocity (h) after t days of any reaction. －１ ) and P Ｂ is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of any reaction, a is the hydrogen partial pressure coefficient, and G Ｂ This is the standard hydrogen / raw material ratio (Nm). ３ G is the hydrogen / raw material ratio (Nm) after any reaction t days. ３ T is (kL), b is the hydrogen / raw oil ratio coefficient, Ec is the activation energy for coke degradation (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol·K)), T Ｂ is the reference reaction temperature (K), and T ＳＯＲ α', P Ｂ a, G Ｂ , b, Ec, T Ｂ , T ＳＯＲ This constant is determined according to the catalyst used. This constant is determined by performing the reaction in the actual machine, or by determining it in advance on a bench scale based on the actual operating conditions. [Math 4] In the above formula 20, Φ Ｓｉ is the degree of degradation, η is the catalyst effectiveness coefficient, SiOC is the amount of silicon deposited on the catalyst from the start of the reaction to a given reaction day t (unit: weight %), and SiOC ∞ is the maximum silicon deposition amount of the catalyst (unit: weight %). η is a catalyst-specific constant, greater than 0 and less than 1. Note that if SiOC = 0, Φ Ｓｉ = 1. η and SiOC ∞ η and SiOC are constants determined according to the catalyst used. ∞ This is determined by performing the reaction in the actual machine, or by determining it in advance on a bench scale based on the actual machine's operating conditions.

3. Regarding the hydrogenation reaction of feedstock oil containing heavy coker cracked diesel fuel, an information acquisition step is performed to obtain information about the feedstock oil, information about the produced oil, and information about the operating conditions after a predetermined time has elapsed since the start of the reaction. A degradation degree calculation step in which the degree of catalyst degradation is calculated using a degradation function based on the acquired information on the raw material oil, the information on the produced oil, and the information on the operating conditions, An information processing method comprising: a step of calculating a reaction temperature based on the degree of deterioration of the catalyst, which calculates information regarding the feedstock oil, information regarding the produced oil, and the reaction temperature necessary to satisfy the operating conditions, The information relating to the feedstock oil includes information relating to the sulfur concentration and silicon concentration in the feedstock oil, the information relating to the produced oil includes information relating to the sulfur concentration and silicon concentration in the produced oil, and the information relating to the operating conditions includes information relating to the hydrogen partial pressure, information relating to the catalyst charge amount, and information relating to the feedstock oil supply amount. The aforementioned degradation function is a function represented by equation 2 below, in this information processing method. Φ = Φ Ｃ Φ Ｓｉ Equation 2 In the above formula 2, Φ is the degree of catalyst degradation, Ｃ Φ is the Coke degradation function represented by equation 13 below, Ｓｉ This is the silicon degradation function represented by equation 20 below. Φ Ｃ =k 1 ×exp(-D) １ t) + k ２ ×exp(-D) ２ t) Equation 13 In the above formula 13, k １ k is the activity site coefficient of the easily deactivating active species of the catalyst, ２ D is the activity site coefficient of the inactivatable active species of the catalyst, and the activity site coefficient represents the relative reaction rate constant of both active species. １ This is the degradation coefficient of the easily deactivating active species of the catalyst due to coke, and is calculated from the following equation 14, D ２ is the degradation coefficient of the inactivating active species of the catalyst due to coke, and is calculated from the following equation 15, where t is the number of days elapsed in the reaction, and k １ +k ２ = 1, and k １ and k ２ This is determined by performing the reaction in the actual machine, or by determining it in advance on a bench scale based on the actual machine's operating conditions. [Math 5] [Math 6] In formulas 14 and 15, S Ｆ is the sulfur concentration (mass%) in the raw material oil after t days of any reaction, and S Ｐ is the sulfur concentration (mass%) in the produced oil after t days of any reaction, n is the reaction order of the hydrogenation reaction of the feedstock oil containing heavy coker cracked light oil, and LHSV is the liquid space velocity (h) after t days of any reaction. －１ ) and P Ｂ is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of any reaction, a is the hydrogen partial pressure coefficient, Ec is the activation energy of coke degradation (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol·K)), and T Ｂ is the reference reaction temperature (K), and T ＳＯＲ is the required temperature (K) on day 0. In the above equation 14, α １ α is the catalytic constant of the easily