Information processing method, reaction temperature calculation device, reaction temperature calculation program, and non-transitory readable recording medium for a computer

Abstract

To provide, regarding hydrotreating reaction of raw oil including atmospheric distillation residue oil, an information processing method capable of estimating a reaction temperature required to achieve a predetermined reaction condition, a reaction temperature calculation device, a reaction temperature calculation program, and a non-temporary readable recording medium for a computer.SOLUTION: An information processing method includes: an information acquisition step to acquire information on raw oil including atmospheric distillation residue oil when a predetermined time has passed since start of reaction, information on product oil and information on an operation condition; a deterioration level calculation step to calculate the deterioration level of a catalyst by a deterioration function on the basis of the acquired information; and a reaction temperature calculation step to calculate a reaction temperature required to satisfy the information on raw oil, the information on product oil, and the operation condition.SELECTED DRAWING: Figure 1

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-transitory readable recording medium for a computer.

Background Art

[0002] The atmospheric distillation residue oil obtained by atmospheric distillation of crude oil contains a high concentration of sulfur. A method of reducing the sulfur content by hydrotreating the atmospheric distillation residue oil is known as direct desulfurization.

[0003] In the hydrotreating of atmospheric distillation residue oil, coke is generated as a by-product, and when the coke accumulates on the hydrotreating catalyst, the activity of the hydrotreating catalyst decreases over time. In addition, the atmospheric distillation residue oil contains metal compounds such as nickel compounds and vanadium compounds, and when these compounds accumulate on the hydrotreating catalyst as metals, the activity of the hydrotreating catalyst also decreases over time. Therefore, in order to keep the sulfur content in the produced oil below a certain level, the reaction temperature must be increased for operation against the decrease in the activity of the hydrotreating catalyst.

[0004] In setting this reaction temperature, if the reaction temperature is too high, the decrease in the activity of the catalyst progresses, so that a predetermined operation time (number of days) cannot be achieved and the productivity decreases. On the other hand, if the reaction temperature is too low, the decrease in the activity of the catalyst is alleviated, so that a surplus occurs by the predetermined operation time, and if the surplus cannot be utilized, the productivity decreases. Therefore, a method for accurately estimating predetermined reaction conditions (temperature, throughput) 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, from information on the properties of atmospheric distillation light oil before switching and operating conditions, and information on the properties of atmospheric distillation light oil after switching and operating conditions other than the reaction temperature, in the hydrogenation treatment of a feedstock oil containing atmospheric distillation light oil.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] The method for estimating the reaction temperature described in Patent Document 1 focuses on the properties of the feedstock oil and has not been studied from the perspective of the decrease in the activity of the hydrogenation treatment catalyst. Therefore, a method for estimating the optimal reaction temperature while considering the decrease in the activity of the hydrogenation treatment catalyst is desired.

[0008] The present invention has been made in view of the above circumstances, and relates to an information processing method capable of estimating the reaction temperature necessary to achieve predetermined reaction conditions in the hydrogenation treatment reaction of a feedstock oil containing atmospheric distillation residue oil, and 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 of a computer storing the program.

Means for Solving the Problems

[0009] To solve the above problems, the present invention has the following aspects. [1] Regarding the hydrotreating reaction of a feedstock oil containing atmospheric distillation residue oil, an information acquisition step of acquiring information regarding the feedstock oil, information regarding the produced oil, and information regarding the operating conditions when a predetermined time has elapsed since the start of the reaction; a deterioration degree calculation step of calculating the deterioration degree of the catalyst using a deterioration function based on the acquired information regarding the feedstock oil, the information regarding the produced oil, and the information regarding the operating conditions; and a reaction temperature calculation step of calculating the reaction temperature necessary to satisfy the information regarding the feedstock oil, the information regarding the produced oil, and the operating conditions based on the deterioration degree of the catalyst. An information processing method including these steps. [2] The information processing method according to [1], wherein the deterioration function is composed of a coke deterioration function regarding the deterioration of the catalyst due to the deposition of coke and a metal deterioration function regarding the deterioration of the catalyst due to the deposition of metal. [3] The information processing method according to [1] or [2], wherein the information regarding the feedstock oil includes information regarding the sulfur concentration in the feedstock oil, and the information regarding the produced oil includes information regarding the sulfur concentration in the produced oil. [4] The information processing method according to any one of [1] to [3], wherein the information regarding the operating conditions includes information regarding the hydrogen partial pressure, information regarding the catalyst filling amount, and information regarding the supply amount of the feedstock oil. [5] Regarding the hydrotreating reaction of a feedstock oil containing atmospheric distillation residue oil, an acquisition unit that acquires information regarding the feedstock oil, information regarding the produced oil, and information regarding the operating conditions when a predetermined time has elapsed since the start of the reaction; and an arithmetic unit that calculates the deterioration degree of the catalyst using a deterioration function based on the information regarding the feedstock oil, the information regarding the produced oil, and the information regarding the operating conditions acquired by the acquisition unit, and calculates the reaction temperature necessary to satisfy the information regarding the feedstock oil, the information regarding the produced oil, and the operating conditions based on the calculated deterioration degree of the catalyst. A reaction temperature calculation device including these units. [6] The reaction temperature calculation device according to [5], wherein the deterioration function is composed of a coke deterioration function regarding the deterioration of the catalyst due to the deposition of coke and a metal deterioration function regarding the deterioration of the catalyst due to the deposition of metal. [7] The information regarding the feedstock oil includes information on the sulfur concentration in the feedstock oil, and the information regarding the product oil includes information on the sulfur concentration in the product oil. The reaction temperature calculation device according to [5] or [6]. [8] The information regarding the operating conditions includes information on the hydrogen partial pressure, information on the catalyst filling amount, and information on the feedstock oil supply amount. The reaction temperature calculation device according to any one of [5] to [7]. [9] A reaction temperature calculation program for causing a computer to function as the reaction temperature calculation device according to any one of [5] to [8].

[10] A non-transitory readable recording medium of a computer storing the program according to [9]. [Advantages of the Invention]

[0010] According to the present invention, an information processing method for estimating the reaction temperature necessary to achieve predetermined reaction conditions for the hydrotreating reaction of a feedstock oil containing atmospheric distillation residue 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-transitory readable recording medium of a computer storing the program can be provided. [Brief Description of the Drawings]

[0011]

Figure 1

Figure 2

Figure 3

Figure 4

[0012] Hereinafter, embodiments of the present invention will be described in detail. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to these contents, and can be implemented with modifications within the scope of the gist thereof.

[0013] ≪Information Processing Method≫ The information processing method of the present embodiment relates to a hydrotreating reaction of a feedstock oil containing atmospheric residue oil, and includes an information acquisition step (S1 in FIG. 1) of acquiring information on the feedstock oil, information on the produced oil, and information on operating conditions when a predetermined time has elapsed since the start of the reaction; a deterioration degree calculation step (S2 in FIG. 1) of calculating the deterioration degree of the catalyst by a deterioration function based on the acquired information on the feedstock oil, the information on the produced oil, and the information on the operating conditions; and a reaction temperature calculation step (S3 in FIG. 1) of calculating a reaction temperature necessary to satisfy the information on the feedstock oil, the information on the produced oil, and the operating conditions based on the deterioration degree of the catalyst. Hereinafter, each step will be described. Note that each step shown below is executed, for example, by the reaction temperature calculation device 1 of the present embodiment. For example, S1 is executed by the acquisition unit 11, and S2 and S3 are executed by the calculation unit 13 in the computer main body 12.

[0014] ≪Information Acquisition Step≫ The information acquisition step of the present embodiment is a step of acquiring information on the feedstock oil, information on the produced oil, and information on operating conditions when a predetermined time has elapsed since the start of the reaction. The time when a predetermined time has elapsed since the start of the reaction is, for example, when an arbitrary t days have elapsed since the start of the reaction. t may be an integer or a decimal. For example, when t is 0.5, it means when 12 hours have elapsed since the start of the reaction. Also, the time when t days have elapsed may be in the past, present, or future as viewed from the time when the information processing method of the present embodiment is implemented. For example, when the time when the information processing method of the present embodiment is implemented is when 2 days have elapsed since the start of the reaction and t is 4, the reaction temperature 2 days later (in the future) will be estimated.

[0015] (Information on the Feedstock Oil) Examples of information on the feedstock oil include information on the composition of the feedstock oil. Examples of information on the composition of the feedstock oil include information on the sulfur concentration and metal concentration in the feedstock oil.

[0016] Information on the sulfur concentration in the feedstock oil can be obtained by a sulfur concentration measurement method known in the art, and can be determined, for example, by an ultraviolet fluorescence method, a wavelength-dispersive X-ray fluorescence method, or the like. Further, the sulfur concentration in the feedstock oil can be controlled by changing the feedstock oil. The information on the sulfur concentration in the feedstock oil is preferably a set value. That is, the sulfur concentration of the feedstock oil planned to be used can be used.

[0017] Information on the metal concentration in the feedstock oil can be obtained by a metal concentration measurement method known in the art, and can be determined, for example, by an ICP-MS method, a X-ray fluorescence analysis method, or the like. Further, the metal concentration in the feedstock oil can be controlled by changing the feedstock oil. The information on the metal concentration in the feedstock oil is preferably a set value. That is, the metal concentration of the feedstock oil planned to be used can be used.

[0018] (Information on the produced oil) Examples of information on the produced oil include information on the composition of the produced oil. Examples of information on the composition of the produced oil include information on the sulfur concentration and metal concentration in the produced oil.

[0019] Information on the sulfur concentration in the produced oil can be determined in the same manner as in the case of the above-described feedstock oil. In the present embodiment, the information on the sulfur concentration in the produced oil is preferably a set value. That is, the sulfur concentration of the target produced oil can be used.

[0020] Information on the metal concentration in the produced oil can be obtained in the same manner as in the case of the raw material oil described above. In the present embodiment, the information on the metal concentration in the produced oil is preferably a set value. That is, the target metal concentration of the produced oil can be used. Note that when the sulfur concentration in the produced oil described above is constant, the metal concentration in the produced oil also becomes constant.