deactivating active site (a constant representing the rate of degradation of the catalyst by coke), and in the above formula 15, ２ α is the catalytic constant of the non-inactivating active site (a constant representing the rate of degradation of the catalyst by coke). １ , α ２ , P Ｂ a, Ec, T Ｂ , T ＳＯＲ This constant is determined according to the catalyst used. This constant is determined by conducting the reaction in the actual machine, or by determining it in advance on a bench scale based on the actual operating conditions. [Number 7] In the above formula 20, Φ Ｓｉ is the degree of degradation, η is the catalyst effectiveness coefficient, SiOC is the amount of silicon deposited on the catalyst from the start of the reaction to a given reaction day t (unit: weight %), and SiOC ∞ is the maximum silicon deposition amount of the catalyst (unit: weight %). η is a catalyst-specific constant, greater than 0 and less than 1. Note that if SiOC = 0, Φ Ｓｉ = 1. η and SiOC ∞ η and SiOC are constants determined according to the catalyst used. ∞ This is determined by performing the reaction in the actual machine, or by determining it in advance on a bench scale based on the actual machine's operating conditions.

4. Regarding the hydrogenation reaction of feedstock oil containing heavy coker cracked diesel fuel, an information acquisition step is performed to obtain information about the feedstock oil, information about the produced oil, and information about the operating conditions after a predetermined time has elapsed since the start of the reaction. A degradation degree calculation step in which the degree of catalyst degradation is calculated using a degradation function based on the acquired information on the raw material oil, the information on the produced oil, and the information on the operating conditions, An information processing method comprising: a step of calculating a reaction temperature based on the degree of deterioration of the catalyst, which calculates information regarding the feedstock oil, information regarding the produced oil, and the reaction temperature necessary to satisfy the operating conditions, The information relating to the feed oil includes information relating to the sulfur concentration and silicon concentration in the feed oil, the information relating to the produced oil includes information relating to the sulfur concentration and silicon concentration in the produced oil, and the information relating to the operating conditions includes information relating to the partial pressure of hydrogen, information relating to the amount of catalyst charged, information relating to the amount of feed oil supplied, and information relating to the amount of hydrogen supplied. The aforementioned degradation function is a function represented by equation 2 below, in this information processing method. Φ = Φ Ｃ Φ Ｓｉ Equation 2 In the above formula 2, Φ is the degree of catalyst degradation, Ｃ Φ is the Coke degradation function represented by equation 17 below, Ｓｉ This is the silicon degradation function represented by equation 20 below. Φ Ｃ =k 1 ×exp(-D) １ 't) + k ２ ×exp(-D) ２ 't) Equation 17 In the formula 17, k １ is the active site coefficient of the easily deactivated active species of the catalyst, and k ２ is the active site coefficient of the hardly deactivated active species of the catalyst. The active site coefficient represents the relative reaction rate constant of both active species. D １ ’ is the coke degradation coefficient of the easily deactivated active species of the catalyst and is calculated from the following formula 18. D ２ ’ is the coke degradation coefficient of the hardly deactivated active species of the catalyst and is calculated from the following formula 19. t is the number of days elapsed since the start of the reaction (days), and k １ + k ２ = 1. k １ and k ２ are determined while conducting the reaction in a real machine or are determined in advance on a bench scale based on the real machine operation conditions. [Number 8] [Number 9] In the above formulas 18 and 19, S Ｆ is the sulfur concentration (mass %) in the feedstock oil at the end of an arbitrary reaction day t, S Ｐ is the sulfur concentration (mass %) in the product oil at the end of an arbitrary reaction day t, n is the reaction order of the hydrotreating reaction of the feedstock oil containing heavy coker cracked gas oil, LHSV is the liquid hourly space velocity (h －１ -1) at the end of an arbitrary reaction day t, P Ｂ is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) at the end of an arbitrary reaction day t, a is the hydrogen partial pressure coefficient, G Ｂ is the reference hydrogen / feedstock oil ratio (Nm ３ 3 / kL), G is the hydrogen / feedstock oil ratio (Nm ３ 3 / kL) at the end of an arbitrary reaction day t, b is the hydrogen / feedstock oil ratio coefficient, Ec is the activation energy of coke deterioration (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol·K)), T Ｂ is the reference reaction temperature (K), T ＳＯＲ is the required temperature (K) on the 0th day. In the above formula 18, α １ ' is the catalyst constant of the easily deactivated active site (a constant representing the deterioration rate of the catalyst due to coke), in the above formula 19, α ２ ' is the catalyst constant of the hardly deactivated active site (a constant representing the deterioration rate of the catalyst due to coke). α １ ', α ２ ', P Ｂ , a, G Ｂ , b, Ec, T Ｂ , T ＳＯＲ are constants determined according to the catalyst used. η and SiO C ∞ are obtained while performing the reaction in a real machine, or are obtained in advance on a bench scale based on the real machine operating conditions. [Number 10] In the above formula 20, Φ Ｓｉ is the degree of degradation, η is the catalyst effectiveness coefficient, SiOC is the amount of silicon deposited on the catalyst from the start of the reaction to a given reaction day t (unit: weight %), and SiOC ∞ is the maximum silicon deposition amount of the catalyst (unit: weight %). η is a catalyst-specific constant, greater than 0 and less than 1. Note that if SiOC = 0, Φ Ｓｉ = 1. η and SiOC ∞ η and SiOC are constants determined according to the catalyst used. ∞ This is determined by performing the reaction in the actual machine, or by determining it in advance on a bench scale based on the actual machine's operating conditions.

5. A reaction temperature calculation device comprising: an acquisition unit that acquires information on the raw material oil, information on the product oil, and information on the operating conditions after a predetermined time has elapsed since the start of the reaction, with respect to a hydrogenation reaction of a raw material oil containing heavy coker cracked light oil; and a calculation unit that calculates the degree of catalyst degradation using a degradation function based on the information on the raw material oil, the information on the product oil, and the information on the operating conditions acquired by the acquisition unit, and calculates the reaction temperature necessary to satisfy the information on the raw material oil, the information on the product oil, and the operating conditions based on the calculated degree of catalyst degradation, wherein The information relating to the feedstock oil includes information relating to the sulfur concentration and silicon concentration in the feedstock oil, the information relating to the produced oil includes information relating to the sulfur concentration and silicon concentration in the produced oil, and the information relating to the operating conditions includes information relating to the hydrogen partial pressure, information relating to the catalyst charge amount, and information relating to the feedstock oil supply amount. The aforementioned degradation function is the function represented by equation 2 below, in the reaction temperature calculation device. Φ = Φ Ｃ Φ Ｓｉ Formula 2 In the above formula 2, Φ is the degree of catalyst degradation, Ｃ Φ is the Coke degradation function represented by equation 3 below, Ｓｉ This is the silicon degradation function represented by equation 20 below. Φ Ｃ =exp(-Dt) Equation 3 In equation 3 above, D is the degradation coefficient of the active species of the catalyst due to coke, which is calculated from equation 4 below, and t is the number of days elapsed in the reaction. [Math 11] In the above equation 4, α is the catalyst constant (a constant representing the rate of degradation of the catalyst due to coke), and S Ｆ is the sulfur concentration (mass%) in the raw material oil after t days of any reaction, and S Ｐ is the sulfur concentration (mass%) in the produced oil after t days of any reaction, n is the reaction order of the hydrogenation reaction of the feedstock oil containing heavy coker cracked light oil, and LHSV is the liquid space velocity (h) after t days of any reaction. －１ ) and P Ｂ is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of any reaction, a is the hydrogen partial pressure coefficient, Ec is the activation energy of coke degradation (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol·K)), and T Ｂ is the reference reaction temperature (K), and T ＳＯＲ α, P is the required temperature (K) on day 0. Ｂ a, Ec, T Ｂ , T ＳＯＲ This constant is determined according to the catalyst used. This constant is determined by performing the reaction in the actual machine, or by determining it in advance on a bench scale based on the actual operating conditions. [Math 12] In the above formula 20, Φ Ｓｉ is the degree of degradation, η is the catalyst effectiveness coefficient, SiOC is the amount of silicon deposited on the catalyst from the start of the reaction to a given reaction day t (unit: weight %), and SiOC ∞ is the maximum silicon deposition amount of the catalyst (unit: weight %). η is a catalyst-specific constant, greater than 0 and less than 1. Note that if SiOC = 0, Φ Ｓｉ = 1. η and SiOC ∞ η and SiOC are constants determined according to the catalyst used. ∞ This is determined by performing the reaction in the actual machine, or by determining it in advance on a bench scale based on the actual machine's operating conditions.