[0021] (Information on operating conditions) Examples of the information on the operating conditions include information on the hydrogen partial pressure, information on the catalyst filling amount, information on the supply amount of the raw material oil, and information on the supply amount of hydrogen. For example, the information on the operating conditions is at least any one of the information on the hydrogen partial pressure, information on the catalyst filling amount, information on the supply amount of the raw material oil, and information on the supply amount of hydrogen. Among them, the information on the operating conditions preferably includes the information on the hydrogen partial pressure, information on the catalyst filling amount, and information on the supply amount of the raw material oil, and more preferably includes all of the information on the hydrogen partial pressure, information on the catalyst filling amount, information on the supply amount of the raw material oil, and information on the supply amount of hydrogen. Further, the operating conditions also include information on time such as when an arbitrary t days have elapsed after starting the reaction. Further, the operating conditions include information on the measured value of the reaction temperature.

[0022] The information on the hydrogen partial pressure, information on the catalyst filling amount, information on the supply amount of the raw material oil, and information on the supply amount of hydrogen can be obtained by methods known in the art. The information on the hydrogen partial pressure, information on the catalyst filling amount, information on the supply amount of the raw material oil, and information on the supply amount of hydrogen can be controlled in the hydrotreating reaction of the raw material oil containing atmospheric residue. The information on the operating conditions is preferably a set value. That is, the planned operating conditions are used.

[0023] <<Degradation degree calculation step>> The degradation degree calculation step of the present embodiment is a step of calculating the degradation degree of the catalyst by a degradation function based on the obtained information on the raw material oil, the information on the produced oil, and the information on 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 formula 1, k0 is the reaction rate constant of the catalyst after 0 days of 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 reaction. t is the temperature T SOR is the reaction rate constant at

[0025] In this embodiment, the degree of catalyst deterioration can be calculated using a deterioration function based on the acquired information on the feedstock oil, information on the refined oil, and information on the operating conditions.

[0026] <Degradation function> The deterioration function is a function for calculating the deterioration level of a catalyst. In this embodiment, the deterioration function is preferably composed of a coke deterioration function relating to catalyst deterioration due to coke deposition and a metal deterioration function relating to catalyst deterioration due to metal deposition. Such a deterioration function is not particularly limited, but an example thereof is the deterioration function expressed by the following equation 2.

[0027] Φ=Φ C Φ M formula 2 In the above formula 2, Φ C is the coke degradation function, and Φ M is the metal degradation function.

[0028] The coke deterioration function and the metal deterioration function will be explained below.

[0029] <Coke deterioration function 1> The coke deterioration function is not particularly limited as long as it is a function that can calculate the degree of deterioration related to coke deterioration of the catalyst. For example, coke deterioration function 1 expressed by the following formula 3 can be given 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). The following 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] In the above formula (4), α is a catalyst constant (a constant representing the deterioration rate due to coke of the catalyst), and S F is the sulfur concentration (mass%) in the feedstock oil at any time t days after the start of the reaction, and S P is the sulfur concentration (mass%) in the product oil at any time t days after the start of the reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric residue oil, LHSV is the liquid hourly space velocity (h -1 ) at any time t days after the start of the reaction, P B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) at any time t days after the start of the reaction, 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), and T SOR is the required temperature (K) on the 0th day.

[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, the "reference hydrogen partial pressure" means the standard pressure of the actual reaction conditions. It is obtained as the average value of the reaction pressures used when determining the hydrogen partial pressure coefficient a described later.

[0035] In this specification, the "reference reaction temperature" means the average value of T obtained within the range of standard operating conditions that can actually be operated. SOR

[0036] In the formula 4 above, T SOR represents the initial activity of the catalyst, and α represents the catalyst deterioration rate. That is, the larger the values of T SOR and α, the greater the catalyst deterioration, and this deterioration behavior will be reflected in the value of D.

[0037] In the formula 4 above, the term represented by (1 / S P n-1 -1 / S F n-1 )LHSV is the desulfurization reaction rate constant. As described above, when S P , S F , and LHSV are set values and the operation is carried out under certain conditions, it becomes a constant. In the formula 4 above, the term represented by (P B / P) a is the term indicating the hydrogen partial pressure dependence. As described above, when P is a set value and the operation is carried out under certain conditions, it becomes a constant. In the formula 4 above, the term represented by exp[Ec / R(1 / T B -1 / T SOR )] is the term indicating the temperature dependence and becomes a constant.

[0038] In the formula 4, 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. Note that LHSV can be obtained by dividing the supply amount of the feedstock oil (volume / h) by the catalyst filling amount (volume).

[0039] 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 formula 4, the above S F , S P ​The deterioration coefficient of the active species of the catalyst due to coke under the reaction conditions of LHSV and P can be calculated. The method for obtaining n, which is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue oil, will be described later.

[0040] (Method for obtaining the basic coke deterioration parameters) In the above formula 4, α, P B , a, Ec, T B , T SOR are constants. Hereinafter, these parameters are collectively referred to as "basic coke deterioration parameter 1". The basic coke deterioration parameter 1 is a parameter determined according to the catalyst to be used, and may be obtained while conducting the reaction in an actual machine, or may be obtained in advance on a bench scale based on the actual machine operating conditions. In the present embodiment, it is preferable to obtain it in advance on a bench scale based on the actual machine operating conditions. Hereinafter, an example of the method for obtaining the basic coke deterioration parameters P B , a, Ec, T B will be shown. It is a method for obtaining from the deterioration behavior of the catalyst (change in reaction rate constant) analyzed from the data obtained from the above-described reaction in an actual machine or the reaction on a bench scale based on the actual machine operating conditions (method for obtaining P B , a, Ec, T B ). Also, two examples of the method for obtaining α and T SOR will be shown, but the present invention is not limited thereto. The first example is a method for obtaining from the deterioration behavior of the catalyst (change in reaction rate constant) analyzed from the data obtained from the above-described reaction in an actual machine or the reaction on a bench scale based on the actual machine operating conditions (method 1 for obtaining α and T SOR ), and the second example is a method for obtaining from the reaction temperature profile analyzed from the data obtained from the above-described reaction in an actual machine or the reaction on a bench scale based on the actual machine operating conditions (method 2 for obtaining α and T SOR ).

[0041] (Method for obtaining P B , a, Ec, T B ) The method for obtaining the basic deterioration parameters of coke in this embodiment is based on the deterioration behavior of the catalyst analyzed from the data obtained in the bench-scale reaction based on the above-described reaction in the actual machine or the actual machine operation conditions. The deterioration behavior (degree of deterioration) of this catalyst has the same concept as the above formula 1 and can be expressed by the following formula 5. Φ’ = k t ’ / k0’ Formula 5 In the above formula 5, k0’ is the reaction rate constant of the catalyst at the time when 0 days of reaction have elapsed (that is, at the start of the reaction), and k t ’ is the reaction rate constant of the catalyst at the time when any reaction t days have elapsed. Note that k0’ and k t ’ are the reaction rate constants at the temperature T SOR ’ described later.

[0042] Similar to the above formula 1, the above formula 5 is a deterioration function based on the reaction rate constant. The reaction rate constant is expressed by the Arrhenius formula of the following formula 6.

[0043]

Number

[0044] The reaction rate constant k0’ at the start of the reaction temperature T SOR ’ decreases to k t ’ at the time when t days of reaction have elapsed. Assuming that the reaction temperature must be T t ’ in order to obtain the activity corresponding to the reaction rate constant k0’ at the time when t days of reaction have elapsed, the following formula 7 is derived from the above formula 5 and the above formula 6. In addition, since the reaction in this embodiment is a hydrotreating reaction of a feedstock oil containing atmospheric residue oil, the activation energy E is set as the activation energy Ea (kJ / mol) for desulfurization.

[0045]

Number

[0046] (For finding Ec and T B (Method of finding)) Set LHSV, hydrogen partial pressure, hydrogen / feedstock oil ratio, sulfur concentration in the feedstock oil, and metal concentration as constant conditions, and carry out the reaction for a certain period so that the sulfur concentration in the product oil becomes a certain value S Pn Since the catalyst deteriorates due to the reaction, in order to make the sulfur concentration in the product oil S Pn , the operation is carried out while increasing the reaction temperature. In this case, the metal concentration in the product oil also becomes constant. Plot the measured reaction temperature on the vertical axis and the reaction time on the horizontal axis, and draw a regression line, then y = a n x + b n (0 < a n ).) A straight line represented by is obtained. a n and b n are values reflecting the deterioration behavior of the catalyst. b n in this straight line becomes T SOR ' in the above formula 7. In the above formula 7, substitute b SOR for T n ' and substitute the measured reaction temperature for T t ', then the degree of deterioration Φ' at any reaction time t days can be obtained. The activation energy Ea for desulfurization can use the value obtained by the method described later. Plot the logarithm of Φ' on the vertical axis and the reaction time on the horizontal axis, and draw a regression line, then y = -a n ’ x (| -a n ’ | = a n ’ ).) A straight line represented by is obtained. a n ’ represents the deterioration rate of the catalyst.

[0047] Perform the same reaction for n types of sulfur concentrations S Pn , and in the same way, find n a n , b n , and by the same method as above, find n a n ’To obtain. n is an integer of 3 or more. The larger the number of n, the higher the accuracy of Ec 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 the present embodiment, n is preferably 3 to 20, and more preferably 3 to 10. The n a's thus obtained n ’ and b n are respectively substituted into the following formula 8. The following formula 8 is a formula capable of calculating the activation energy of coke and the reference reaction temperature, and is a formula 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 ) Formula 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] The n a's n ’ and b n Regarding the combination of, with ln(a n ’ ) on the vertical axis and 1 / b n on the horizontal axis, plot, draw a regression line, and obtain its slope. Since this slope is Ec / R, the activation energy of coke deterioration Ec can be obtained by dividing the slope by R.

[0050] Also, by averaging the n b's n T B can be obtained.

[0051] Ec and T B In obtaining Ec and T, the LHSV, hydrogen partial pressure, hydrogen / feedstock oil ratio, and sulfur concentration in the feedstock oil are preferably conditions in accordance with the actual machine operating conditions. As such LHSV, for example, 0.1 to 1.0 h -1and the hydrogen partial pressure is, for example, 5 to 18 MPa, and the hydrogen / feedstock oil ratio is, for example, 170 to 1400 [Nm 3 / kL], the sulfur concentration in the feedstock oil is, for example, 1 to 5% by mass, and the metal concentration in the feedstock oil is, for example, 10 to 200 ppm by mass. The n types of sulfur concentration S Pn are also preferably set to conditions in accordance with the actual operating conditions. Such S Pn is, for example, 0.5% by mass or less. The reaction period is, for example, 100 to 500 days.