6. A reaction temperature calculation device comprising: an acquisition unit that acquires information on the raw material oil, information on the product oil, and information on the operating conditions after a predetermined time has elapsed since the start of the reaction, with respect to a hydrogenation reaction of a raw material oil containing heavy coker cracked light oil; and a calculation unit that calculates the degree of catalyst degradation using a degradation function based on the information on the raw material oil, the information on the product oil, and the information on the operating conditions acquired by the acquisition unit, and calculates the reaction temperature necessary to satisfy the information on the raw material oil, the information on the product oil, and the operating conditions based on the calculated degree of catalyst degradation, wherein The information relating to the feed oil includes information relating to the sulfur concentration and silicon concentration in the feed oil, the information relating to the produced oil includes information relating to the sulfur concentration and silicon concentration in the produced oil, and the information relating to the operating conditions includes information relating to the partial pressure of hydrogen, information relating to the amount of catalyst charged, information relating to the amount of feed oil supplied, and information relating to the amount of hydrogen supplied. The aforementioned degradation function is the function represented by equation 2 below, in the reaction temperature calculation device. Φ = Φ Ｃ Φ Ｓｉ Formula 2 In the above formula 2, Φ is the degree of catalyst degradation, Ｃ Φ is the Coke degradation function represented by the following equation 10, Ｓｉ This is the silicon degradation function represented by equation 20 below. Φ Ｃ =exp(-D't) Equation 10 In the above equation 10, D' is the degradation coefficient of the active species of the catalyst due to coke, which is calculated from the following equation 11, and t is the number of days elapsed in the reaction. [Number 13] In the above equation 11, α' is the catalyst constant (a constant representing the degradation rate of the catalyst coke), and S Ｆ is the sulfur concentration (mass%) in the raw material oil after t days of any reaction, and S Ｐ is the sulfur concentration (mass%) in the produced oil after t days of any reaction, n is the reaction order of the hydrogenation reaction of the feedstock oil containing heavy coker cracked light oil, and LHSV is the liquid space velocity (h) after t days of any reaction. －１ ) and P Ｂ is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of any reaction, a is the hydrogen partial pressure coefficient, and G Ｂ This is the standard hydrogen / raw material ratio (Nm). ３ G is the hydrogen / raw material ratio (Nm) after any reaction t days. ３ T is (kL), b is the hydrogen / raw oil ratio coefficient, Ec is the activation energy for coke degradation (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol·K)), T Ｂ is the reference reaction temperature (K), and T ＳＯＲ α', P Ｂ a, G Ｂ , b, Ec, T Ｂ , T ＳＯＲ This constant is determined according to the catalyst used. This constant is determined by performing the reaction in the actual machine, or by determining it in advance on a bench scale based on the actual operating conditions. [Number 14] In the above formula 20, Φ Ｓｉ is the degree of degradation, η is the catalyst effectiveness coefficient, SiOC is the amount of silicon deposited on the catalyst from the start of the reaction to a given reaction day t (unit: weight %), and SiOC ∞ is the maximum silicon deposition amount of the catalyst (unit: weight %). η is a catalyst-specific constant, greater than 0 and less than 1. Note that if SiOC = 0, Φ Ｓｉ = 1. η and SiOC ∞ η and SiOC are constants determined according to the catalyst used. ∞ This is determined by performing the reaction in the actual machine, or by determining it in advance on a bench scale based on the actual machine's operating conditions.

7. A reaction temperature calculation device comprising: an acquisition unit that acquires information on the raw material oil, information on the product oil, and information on the operating conditions after a predetermined time has elapsed since the start of the reaction, with respect to a hydrogenation reaction of a raw material oil containing heavy coker cracked light oil; and a calculation unit that calculates the degree of catalyst degradation using a degradation function based on the information on the raw material oil, the information on the product oil, and the information on the operating conditions acquired by the acquisition unit, and calculates the reaction temperature necessary to satisfy the information on the raw material oil, the information on the product oil, and the operating conditions based on the calculated degree of catalyst degradation, wherein The information relating to the feedstock oil includes information relating to the sulfur concentration and silicon concentration in the feedstock oil, the information relating to the produced oil includes information relating to the sulfur concentration and silicon concentration in the produced oil, and the information relating to the operating conditions includes information relating to the hydrogen partial pressure, information relating to the catalyst charge amount, and information relating to the feedstock oil supply amount. The aforementioned degradation function is the function represented by equation 2 below, in the reaction temperature calculation device. Φ = Φ Ｃ Φ Ｓｉ Formula 2 In the above formula 2, Φ is the degree of catalyst degradation, Ｃ Φ is the Coke degradation function represented by equation 13 below, Ｓｉ This is the silicon degradation function represented by equation 20 below. Φ Ｃ =k 1 ×exp(-D) １ t) + k ２ ×exp(-D) ２ t) Equation 13 In the above formula 13, k １ k is the activity site coefficient of the easily deactivating active species of the catalyst, ２ D is the activity site coefficient of the inactivatable active species of the catalyst, and the activity site coefficient represents the relative reaction rate constant of both active species. １ This is the degradation coefficient of the easily deactivating active species of the catalyst due to coke, and is calculated from the following equation 14, D ２ is the degradation coefficient of the inactivating active species of the catalyst due to coke, and is calculated from the following equation 15, where t is the number of days elapsed in the reaction, and k １ +k ２ = 1, and k １ and k ２ This is determined by performing the reaction in the actual machine, or by determining it in advance on a bench scale based on the actual machine's operating conditions. [Number 15] [Number 16] In formulas 14 and 15, S Ｆ is the sulfur concentration (mass%) in the raw material oil after t days of any reaction, and S Ｐ is the sulfur concentration (mass%) in the produced oil after t days of any reaction, n is the reaction order of the hydrogenation reaction of the feedstock oil containing heavy coker cracked light oil, and LHSV is the liquid space velocity (h) after t days of any reaction. －１ ) and P Ｂ is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of any reaction, a is the hydrogen partial pressure coefficient, Ec is the activation energy of coke degradation (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol·K)), and T Ｂ is the reference reaction temperature (K), and T ＳＯＲ is the required temperature (K) on day 0. In the above equation 14, α １ α is the catalytic constant of the easily deactivating active site (a constant representing the rate of degradation of the catalyst by coke), and in the above formula 15, ２ α is the catalytic constant of the non-inactivating active site (a constant representing the rate of degradation of the catalyst by coke). １ , α ２ , P Ｂ a, Ec, T Ｂ , T ＳＯＲ This constant is determined according to the catalyst used. This constant is determined by conducting the reaction in the actual machine, or by determining it in advance on a bench scale based on the actual operating conditions. [Number 17] In the above formula 20, Φ Ｓｉ is the degree of degradation, η is the catalyst effectiveness coefficient, SiOC is the amount of silicon deposited on the catalyst from the start of the reaction to a given reaction day t (unit: weight %), and SiOC ∞ is the maximum silicon deposition amount of the catalyst (unit: weight %). η is a catalyst-specific constant, greater than 0 and less than 1. Note that if SiOC = 0, Φ Ｓｉ = 1. η and SiOC ∞ η and SiOC are constants determined according to the catalyst used. ∞ This is determined by performing the reaction in the actual machine, or by determining it in advance on a bench scale based on the actual machine's operating conditions.