[0052] (P B and the method for obtaining a) With the LHSV, hydrogen / feedstock oil ratio, sulfur concentration in the feedstock oil, metal concentration, and sulfur concentration in the product oil being constant conditions, the reaction is carried out for a certain period under the condition of hydrogen partial pressure P m . Since the catalyst deteriorates due to the reaction, in order to keep the sulfur concentration in the product oil at a constant value, the operation is carried out while increasing the reaction temperature. When the reaction time is plotted on the horizontal axis and the measured reaction temperature is plotted on the vertical axis and a regression line is drawn, y = a m x + b m (0 < a m ).) A straight line represented by is obtained. The b m in this straight line becomes T SOR ’ in the above formula 7. In the above formula 7, when b SOR is substituted into T m ’ and the measured reaction temperature is substituted into T t ’, the degree of deterioration Φ’ at any reaction time t days can be obtained. When the reaction time is plotted on the horizontal axis and the logarithm of Φ’ is plotted on the vertical axis and a regression line is drawn, y = -a m ’ x (|―a m ’ | = a m ’ ).) A straight line represented by is obtained. a m ’ represents the deterioration rate of the catalyst.

[0053] For m types of hydrogen partial pressure P m , the same reaction is carried out, and in the same way, m a's are obtained.m , b m are obtained, and in the same manner as described above, m a's m ’ are obtained. m is an integer of 3 or more. The larger the number of m, the higher the accuracy of a that can be obtained. On the other hand, if the number of m is too large, it takes time to obtain a and it is not efficient. In the present embodiment, m is preferably 3 to 20, and more preferably 3 to 10. The m a's thus obtained m ’ and P m are respectively substituted into the following formula 9. The following formula 9 is a formula capable of calculating the hydrogen partial pressure coefficient and the reference hydrogen partial pressure, and is a formula first found by the inventors of the present application based on the operation results of the actual machine and the like.

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

[0055] Regarding the combination of m a's m ’ and P m , ln(a m ’ ) is plotted on the vertical axis, ln(P m ) is plotted on the horizontal axis, a regression line is drawn, and its slope is obtained. This slope is the hydrogen partial pressure coefficient a.

[0056] Also, P m can be obtained by averaging the above m hydrogen partial pressures P B .

[0057] The LHSV, hydrogen / feedstock oil ratio, sulfur concentration in the feedstock oil, and sulfur concentration in the product oil in obtaining a and P B are preferably set to conditions in accordance with the actual machine operating conditions. As such an LHSV, for example, it is 0.1 to 1.0 h -1 , and as the hydrogen / feedstock oil ratio, for example, it is 170 to 1400 [Nm 3is in [ / kL], the sulfur concentration in the feedstock oil is, for example, 1 to 5% by mass, the metal concentration in the feedstock oil is, for example, 10 to 200 ppm by mass, and the sulfur concentration in the product oil is, for example, 0.5% by mass or less. m kinds of hydrogen partial pressures P m It is also preferably set to conditions that conform to the actual operating conditions. Such P m is, for example, 5 to 18 MPa. The reaction period is, for example, 100 to 500 days.

[0058] (α and T SOR Calculation method 1) In a full-scale or bench-scale unit, perform the reaction for a certain period so that the LHSV, hydrogen partial pressure, hydrogen / feedstock oil ratio, sulfur concentration in the feedstock oil, metal concentration, and sulfur concentration in the product oil under the assumed full-scale operating conditions are obtained. Since the catalyst deteriorates due to the reaction, the operation is carried out while increasing the reaction temperature. The assumed full-scale operating conditions are, for example, the operating conditions described in (the calculation method of Ec and T B ), (the calculation method of P B and a). Plot the reaction time on the horizontal axis and the measured reaction temperature on the vertical axis, and draw a regression line. Then, a straight line represented by y = a α x + b α is obtained. The a α in this straight line is a value correlated with α in the above formula 4, and b α is T SOR in the above formula 4. In the above formula 7, substitute b SOR into T α ’ and substitute the measured reaction temperature into T t ’. Then, the degree of deterioration Φ’ at any reaction time 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, a straight line represented by y = -a α ’ x (| - a α ’ | = a α ’ is set). is obtained. a α ’ represents the deterioration rate of the catalyst.

[0059] The operating condition S P, S F , LHSV, P, and P obtained by the above method B ,a,Ec,T B、 T SOR (i.e., b α ) into the above formula 4 to find D. Substituting the found D into the above formula 3 gives Φ C In this case, Φ C is a function of α. In the above formula 2, Φ M = 1, then Φ = Φ C Φ is a function of α. If we plot the reaction time on the horizontal axis and the logarithm of Φ on the vertical axis, and draw a regression line by changing α so that α is 0<α, we get y=-α α ” x(|-a α ” |=a α ” ) are obtained for each value of α. α ” and the above-mentioned a α ’ The value of α when these values are equal can be used as α in the above formula 4.

[0060] (α and T SOR How to find 2) (α and T SOR Carry out the same reaction as in 1) above, and find y=a α x+b α Obtain a line represented by b α T in the above formula 4 SOR The operating condition is S P , S F , LHSV, P, and P obtained by the above method B ,a,Ec,T B、 T SOR (i.e., b α ) into the above formula 4 to find D. Substituting the found D into the above formula 3 gives Φ C In this case, Φ C is a function of α. In the above formula 2, Φ M =1, then Φ=Φ C Φ is a function of α. The obtained Φ is converted into Φ' in the above equation 7, and T SOR (i.e., bα ) substitute T in Formula 7 above SOR ’ and arrange for T t ’. When arranged, T t ’ becomes a function of α. The ratio of T obs ’ to the measured reaction temperature T t (T t ’ / T obs ) When it becomes 1, α can be used as α in Formula 4 above. Similarly, for N reaction temperatures T obs the ratio of T t ’ to T t (T obs ’ / T

[0061] (Modification example of coke deterioration function 1) A modification example of coke deterioration function 1 will be described below. As coke deterioration function 1, coke deterioration function 1-1 represented by the following Formula 10 may be used.

[0062] Φ C = exp(-D’t) Formula 10 In Formula 10 above, D’ is the coke deterioration coefficient of the active species of the catalyst, and t is the number of days elapsed in the reaction (days).

[0063] D’ can be obtained by the following Formula 11.

[0064] [Number] In Formula 11 above, α’ is a catalyst constant (a constant representing the coke deterioration rate of the catalyst), S F is the sulfur concentration (mass%) in the feedstock oil at any time t during the reaction, S P is the sulfur concentration (mass%) in the product oil at any time t during the reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric residue, LHSV is the liquid hourly space velocity at any time t during the reaction (h -1 ), and P Bis 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 / kL), G is the hydrogen / feedstock oil ratio (Nm 3 / kL) at the end of an arbitrary reaction day t, b is the hydrogen / feedstock 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), T SOR is the required temperature (K) on day 0.

[0065] S in the above formula 11 F and S P , LHSV, and P are the same as described for formula 4 above. In formula 11, G is a value substituted based on the information about the feedstock oil and operating conditions obtained in the information acquisition step described above. Specifically, G can be obtained by dividing the hydrogen supply rate (Nm 3 / hour) by the feedstock oil supply rate (kL / hour).

[0066] In this specification, the "reference hydrogen / feedstock oil ratio" means the standard hydrogen / feedstock oil ratio under actual reaction conditions. It is obtained as the average value of the hydrogen / feedstock oil ratio used when determining the hydrogen / feedstock oil ratio coefficient b described below.

[0067] In the above formula 11, the term represented by (G B / G) b is a term indicating the hydrogen / feedstock oil ratio dependence. As described above, when G is set as a set value and the operation is carried out under certain conditions, it becomes a constant.

[0068] P B , a, Ec, T B , T SOR can be obtained by the same method as described for formula 4 above. Hereinafter, the methods for obtaining G B , b, and α' will be described.

[0069] G B , and b are P B, a, Ec, T B , T SOR Similarly, it is a parameter determined according to the catalyst to be used, and it may be obtained while performing the reaction in an actual machine, or may be obtained in advance on a bench scale based on the actual machine operation conditions. In the present embodiment, it is preferable to obtain it in advance on a bench scale based on the actual machine operation conditions. Hereinafter, G B , the method for obtaining b will be described.

[0070] (G B , the method for obtaining b) The method for obtaining the basic deterioration parameter of the present embodiment is based on the deterioration behavior of the catalyst analyzed from the data obtained from the reaction in the above-described actual machine or the reaction on a bench scale based on the actual machine operation conditions.

[0071] Set LHSV, hydrogen partial pressure, sulfur concentration, metal concentration in the feedstock oil, and sulfur concentration in the product oil as constant conditions, and the hydrogen / feedstock oil ratio G h Under the conditions of, the reaction is carried out for a certain period. Since the catalyst deteriorates due to the reaction, in order to keep the sulfur concentration in the product oil at 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 h x + b h (0 < a h .) A straight line represented by is obtained. b h in this straight line becomes T SOR ' in the above formula 7. In the above formula 7, substitute b SOR ' into T h , and substitute the measured reaction temperature into T t ’ , then the degree of deterioration Φ' at any reaction time t days elapsed 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 h ’ x (|―a h ’ | = a h ’ .) A straight line represented by is obtained. a h ] ’ represents the deterioration rate of the catalyst.

[0072] h types of hydrogen / feedstock oil ratio G h Perform the same reaction for each, and in the same way, h a h , b h are obtained, and in the same manner as above, h a h ’ are obtained. h is an integer of 3 or more. The larger the number of h, the higher the accuracy of b that 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 this embodiment, h is preferably 3 to 20, and more preferably 3 to 10. The h a h ’ and G h thus obtained are respectively substituted into the following formula 12. The following formula 12 is a formula capable of calculating the hydrogen / feedstock oil ratio coefficient and the reference hydrogen / feedstock oil ratio, and is a formula first found by the inventors of the present application based on the operating results of actual machines and the like.

[0073] ln(a h ’)=-bln(G h )+B3 Formula 12 In the above formula 12, B3 can be set to 0.

[0074] For the combination of h a h ’ and G h , plot ln(a h ’) on the vertical axis and ln(G h ) on the horizontal axis, draw a regression line, and obtain its slope. This slope is the hydrogen / feedstock oil ratio coefficient b.

[0075] Also, by averaging the above h types of hydrogen / feedstock oil ratio G h , G B can be obtained.

[0076] b and G B In determining b and G The LHSV, hydrogen partial pressure, sulfur concentration in the feedstock oil, and sulfur concentration in the product oil are preferably set to conditions in accordance with the actual machine operating conditions. -1 As such LHSV, for example, 0.1 to 1.0 h -1and the hydrogen partial pressure is, for example, 5 to 18 MPa, the sulfur concentration in the feedstock oil is, for example, 1 to 5% by mass, the metal concentration in the feedstock oil is, for example, 10 to 200 ppm by mass, and the sulfur concentration in the produced oil is, for example, 0.5% by mass or less. h types of hydrogen / feedstock oil ratio G h It is also preferable to set the conditions in accordance with the actual operating conditions. Such G h is, for example, 170 to 1400 [Nm 3 / kL]. The reaction period is, for example, 100 to 500 days.

[0077] In addition, α' can be obtained by the same method as the method for obtaining α in the coke deterioration function 1 (the method for obtaining (α and T SOR Method 1) and (α and T SOR Method 2)) except that the formula 11 is used instead of the formula 4.

[0078] <Coke deterioration function 2> In the present embodiment, the coke deterioration function regarding the deterioration of the catalyst due to the deposition of coke is preferably the coke deterioration function 2 represented by the following formula 13, which is composed of the easily deactivated active species deterioration function regarding the deterioration of the easily deactivated active species of the catalyst and the hardly deactivated active species deterioration function regarding the deterioration of the hardly deactivated active species of the catalyst.

[0079] Φ C =k1×exp(-D1t)+k2×exp(-D2t) Formula 13 In the formula 13, k1 is the active site coefficient of the easily deactivated active species of the catalyst, k2 is the active site coefficient of the hardly deactivated active species of the catalyst, and the active site coefficient represents the relative reaction rate constant of both active species. D1 is the deterioration coefficient due to coke of the easily deactivated active species of the catalyst, D2 is the deterioration coefficient due to coke of the hardly deactivated active species of the catalyst, t is the number of days elapsed since the start of the reaction (days), and k1 + k2 = 1.

[0080] In the hydrotreating reaction of atmospheric distillation residue oil, as described above, since the catalyst deteriorates due to the deposition of coke, in order to keep the sulfur content in the product oil below a certain level, it is necessary to increase the reaction temperature for operation. In the hydrotreating reaction of atmospheric distillation residue oil, at the initial stage of the start of the reaction, 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 start of the reaction. 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 atmospheric distillation residue oil, 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 start of the reaction 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 reaction time as described above, 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 start of the reaction and hardly deactivated 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 with higher accuracy than the coke deterioration function 1. The easily deactivated active species are mainly active species whose activity is lost at the initial stage of the reaction, and the hardly deactivated active species mean 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 hardly deactivated 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 formulas 14 and 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 atmospheric residue. LHSV is the liquid hourly space velocity (h -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 of coke deterioration (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 the 0th day. In the above formula 14, α1 is the catalyst constant of the easily deactivated active site (a constant representing the deterioration rate due to coke on the catalyst). In the above formula 15, α2 is the catalyst constant of the hardly deactivated active site (a constant representing the deterioration rate due to coke on the catalyst).

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

[0089] As described above, S F , LHSV, and P are parameters that can be controlled. Also, S[[ID= / / ID=37]] P is the sulfur concentration of the target product oil. That is, from the above formulas 14 and 15, the above S F , S PThe deterioration coefficients of the easily deactivated active species of the catalyst due to coke and the deterioration coefficients of the hardly deactivated active species of the catalyst due to coke under the reaction conditions of LHSV and P can be calculated respectively. The method for obtaining n, which is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue oil, will be described later.

[0090] (Method for obtaining the basic coke deterioration parameters) In the above formulas 14 and 15, α1, α2, P B , a, Ec, T B , T SOR are constants, similar to formula 4 above, and these parameters are collectively referred to as "basic coke deterioration parameters 2". The basic coke deterioration parameters 2 are parameters determined according to the catalyst used, and may be obtained while performing the reaction in an actual machine, or may be obtained in advance on a bench scale based on the actual machine operating conditions. In the present embodiment, it is preferable to obtain them in advance on a bench scale based on the actual machine operating conditions. In the above formulas 14 and 15, P B , a, Ec, T B can be obtained by the same method as formula 4. On the other hand, α1, α2, T SOR can be obtained, for example, by the following two methods. Also, the active site number coefficients k1 of the easily deactivated active species of the catalyst and k2 of the hardly deactivated active species of the catalyst in formula 13 can be obtained simultaneously as follows.

[0091] (α1, α 2、 T SOR , k1, and k2 obtaining method 1) In an actual machine or on a bench scale, perform the reaction for a certain period so that the LHSV, hydrogen partial pressure, hydrogen / feedstock oil ratio, sulfur concentration in the feedstock oil, metal concentration, and sulfur concentration in the product oil are those of the assumed actual machine operating conditions. Since the catalyst deteriorates due to the reaction, operate while increasing the reaction temperature. Plot the reaction time on the horizontal axis and the reaction temperature on the vertical axis. When drawing the regression line of these plots, as described above, for the sharp increase in the reaction temperature at the initial stage of the reaction start (x1~x n ), the straight line represented by y = a1x + b1 that correlates with it, and after the middle stage of the reaction (x n+1 ~xm ) Two straight lines represented by y = a2x + b2 that correlate with a gentle increase in the reaction temperature are obtained. In the above formula, a1 > a2 > 0, b1 < b2, and x1 < x n <x n+1 <x m is satisfied. x n , x m means the reaction time correlated with the n(m)-th plot from the start of the reaction.

[0092] The above-mentioned a1 is a value correlated with α1, b1 is a value correlated with k1 + k2, and T SOR is satisfied. Also, a2 is a value correlated with α2, and b2 is a value correlated with k2. Next, the intersection point (x ip , y ip ) of y = a1x + b1 and y = a2x + b2 is calculated. This intersection point means the inflection point of y = a1x + b1 and y = a2x + b2. That is, up to (x ip , y ip ), it is considered that only the easily deactivated active species of the catalyst exist, and from (x ip , y ip ), it is considered that two active species, the easily deactivated active species and the hardly deactivated active species of the catalyst, exist.

[0093] In the above formula 7, substituting b1 into T SOR ’ and substituting the reaction temperature into T t ’, the degree of deterioration Φ’ at any reaction time t days elapsed is obtained. Plotting the reaction time on the horizontal axis and the logarithm of Φ’ on the vertical axis, and drawing a regression line from x1 to x ip , a straight line represented by y = -a1 ’ x (| - a1 ’ | = a1 ’ is satisfied.) is obtained. Also, drawing a regression line from x ip to x m , a straight line represented by y = -a2 ’ x - b2 ’ (| - a2 ’ | = a2 ’ is satisfied, and | - b2 ’ | = b2 ’ is satisfied.) is obtained. a1 ’ is a value correlated with α1, a2’ is a value correlated with α2, and b2 ’ is a value correlated with k2.

[0094] k2 can be obtained by substituting b2 obtained from the above regression line ’ into the following Equation 16. Since k1 + k2 = 1, k1 can be obtained from k1 = 1 - k2. k2 = exp(-b2 ’ ) Equation 16

[0095] S which is an operating condition P , S F , LHSV, P, and P obtained by the above method B , a, Ec, T B , T SOR (b1) is substituted into the above Equation 14 and Equation 15 to obtain D1 and D2. When the obtained D1, D2, k1, and k2 are substituted into the above Equation 13, Φ C is obtained. In this case, Φ C becomes a function of α1 and α2. In the above Equation 2, when Φ M = 1, then Φ = Φ C and Φ becomes a function of α1 and α2. Plotting the logarithm of Φ with the reaction time on the horizontal axis and α2 = 0 and changing α1 so that 0 < α1 to x1 ~ x ip and drawing a regression line up to, y = -a α1 ” x (|-a α1 " | = a α1 ” ). A plurality of lines represented by () are obtained for each value of α1. The a α1 ” in each line and the above a1 ’ can be set as α1 in the above Equation 14 when they become equal values. Next, substitute the obtained α1 into Φ C (Φ) which is a function of α1 and α2 obtained by the above method, change α2 so that 0 < α2 to x ip ~ x m and draw a regression line up to, y = -a α2 ” x - b α2 "(|-a α2 ” |=a α2 " A plurality of straight lines represented by) are obtained for each value of α2. For a in each straight line α2 ” and the above-mentioned a2 ’ when they become equal values, α2 can be set as α2 in the above formula 15.

[0096] ]](α1, (α2)(α1, (α2) 、 T SOR , k1, and the method 2 of obtaining k2) In this embodiment, since α2 is obtained simultaneously with the basic deterioration parameter of the metal in the metal deterioration function described later, α1, T SOR , k1, and k2 are obtained. The method of obtaining α2 in this embodiment will be described later. T SOR , k1, and k2 are obtained by exactly the same method as (the method 1 of obtaining α1, α 2、 T SOR , k1, and k2). (In the method 1 of obtaining α1, α 2、 T SOR , k1, and k2), in Φ C which is the function of the obtained α1 and α2, with the reaction time on the horizontal axis and the logarithm of Φ C on the vertical axis, plot, set α2 = 0 and change α1 so that 0 < α1, and draw a regression line from x1 to x ip until, then y = -a α1-1 ” x(|-a α1-1 " |=a α1-1 ” A plurality of straight lines represented by) are obtained for each value of α1. For a in each straight line α1-1 ” and the above-mentioned a1 ’ when they become equal values, α1 can be set as α1 in the above formula 14.