8. A reaction temperature calculation device comprising: an acquisition unit that acquires information on the raw material oil, information on the product oil, and information on the operating conditions after a predetermined time has elapsed since the start of the reaction, with respect to a hydrogenation reaction of a raw material oil containing heavy coker cracked light oil; and a calculation unit that calculates the degree of catalyst degradation using a degradation function based on the information on the raw material oil, the information on the product oil, and the information on the operating conditions acquired by the acquisition unit, and calculates the reaction temperature necessary to satisfy the information on the raw material oil, the information on the product oil, and the operating conditions based on the calculated degree of catalyst degradation, wherein The information relating to the feed oil includes information relating to the sulfur concentration and silicon concentration in the feed oil, the information relating to the produced oil includes information relating to the sulfur concentration and silicon concentration in the produced oil, and the information relating to the operating conditions includes information relating to the partial pressure of hydrogen, information relating to the amount of catalyst charged, information relating to the amount of feed oil supplied, and information relating to the amount of hydrogen supplied. The aforementioned degradation function is the function represented by equation 2 below, in the reaction temperature calculation device. Φ = Φ Ｃ Φ Ｓｉ Formula 2 In the above formula 2, Φ is the degree of catalyst degradation, Ｃ Φ is the Coke degradation function represented by equation 17 below, Ｓｉ This is the silicon degradation function represented by equation 20 below. Φ Ｃ =k 1 ×exp(-D) １ 't) + k ２ ×exp(-D) ２ 't) Equation 17 In the above formula 17, k １ k is the activity site coefficient of the easily deactivating active species of the catalyst, ２ D is the activity site coefficient of the inactivatable active species of the catalyst, and the activity site coefficient represents the relative reaction rate constant of both active species. １ ' is the degradation coefficient of the easily deactivating active species of the catalyst, and is calculated from the following equation 18, D ２ ' is the degradation coefficient of the coke of the inactivating active species of the catalyst, calculated from equation 19 below, where t is the number of days elapsed in the reaction, and k １ +k ２ = 1, and k １ and k ２ This is determined by performing the reaction in the actual machine, or by determining it in advance on a bench scale based on the actual machine's operating conditions. [Number 18] [Number 19] In formulas 18 and 19, S Ｆ is the sulfur concentration (mass%) in the raw material oil after t days of any reaction, and S Ｐ is the sulfur concentration (mass%) in the produced oil after t days of any reaction, n is the reaction order of the hydrogenation reaction of the feedstock oil containing heavy coker cracked light oil, and LHSV is the liquid space velocity (h) after t days of any reaction. －１ ) and P Ｂ is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of any reaction, a is the hydrogen partial pressure coefficient, and G Ｂ This is the standard hydrogen / raw material ratio (Nm). ３ G is the hydrogen / raw material ratio (Nm) after any reaction t days. ３ T is (kL), b is the hydrogen / raw oil ratio coefficient, Ec is the activation energy for coke degradation (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol·K)), T Ｂ is the reference reaction temperature (K), and T ＳＯＲ is the required temperature (K) on day 0. In the above equation 18, α １ ' is the catalytic constant of the easily deactivating active site (a constant representing the rate of degradation of the catalyst by coke), and in the above formula 19, α ２ ' is the catalytic constant of the non-inactivating active site (a constant representing the rate of degradation of the catalyst due to coke). α １ ', α ２ ', P Ｂ a, G Ｂ , b, Ec, T Ｂ , T ＳＯＲ This constant is determined according to the catalyst used. This constant is determined by conducting the reaction in the actual machine, or by determining it in advance on a bench scale based on the actual operating conditions. [Number 20] In the above formula 20, Φ Ｓｉ is the degree of degradation, η is the catalyst effectiveness coefficient, SiOC is the amount of silicon deposited on the catalyst from the start of the reaction to a given reaction day t (unit: weight %), and SiOC ∞ is the maximum silicon deposition amount of the catalyst (unit: weight %). η is a catalyst-specific constant, greater than 0 and less than 1. Note that if SiOC = 0, Φ Ｓｉ = 1. η and SiOC ∞ η and SiOC are constants determined according to the catalyst used. ∞ This is determined by performing the reaction in the actual machine, or by determining it in advance on a bench scale based on the actual machine's operating conditions.

9. A reaction temperature calculation program for causing a computer to function as a reaction temperature calculation device according to any one of claims 5 to 8.

10. A non-temporary readable recording medium for a computer storing the program described in claim 9.

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