[0097] (α1, α 2、 T SOR , k1, and the method 3 of obtaining k2) (α1, α 2、 T SOR , k1, and k2) perform the same reaction as (the method 1 of obtaining α1, α SORObtain (b1). S which is the operating condition P , S F , LHSV, P, and P obtained by the above method B , a, Ec, T B , T SOR Substitute (b1) into Formula 14 and Formula 15 to obtain D1 and D2. Substitute the obtained D1 and D2 into Formula 13, then Φ C is obtained. In this case, Φ C becomes a function of α1, α2, k1, and k2. In Formula 2, when Φ M = 1, then Φ = Φ C and Φ becomes a function of α. Substitute the obtained Φ into Φ' in Formula 7, and T SOR (that is, b1) into T in Formula 7 SOR ’ and rearrange for T t ', then T t ' becomes a function of α1, α2, k1, and k2. When α2 is set to 0 and k2 = 1 - k1, then T t ' becomes a function of α1 and k1. The combination of α1 and k1 when the ratio (T ip ' / T obs ) of the measured reaction temperature T t ' to T t ' in x1 to x obs is 1 is obtained, and this α1 can be used as α1 in Formula 14. Note that k1 at this time is a provisional value. Similarly, calculate the ratio (T obs ' / T t ) of T t ' to T obs for M reaction temperatures T It is preferable to use the obtained α1 and set k1 = 1 - k2, then T t ' becomes a function of α2 and k2. The ratio (T ip ' / T m ) of the measured reaction temperature T obs to T t ' in x t ' / T obs) When it becomes 1, obtain the combination of α2 and k2, and these α2 and k2 can be used as α2 and k2 in the above formula 15. By substituting the obtained k2 into k1 = 1 - k2, k1 can be obtained, and this k1 can be used as k1 in the above formula 14. Similarly, for L reaction temperatures T obs For T t ’s ratio (T t ’ / T obs ), calculate it, and it is preferable that α2 and k2 when the average of these is closest to 1 be used as α2 and k2 in the above formula 15. Also, it is preferable that k1 obtained from the obtained k2 be used as k1 in the above formula 14. L is an integer of 10 or more, preferably 10 to 500, and more preferably 50 to 200.

[0098] Thus, in order to obtain α1, α 2、 T SOR , k1, and k2, it is necessary to obtain y = a1x + b1 and y = a2x + b2. y = a1x + b1 and y = a2x + b2 can be obtained, for example, as follows.

[0099] Using the above method, plot the reaction time on the horizontal axis and the reaction temperature on the vertical axis. Draw a regression line from the start of the reaction to the end of the reaction, and a straight line represented by y = a’x + b’ is obtained. This straight line does not consider the inflection point. Delete the plots in order from the end of the reaction, adjust the above y = a’x + b’ so that the correlation coefficient approaches 1, and obtain y = a1’x + b1’. Similarly, delete the plots in order from the start of the reaction, adjust the above y = a’x + b’ so that the correlation coefficient approaches 1, and obtain y = a2’x + b2’. Each straight line when the average of the correlation coefficients of y = a1’x + b1’ and y = a2’x + b2’ is closest to 1 becomes y = a1x + b1 and y = a2x + b2. Note that all plots should belong to either y = a1x + b1 or y = a2x + b2.

[0100] 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 the above y = a’x + b’ becomes 0.5 or more.

[0101] (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.

[0102] 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 those in the above formula 13, D1’ is the coke deterioration coefficient of the easily deactivated active species of the catalyst, and D2’ is the coke deterioration coefficient of the hardly deactivated active species of the catalyst.

[0103] D1’ can be obtained by the following formula 18, and D2’ can be obtained by the following formula 19.

[0104] [Number]

[0105] [Number]

[0106] In the above formula 18 and the above formula 19, S F , S P , n, LHSV, P B , P, a, Ec, R, T B , T SOR are the same as those in the above formula 14 and the above formula 15, G B , G, b are the same as those in the above formula 11. In the above formula 18, α1’ is the catalyst constant of the easily deactivated active site (a constant representing the deterioration rate of the catalyst due to coke), and in the above formula 19, α2’ is the catalyst constant of the hardly deactivated active site (a constant representing the deterioration rate of the catalyst due to coke).

[0107] P B , a, Ec, T B , T SOR can be obtained by the same method as described in the above formula 14 and the above formula 15, and G B, b can be obtained by the same method as described in the method of Formula 11.

[0108] Also, α1’ and α2’ can be obtained by the same method as the method for obtaining α1 and α2 described in the deterioration function 2, except that Formula 17 is used instead of Formula 13, Formula 18 is used instead of Formula 14, and Formula 19 is used instead of Formula 15.

[0109] <Metal deterioration function> The metal deterioration function is not particularly limited as long as it is a function capable of calculating the degree of deterioration related to the metal deterioration of the catalyst. For example, the metal deterioration function 1 represented by the following Formula 20 can be cited as an example. The metal deterioration function 1 represented by Formula 20 is a metal deterioration function described in a non-patent document (Journal of Chemical Engineering of Japan, Vol. 24, No. 4 (1998), p656).

[0110]

Equation

[0111] In the hydrotreating reaction of a feedstock oil containing atmospheric distillation residue oil, as described above, since the catalyst deteriorates due to metal deposition, in order to keep the sulfur content in the product oil below a certain level, it is necessary to increase the reaction temperature for operation. The phenomenon of catalyst deterioration due to this metal deposition can be explained by the decrease in the diffusion rate of the feedstock oil into the catalyst pores. That is, in the hydrotreating reaction of atmospheric distillation residue oil, the feedstock oil needs to diffuse into the catalyst pores and access the active sites. At this time, when the diffusion rate is sufficiently larger than the reaction rate, all the feedstock oil can access all the active sites, but when the diffusion rate is smaller than the reaction rate, the feedstock oil cannot access all the active sites and not all the active sites function effectively. The diffusion rate decreases over time due to the blockage of the catalyst pores by metal deposition.

[0112] The extent to which the active sites in the catalyst pores are effectively used is determined by the relationship between the reaction rate and the diffusion rate. This relationship can be theoretically expressed by the catalyst effectiveness factor η. When there is no influence of diffusion inhibition and substantially all the active sites in the catalyst pores are used, η becomes 1. On the other hand, when substantially all the active sites in the catalyst pores are not used, η becomes smaller than 1. And when only the active sites near the outer surface of the catalyst are used, η approaches 0.

[0113] As described above, in the hydrotreating reaction of atmospheric distillation residue oil, it is suggested from the profile of the reaction temperature with respect to the reaction time that rapid catalyst deterioration occurs at the initial stage of the reaction and slow catalyst deterioration occurs after the middle stage of the reaction.

[0114] As described above, based on the assumption that there are easily deactivated active species that are deactivated by coke at the initial stage of reaction initiation and hardly deactivated active species that are deactivated by coke after the middle stage of reaction, the inventors of the present application have found a coke deterioration function. Here, it is considered that a decrease in activity due to metal deposition also occurs after the middle stage of reaction, and the gradual deterioration of the catalyst after the middle stage of reaction is considered to be due to the deactivation of hardly deactivated active species deactivated by coke and the deposition of metal. Based on the profile of the reaction temperature with respect to the reaction time as described above, the inventors of the present application have found a metal deterioration function based on the assumption that the gradual deterioration of the catalyst after the middle stage of reaction is due to the deactivation of hardly deactivated active species deactivated by coke and the deposition of metal. As a result, it has been found that by combining the coke deterioration function and the metal deterioration function, the degree of deterioration of the catalyst can be calculated more accurately.

[0115] In the above formula 20, η, t end are constants (however, η becomes two types of constants depending on the progress of the reaction). Hereinafter, these parameters are collectively referred to as "basic metal deterioration parameters". The basic metal deterioration parameters are parameters determined according to the catalyst to be used, and may be obtained while performing the reaction in an actual machine, or may be obtained in advance on a bench scale based on the actual machine operating conditions. In the present embodiment, it is preferable to obtain them in advance on a bench scale based on the actual machine operating conditions. Hereinafter, an example of how to obtain the basic deterioration parameters η, t end will be described, but the present invention is not limited thereto.

[0116] (η, t end , Method for obtaining α2 1) This embodiment is (α1, (α2) 、 T SOR , Method for obtaining k1, and k2 2) in combination to obtain η, t end , α2. By the same method as the method described in the above (α1, (α2) 、 T SOR , k1, and method for obtaining k2 2), the straight line represented by y = a1x + b1 corresponding to the rapid increase in reaction temperature at the initial stage of reaction initiation (x1 to x n ), and after the middle stage of reaction (xn+1 ~x m ) corresponding to the gentle increase in reaction temperature, two straight lines represented by y = a2x + b2, and an inflection point (x ip , y ip ) are obtained. (From (x ip , y ip ), there exist two deactivating active species of coke, namely, easily deactivated active species and hardly deactivated active species, and it is considered that metal deterioration has occurred. That is, until the inflection point (x ip , y ip ), η is 1, and from the above formula 20, Φ M becomes 1. Therefore, until the inflection point (x ip , y ip ), the above formula 2 is represented by Φ = Φ C . On the other hand, after the inflection point (x ip , y ip ), η becomes a constant smaller than 1.

[0117] The above (α1, (α2) 、 T SOR , k1, and k2 are obtained in the same manner as the method described in the method of obtaining 2). By drawing a regression line from x ip to x m , a straight line represented by y = -a2 ’ x - b2 ’ (| - a2 ’ | = a2 ’ , and | - b2 ’ | = b2 ’ ) is first obtained.

[0118] Substitute the operating conditions S P , S F , LHSV, P, and P B , a, Ec, T B , T SOR (b1), α1 obtained by the above method into the above formulas 14 and 15 to obtain D1 and D2. Substitute the obtained D1, D2, and k1, k2 obtained by the above method into the above formula 13, and Φ C is obtained. In this case, Φ C is a function of α2. Substitute this Φ C and the Φ M of the above formula 20 into the above formula 2, and Φ is obtained. In this case, Φ is a function of α2, η, tend It becomes a function. Plot the logarithm of Φ on the vertical axis and the reaction time on the horizontal axis, with 0 < α2, 0 < η < 1, and x ip <t end In the range of, for the combination of (α2, η, t end ), change x ip ~x m Draw a regression line up to, and y = -a α3 ” x - b α3 " (| - a α3 ” | = a α3 " is. ) A plurality of straight lines represented by are obtained for each combination of (α2, η, t end ). When a α3 in each straight line is equal to the above-mentioned a2 ’ , α2 at that time can be set as α2 in the above formula 15. Also, when b α3 in each straight line is equal to the above-mentioned b2 ’ , the combination of (η, t end ) at that time can be set as η, t end in the above formula 20.

[0119] (Method for obtaining (η, t end ) 2) This embodiment can be applied when Φ M = 1 is set in the above method and α2 is obtained in advance. By the same method as the method described in the above (Method for obtaining (α1, α 2、 T SOR , k1, and k2) 1), for the rapid increase in reaction temperature at the initial stage of reaction start (x1~x n ), the straight line represented by y = a1x + b1, and for the gentle increase in reaction temperature after the middle stage of reaction (x n+1 ~x m ), two straight lines represented by y = a2x + b2, and the inflection point (x ip , y ip ) are obtained. From (x ip , y ip ), it is considered that there are two deactivating active species of coke, namely, easily deactivated active species and hardly deactivated active species, and metal deterioration is occurring. That is, the inflection point (x ip, y ip ) until η is 1 and Φ from the above formula 20 M becomes 1. Therefore, up to the inflection point (x ip , y ip ), the above formula 2 is expressed as Φ = Φ C . On the other hand, after the inflection point (x ip , y ip ), η becomes a constant smaller than 1.

[0120] The above-mentioned (α1, α 2、 T SOR , k1, and the method of obtaining k2 1) By the same method as described, a regression line is drawn from x ip to x m , and a straight line expressed by y = -a2 ’ x - b2 ’ (| - a2 ’ | = a2 ’ and | - b2 ’ | = b2 ’ ) is first obtained.

[0121] S which is an operating condition P , S F , LHSV, P, and P obtained by the above method B , a, Ec, T B , T SOR (b1), α1, α2 are substituted into the above formula 14 and the above formula 15 to obtain D1 and D2. When the obtained D1, D2, and k1, k2 obtained by the above method are substituted into the above formula 13, Φ C is obtained. When this Φ C and Φ of the above formula 20 M are substituted into the above formula 2, Φ is obtained. In this case, Φ is a function of η, t end . Plotting the logarithm of Φ on the vertical axis with the reaction time on the horizontal axis, and changing the combination of (η, t ip <t end ) in the range of 0 < η < 1, x end and drawing a regression line from x ip to x m , we get y = -a α3-1 ” x - b α3-1 " (| - a α3-1 ”|=a α3-1 " is. A plurality of straight lines represented by () are obtained for each combination of (η, t end ). For each straight line, b α3 and the above-mentioned b2 ’ When they become equal values, the combination of (η, t end ) can be used as η and t in the above formula 20 end . In the above description, the coke deterioration function 2 is used for explanation. However, in the case of the coke deterioration function 1, the coke deterioration function 1-1, and the coke deterioration function 2-1, η and t end can also be obtained in the same manner. In this case, Φ C obtained by the coke deterioration function 1, the coke deterioration function 1-1, and the coke deterioration function 2-1 may be used.

[0122] Also, as a metal deterioration function, for example, the metal deterioration function 2 represented by the following formula 21 can be cited as an example.

Equation

[0123] The metal deterioration function 2 is a formula derived based on the metal deterioration function 1. Hereinafter, the derivation of the metal deterioration function 2 will be described.

[0124] MOC in the above formula 21 is represented by the following formula 22.

[0125]

Equation

[0126] From the above formula 22, M C in the above formula 21 is represented by the following formula 23.

[0127] [Number] In the above formula, WHSV, M F , M P are the same as in the above formula 22, and t end is the number of days of reaction progress (days) until the catalyst pores are blocked.

[0128] From the above formula 22 and the above formula 23, t end is represented by the following formula 24. t end = Mc / (MOC / t) Formula 24

[0129] Substituting the above formula 24 into the above formula 20 can derive the above formula 21. According to the metal deterioration function 2, t end can be obtained by MOC and M C .

[0130] (Method for obtaining MOC) MOC can be obtained by the above formula 22. In the above formula, WHSV, M F , M 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. Note that WHSV can be obtained by dividing the supply amount of the feedstock oil (weight / h) by the catalyst filling amount (weight).

[0131] As described above, WHSV, M F is a parameter that can be controlled. Also, M P is the metal concentration of the target produced oil. That is, according to the above formula 21, the noble metal deterioration function under the reaction conditions of the above WHSV, M F , M P can be calculated.

[0132] (Method for obtaining M C ) M C is a value specific to the catalyst and can be obtained by a method known in this field. As an example of the method for obtaining M C , for example, in a full-scale unit or bench scale, the reaction is carried out for a certain period so that the LHSV, hydrogen partial pressure, hydrogen / feedstock oil ratio, sulfur concentration in the feedstock oil, metal concentration, and sulfur concentration in the produced oil are those of the assumed full-scale unit operating conditions. Since the catalyst deteriorates due to the reaction, the operation is carried out while increasing the reaction temperature. The full-scale unit operating conditions are, for example, the operating conditions described in (Method for obtaining Ec and T B ), (Method for obtaining P B and a). When the reaction is continued for a long time, even if the reaction temperature is set to the maximum temperature allowed for equipment use (for example, 410 °C), the sulfur concentration in the produced oil will not reach a predetermined value. Continuing the reaction in this way, finally, when the sulfur concentration in the feedstock oil = the sulfur concentration in the produced oil, the reaction is stopped and the catalyst is withdrawn. The metal concentration of the withdrawn catalyst is measured, and the obtained value can be taken as M C . From the perspective of obtaining M C in a short period, a feedstock oil with an extremely high metal concentration may be used and the operation may be carried out at an LHSV higher than the full-scale unit operating conditions.

[0133] In the noble metal deterioration function 2, t end can be obtained by MOC and M C . Therefore, the fitting in the above (Method for obtaining η, t end , α2) becomes easier. Specifically, in the above (Method for obtaining η, t end , α2), b α3 and b2 ’When (η, t end ) reaches equal values, it was necessary to determine the combination, but in the metal deterioration function 2, t end is MOC and M C has been determined in advance by, so b α3 and b2 ’ It is only necessary to determine η when they reach equal values, and η can be obtained more simply and with higher accuracy.

[0134] (Switching timing of η) As described above, η takes two values of 1 and a constant greater than 0 and less than 1 obtained by the above method. It is 1 at the initial stage of the reaction and a constant greater than 0 and less than 1 after the middle stage of the reaction. Two examples of the timing for switching η from 1 to the constant greater than 0 and less than 1 will be described below, but the present invention is not limited to the following two examples. The information processing method of this embodiment preferably has a step of determining the timing for switching η. In this case, it is preferable that the information regarding the measured value of the reaction temperature is included as the information regarding the operating conditions acquired in the above-described information acquisition step. The step of determining the timing for switching η is executed, for example, by the reaction temperature calculation device 1 of this embodiment. For example, it is executed by the arithmetic unit 13 in the computer main body 12.

[0135] (Switching timing of η1) Φ M =1 is set to start the reaction. In this case, Φ = Φ C becomes. Using this Φ, the reaction temperature T t required to satisfy a predetermined condition is calculated by the reaction temperature calculation step described later, and the reaction is continued at this reaction temperature T t . After the middle stage of the reaction, even if the reaction temperature is T t , a predetermined condition (sulfur concentration in the predetermined product oil) is not satisfied. In this case, the reaction temperature is increased to search for a reaction temperature that satisfies the predetermined condition (sulfur concentration in the predetermined product oil). Assume that the reaction temperature at this time is Tt + Z (°C). It is preferable to switch η from 1 to the constant greater than 0 and less than 1 when Z becomes 2 (°C) or more.

[0136] (Timing 2 of η switching) Φ M Set Φ = 1 and start the reaction. In this case, Φ = Φ C is obtained. Using this Φ, the reaction temperature T t required to satisfy the predetermined conditions is calculated by the reaction temperature calculation step described later, and the reaction is continued at this reaction temperature T t . As described above, after the middle stage of the reaction, even when the reaction temperature is T t , the predetermined conditions (sulfur concentration in the predetermined product oil) are not satisfied. In this case, the reaction temperature is increased to search for a reaction temperature that satisfies the predetermined conditions (sulfur concentration in the predetermined product oil). Substitute T SOR obtained by the above method into T SOR in Equation 25 described later, and substitute T t obtained by the reaction temperature calculation step into T t to obtain Φ (Φ t ). Also, substitute T SOR [[ID=2nd]]obtained by the above method into T SOR in Equation 25 described later, and substitute the reaction temperature (measured value) that satisfies the above-mentioned predetermined conditions (sulfur concentration in the predetermined product oil) into T t to obtain Φ (Φ obs ). Observe Φ obs / Φ t over time, and it is preferable to switch η from 1 to a constant greater than 0 and less than 1 when Φ obs / Φ t becomes 0.9 or less.

[0137] <<Reaction Temperature Calculation Step>> The reaction temperature calculation step of the present embodiment is a step of calculating the reaction temperature required to satisfy the information on the raw material oil, the information on the product oil, and the operating conditions based on the degree of deterioration of the catalyst. The reaction temperature is preferably calculated by a deterioration rate equation based on the Arrhenius equation.

[0138] <Deterioration Rate Equation> The deterioration rate equation is an equation based on the Arrhenius equation represented by Equation 6 above. Similar to the calculation method of Equation 7 above, Equation 25 below is derived from Equation 1 and Equation 6.

[0139]

Number

[0140]

Number

[0141] By substituting T SOR , Φ obtained by the above method into the above formula 26, T t (K) at the time of progress of an arbitrary reaction on the t-th day can be obtained. The activation energy of the desulfurization reaction in the above formula 26 can be obtained as follows.

[0142] (Method for obtaining the activation energy of the desulfurization reaction) The activation energy of the desulfurization reaction can be obtained by a method known in the art based on the Arrhenius formula represented by the above formula 6. An example is described below.

[0143] First, the reaction order of the desulfurization reaction of the feedstock oil containing atmospheric distillation residue oil is determined. The reaction temperature, hydrogen partial pressure, hydrogen / feedstock oil ratio, and sulfur concentration in the feedstock oil are set as constant conditions, and the reaction is carried out under the condition of LHSV(x), and the sulfur concentration in the product oil is measured. S in the desulfurization reaction rate formula represented by the following formula 27 F is substituted with the sulfur concentration in the feedstock oil, and S P is substituted with the sulfur concentration in the obtained product oil, and LHSV is substituted with LHSV(x). The obtained result on the left side is plotted on the vertical axis, and 1 / LHSV is plotted on the horizontal axis. In this case, the vertical axis is a function of n.

[0144]

Number

[0145] Perform the same reaction for x types of LHSV(x) to obtain x plots as described above. Based on the obtained plots, draw a regression line passing through the origin to obtain a line represented by y = cx. y is (1 / n - 1((1 / S P n-1 )) - (1 / S F n-1 ))), x is 1 / LHSV, and c becomes k. Use software like Excel to find the correlation function and determine the n for which the correlation coefficient is closest to 1. The obtained n is the reaction order. Note that n may be determined to the order of the first decimal place.

[0146] The above x is an integer of 3 or more. The larger the number of x, the higher the accuracy of n that can be obtained. On the other hand, if the number of x is too large, it takes time to obtain n and it is not efficient. In this embodiment, x is preferably 3 to 20, and more preferably 3 to 10.

[0147] The reaction temperature, hydrogen partial pressure, hydrogen / feedstock oil ratio, and sulfur concentration in the feedstock oil for determining n are preferably set to conditions in accordance with the actual operating conditions. Such a reaction temperature is, for example, 330 to 410°C, the hydrogen partial pressure is 5 to 15 MPa, the hydrogen / feedstock oil ratio is 170 to 1400 [Nm 3 / kL], and the sulfur concentration in the feedstock oil is 1 to 5 mass%. The x types of LHSV(x) are also preferably set to conditions in accordance with the actual operating conditions. Such LHSV(x) is 0.1 to 1.0 h -1 .

[0148] Regarding the activation energy E in the Arrhenius equation represented by Equation 6 as the activation energy Ea for desulfurization and taking the natural logarithm of both sides, the equation represented by the following Equation 28 is obtained.

Equation

[0149] The hydrogen partial pressure, hydrogen / feedstock oil ratio, LHSV, and sulfur concentration in the feedstock oil are set as constant conditions, and the reaction is carried out under the condition of the reaction temperature T(y), and the sulfur concentration in the product oil is measured. In the S of the desulfurization reaction rate equation represented by the above formula 27 F substitute the sulfur concentration in the feedstock oil, and for S P substitute the sulfur concentration in the product oil obtained, substitute LHSV for LHSV, and substitute the obtained n into the above to obtain the reaction rate constant k. Substitute the obtained reaction rate constant into the above formula 28, and plot the result (lnk) of the obtained left side on the vertical axis and 1 / T(1 / T(y)) on the horizontal axis.

[0150] Perform the same reaction for y types of reaction temperatures T(y) to obtain y plots as described above. Draw a regression line from the obtained plots and determine its slope. Since this slope is Ea / R, the activation energy Ea for desulfurization can be determined by dividing by R from the slope.

[0151] The above y is an integer of 3 or more. The larger the number of y, the higher the accuracy of Ea that can be obtained. On the other hand, if the number of y is too large, it takes time to obtain Ea and it is not efficient. In the present embodiment, y is preferably 3 to 20, and more preferably 3 to 10.

[0152] The hydrogen partial pressure, hydrogen / feedstock oil ratio, LHSV, and sulfur concentration in the feedstock oil for determining Ea are preferably set to conditions in accordance with the actual machine operation conditions. As such a hydrogen partial pressure, for example, it is 5 to 18 MPa, the hydrogen / feedstock oil ratio is 170 to 1400 [Nm 3 / kL], the LHSV is 0.1 to 1.0 h -1 and the sulfur concentration in the feedstock oil is 1 to 4 mass%. The y types of reaction temperatures T(y) are also preferably set to conditions in accordance with the actual machine operation conditions. Such T(y) is 330 to 410 °C.

[0153] By substituting each parameter obtained in this way into the above formula 26, the reaction temperature T t required to achieve a predetermined reaction condition can be determined.

[0154] Measured reaction temperature T obs The reaction temperature T obtained by the information processing method of this embodiment with respect to t The ratio of T t / T obs Is preferably 0.97 to 1.03, more preferably 0.985 to 1.015 in °C conversion. T t / T obs When T / T is within the above range, it can be determined that the reaction temperature is accurately estimated.

[0155] <<Information output step>> It may further have an information output step (S4 in FIG. 1) for outputting information indicating the reaction temperature thus obtained. For example, S4 is executed by the output unit 14.

[0156] <<Hydrogenation treatment reaction of feedstock oil containing atmospheric distillation residue oil>> The outline of the hydrogenation treatment reaction of the feedstock oil containing atmospheric distillation residue oil will be described. The atmospheric distillation residue oil is a fraction with a boiling range of 370 °C or higher obtained by atmospheric distillation of crude oil. The density of the atmospheric distillation residue oil is 0.92 to 1.00 g / mL. The content of the atmospheric distillation residue oil in the feedstock oil may be, for example, 50% by volume or more, or 70% by volume or more. In addition, examples of oil types other than the atmospheric distillation residue oil contained in the feedstock oil include vacuum distillation residue oil obtained by vacuum distillation of the atmospheric distillation residue oil. When the feedstock oil contains vacuum distillation residue oil, the content of the vacuum distillation residue oil in the feedstock oil is, for example, 0 to 50% by volume.

[0157] The hydrogenation treatment reaction of the feedstock oil containing atmospheric distillation residue oil can be carried out by contacting the feedstock oil containing atmospheric distillation residue oil with a hydrogenation treatment catalyst in the presence of hydrogen. The hydrotreating catalyst is not particularly limited, and a hydrotreating catalyst known in the art can be used. As the catalyst carrier, various materials can be used, such as silica, alumina, boria, magnesia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-boria, alumina-zirconia, alumina-titania, alumina-boria, alumina-chromia, titania-zirconia, silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, etc., or a mixture of two or more of these. Among these inorganic oxides, preferred ones include alumina, silica-alumina, alumina-titania, alumina-boria, alumina-zirconia, and particularly preferably alumina, and among alumina, γ-alumina is particularly preferred. These inorganic oxides may be used alone or in combination of two or more.

[0158] The metal contained as an active component in the carrier is at least one metal selected from Group 6 metals and Group 8-10 metals of the periodic table, preferably molybdenum, tungsten, cobalt, and nickel metals. These metals are effective in any form of metal state, metal oxide, or metal sulfide, and may also exist in a form in which the metal is bonded to the catalyst carrier by ion exchange or the like. The content of this metal component is usually in the range of about 1 to 25% by mass on a catalyst basis and in terms of oxide conversion. If the metal content is less than 1% by mass, the absolute amount of the metal acting as the active site is small, so the hydrotreating activity (hereinafter simply referred to as hydrotreating activity), including desulfurization activity, is not exhibited. Conversely, if the content of the supported metal is too much more than 25% by mass, metal aggregation occurs and the number of active sites decreases, and as a result, the hydrotreating activity decreases instead. Furthermore, if necessary, in addition to the active metals composed of Group 6 metals and Group 8 metals of the periodic table, phosphorus, boron, zinc, zirconia, etc. can be included. When applying the method of the present invention, there is no restriction 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.

[0159] As conditions in the hydrotreating reaction of a feedstock oil containing atmospheric distillation residue oil, generally, the reaction temperature is 330 to 410 °C, preferably 360 to 400 °C, the hydrogen partial pressure is 5 to 15 MPa, preferably 10 to 18 MPa, and the LHSV is 0.1 to 1.0 h -1 , preferably 0.1 to 0.35 h -1 and the hydrogen / feedstock oil ratio is 170 to 1400 [Nm 3 / kL], preferably 670 to 1200 [Nm 3 / kL].

[0160] The sulfur concentration in the feedstock oil containing atmospheric distillation residue oil is usually 1 to 5 mass%. Also, the sulfur concentration in the produced oil is usually 0.1 to 0.5 mass%. The metal concentration in the feedstock oil containing atmospheric distillation residue oil is usually 30 to 300 weight ppm. Also, the metal concentration in the produced oil is usually 5 to 30 weight ppm.

[0161] ≪Reaction Temperature Calculation Device≫ The reaction temperature calculation device of the present embodiment includes an acquisition unit that acquires information on the feedstock oil, information on the produced oil, and information on the operating conditions when a predetermined time has elapsed since the start of the reaction regarding the hydrotreating reaction of a feedstock oil containing atmospheric distillation residue oil, and a calculation unit that calculates the degree of catalyst deterioration using a deterioration function based on the information on the feedstock oil, the information on the produced 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 feedstock oil, the information on the produced oil, and the operating conditions based on the calculated degree of catalyst deterioration. The reaction temperature calculation device of the present embodiment may have an output unit that outputs information indicating the calculated reaction temperature.

[0162] 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 a plurality of information processing devices. For example, the reaction temperature calculation device 1 may be constructed as a cluster machine, may be constructed as a cloud, or may be constructed in any manner. The reaction temperature calculation device 1 has, for example, an acquisition unit 11 as shown in FIG. 4 and a computer main body 12 that processes information from the acquisition unit. The reaction temperature calculation device 1 may have an output unit 14 that outputs the information processed in the computer main body 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). Also, some or all of these components may be realized by hardware (including a circuit unit; circuitry) such as an LSI (Large Scale Integrated circuit), an ASIC (Application Specific Integrated Circuit), an FPGA (Field-Programmable Gate Array), or a GPU (Graphics Processing Unit), or may be realized by the cooperation of software and hardware. The program may be stored in advance in a storage device (a storage device having a non-transitory storage medium) such as an HDD (Hard Disk Drive) or a flash memory, or may be stored in a removable storage medium (a non-transitory storage medium) such as a DVD or a CD-ROM, and may be installed in the storage device when the storage medium is mounted on a drive device. The storage device is composed of, for example, an HDD, a flash memory, an EEPROM (Electrically Erasable Programmable Read Only Memory), a ROM (Read Only Memory), or a RAM (Random Access Memory), etc.

[0163] The acquisition unit 11 is configured such that predetermined information is input by the operator of the reaction, and the information acquired by this input is transmitted to the computer main body 12. The information acquired by the acquisition unit 11 in the present embodiment is information regarding the raw material oil, the produced oil, and the operating conditions at the time when a predetermined time has elapsed since the start of the reaction, with respect to the hydrotreating reaction of the raw material oil containing atmospheric residue. The information regarding the raw material oil, the produced oil, and the operating conditions at the time when a predetermined time has elapsed since the start of the reaction is as described above. For example, the acquisition unit 11 executes the above-described information acquisition step. The acquisition unit 11 may acquire the information regarding the raw material oil, the produced oil, and the operating conditions at the time when a predetermined time has elapsed since the start of the reaction, and there is no particular limitation on the acquisition method therefor.

[0164] In the present embodiment, the acquisition unit 11 is constituted by a single keyboard. The specific configuration of the acquisition unit 11 is not limited, and in the present embodiment, it is a keyboard, but it may be a touch panel or the like. Note that the acquisition units for acquiring various information may be separately configured and each may be independently connected to the computer main body 12. Further, the acquisition unit 11 may be configured to directly acquire each of the above information from a computer or the like used for controlling the reactor or the like, either by wire or wirelessly.

[0165] The computer main body 12 is, for example, a so-called computer capable of processing various kinds of information. The computer main body 12 includes an arithmetic unit 13. For example, a predetermined program is incorporated in this computer main body 12, and functionally, the arithmetic unit 13 is configured by the execution of this program. Specifically, in this arithmetic unit 13, based on the information on the feedstock oil, the information on the product oil, and the information on the operating conditions when a predetermined time has elapsed since the reaction acquired by the acquisition unit 11 was started, the degree of catalyst deterioration is calculated by a deterioration function, and based on the degree of catalyst deterioration, the information on the feedstock oil, the information on the product oil, and the reaction temperature required to satisfy the operating conditions are calculated. The deterioration function is as described above. As described above, the reaction temperature can be obtained from, for example, a deterioration rate formula. For example, the arithmetic unit 13 executes the above-described deterioration degree calculation step and reaction temperature calculation step. Also, in the arithmetic unit 13, it is preferable to execute a step of determining the timing for switching the above-described η. The arithmetic unit 13 may include, for example, a processor such as a CPU (Central Processing Unit) or an MPU (Micro Processing Unit) and a non-volatile or volatile semiconductor memory (for example, 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.

[0166] The arithmetic unit 13 may output to the output unit 14 the information on the feedstock oil obtained as described above, the information on the product oil, and the information indicating the reaction temperature required to satisfy the operating conditions.

[0167] The output unit 14 receives the calculation results (reaction temperatures) output by the computer main body 12 (more specifically, the calculation unit 13) and outputs the received calculation results to the outside. The output unit 14 of this embodiment is configured by a display unit such as a CRT display, a liquid crystal display, or a PDP, but is not limited to this and may be configured to output to a printing unit such as a printer, or to other devices (for example, a computer used to control the hydrotreating reaction of feed oil including atmospheric distillation residue oil), etc. The output unit 14 may also be a combination of these. For example, the output unit 14 executes the information output step described above.

[0168] Furthermore, in this embodiment, there is provided a reaction temperature calculation program for causing a computer to function as a reaction temperature calculation device, and a non-transitory computer-readable recording medium storing the program. Examples of non-transitory computer-readable recording media include magnetic tapes (such as digital data storage (DSS)), magnetic disks (such as hard disk drives (HDDs) and flexible disks (FDs)), optical disks (such as compact disks (CDs), digital versatile disks (DVDs), and Blu-ray disks (BDs)), magneto-optical disks (MOs), and flash memories (such as solid-state drives (SSDs), memory cards, and USB memories).

[0169] <Method of using information processing method and reaction temperature calculation device> The information processing method and reaction temperature calculation device of this embodiment can estimate the reaction temperature required to achieve specified reaction conditions for the hydrotreating reaction of feedstock oil containing atmospheric distillation residue. The information processing method and reaction temperature calculation device of this embodiment can obtain a plot of estimated reaction temperatures over time. The relationship between the plot and the maximum equipment operating temperature, etc., can be used in the following ways.

[0170] As a first utilization method, it is to estimate the operation time (number of days) required to replace the catalyst under predetermined reaction conditions. That is, from the plot, the time when the temperature reaches the maximum temperature of equipment use can be estimated, and from this time, the operation time (number of days) required to replace the catalyst can be estimated. Also, when the estimated reaction temperature is not less than the equipment set temperature, the information processing method shown in S4-1 to S4-3 of FIG. 2 may be performed. The information processing method shown in S4-1 to S4-3 of FIG. 2 includes an information acquisition step (S4-1 of FIG. 2) for acquiring information regarding the target reaction temperature, a degradation degree calculation step (S4-2 of FIG. 2) for calculating the degradation degree of the catalyst by a degradation function based on the acquired target reaction temperature, and a reaction condition calculation step (S4-3 of FIG. 2) for calculating information regarding the feedstock oil, information regarding the product oil, and information regarding the operation conditions necessary to satisfy the target reaction temperature based on the degradation degree. It may further have an information output step (S4-4 of FIG. 2) for outputting the information regarding the feedstock oil, the information regarding the product oil, and the information regarding the operation conditions thus obtained. Specifically, for example, when using the coke degradation function 1 and the metal degradation function 1, substitute the target reaction temperature into T in the formula 26 and obtain Φ. Substitute the obtained Φ into the formula 2 to obtain Φ t , Φ C , Φ M . Substitute the obtained Φ C into the formula 3 to obtain D. Substitute the obtained D into the formula 4 to obtain a combination of S P , S F , LHSV, and P such that the equation of the formula 4 holds. Also, in the above combination, for example, when S P , S F are set values, P and LHSV may be obtained. Also, as the coke degradation function, any of the coke degradation function 1, coke degradation function 1-1, coke degradation function 2, and coke degradation function 2-1 may be used. Also, as the metal degradation function, any of the metal degradation function 1 and metal degradation function 2 may be used. When using the metal degradation function 2, M F , M pThe conditions of WHSV may be changed. Note that each of the above steps is executed, for example, by the reaction temperature calculation device 1 of the present embodiment. For example, S4-1 is executed by the acquisition unit 11, S4-2 and S4-3 are executed by the calculation unit 13 in the computer main body 12, and S4-4 is executed by the output unit 14. Note that the target temperature may be stored in advance in the calculation unit 13 in the computer main body 12.

[0171] As a second utilization method, it is to estimate reaction conditions (such as throughput (LHSV), etc.) for achieving a predetermined operation time. Such an information processing method is represented by S1A to 3A in FIG. 3. The information processing method shown in steps 1A to 3A in FIG. 3 includes an information acquisition step (S1A in FIG. 3) for acquiring information regarding the target reaction temperature at a predetermined operation time, and based on the acquired target reaction temperature, a deterioration degree calculation step (S2A in FIG. 3) for calculating the deterioration degree of the catalyst by a deterioration function, and a reaction condition calculation step (S3A in FIG. 3) for calculating information regarding the raw material oil, information regarding the produced oil, and information regarding the operation conditions necessary to satisfy the target reaction temperature based on the deterioration degree. It may further have an information output step (S4A in FIG. 3) for outputting the information regarding the raw material oil, the information regarding the produced oil, and the information regarding the operation conditions thus obtained. Specifically, for example, when using the coke deterioration function 1 and the metal deterioration function 1, substitute the target reaction temperature into T in the formula 26 to obtain Φ. Substitute the obtained Φ into the formula 2 to obtain Φ t , Φ C , Φ M and obtain Φ. Substitute the obtained Φ into the formula 3 to obtain D. Substitute the obtained D into the formula 4 to obtain a combination of S C , S P , S F , LHSV, and P such that the equation of the formula 4 holds. Also, in the above combination, for example, S P , S FAs a set value, P and LHSV may be determined. Further, as the coke deterioration function, any of coke deterioration function 1, coke deterioration function 1-1, coke deterioration function 2, and coke deterioration function 2-1 may be used. Further, as the metal deterioration function, any of metal deterioration function 1 and metal deterioration function 2 may be used. When using metal deterioration function 2, M F , M p , the conditions of WHSV may be changed. Note that each of the above steps is executed, for example, by the reaction temperature calculation device 1 of the present embodiment. For example, S1A is executed by the acquisition unit 11, S2A and S3A are executed by the calculation unit 13 in the computer main body 12, and S4A is executed by the output unit 14. Note that the target temperature may be stored in advance in the calculation unit 13 in the computer main body 12.

Example

[0172] Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples.

[0173] [Example] In a bench scale, a hydrotreating reaction was carried out by bringing a feedstock oil containing 70% by volume of atmospheric distillation residue oil into contact with a hydrotreating catalyst. Based on the obtained results, a deterioration function was calculated. In this example, coke deterioration function 2 represented by the above formula 17 was used. When the parameters in the above formulas 17 to 19 were determined by the above method, k1 = 0.47, k2 = 0.53, α1 = 0.078, α2 = 0.00072, P B = 13 (MPa), a = 2.6, Ec = 182 (kJ / mol), T B = 643.15 (K), T SOR = 641.15 (K), n = 2, η = 0.91, t end = 368 days.

[0174] Using the same feedstock oil and hydrotreating catalyst as those in the hydrotreating reaction carried out on a bench scale, a reaction was carried out on a full-scale unit. As the operating conditions in the above formulas 13, 14, and 15, S F = 4.12 (mass%), M F= 119 (weight ppm), P = 14.2 (MPa), LHSV = 0.194 (h -1 ), S P = 0.3 (mass %), M P = 13 (weight ppm). Also, when the activation energy for desulfurization was determined in advance by the above method, Ea = 147 (kJ / mol).

[0175] These basic deterioration parameters and reaction conditions were substituted into the above formulas 14 and 15 to obtain D1 and D2 at an arbitrary reaction time t days. The obtained D1, D2 and the number of reaction days t were substituted into the above formula 13 to obtain Φ C Also, the above basic deterioration parameters and the number of reaction days t were substituted into the above formula 20 to obtain Φ M The obtained Φ C and Φ M were used to obtain Φ from the above formula 2. At the initial stage of the reaction, η = 1 and Φ M = 1. When Z became 2 °C or higher at (η switching timing 1) above (when 151 days of reaction had elapsed), ΦM was obtained from the above formula 20 as the obtained Φ M and the reaction was continued. The Φ, Ea, and T thus obtained SOR were substituted into the above formula 26 to obtain the required temperature T t at an arbitrary reaction time t days. Table 1 shows the measured values of the reaction temperatures at t = 30 days, 150 days, and 250 days, the required temperature T t obtained by the above method, and the ratio of the required temperature T t to the measured value of the reaction temperature.

[0176]

Table 1

[0177] As shown in Table 1, it was found that the required temperature T t obtained by the present invention was almost equivalent to the measured value of the reaction temperature.

Explanation of Signs

[0178] 1 ··· Reaction temperature calculation device 11 ··· Acquisition unit 12 ··· Computer main body 13 ··· Arithmetic unit 14 ··· Output unit

Claims

1. Regarding the hydrotreating reaction of a feedstock oil containing atmospheric distillation residue oil, an information acquisition step of acquiring information regarding the feedstock oil, information regarding the product oil, and information regarding the operating conditions when a predetermined time has elapsed since the start of the reaction; A deterioration degree calculation step of calculating the deterioration degree of the catalyst by a deterioration function based on the acquired information regarding the feedstock oil, the information regarding the product oil, and the information regarding the operating conditions; A reaction temperature calculation step of calculating the reaction temperature necessary to satisfy the information regarding the feedstock oil, the information regarding the product oil, and the operating conditions based on the deterioration degree of the catalyst, which is an information processing method including: The information regarding the feedstock oil includes information regarding the sulfur concentration in the feedstock oil, the information regarding the product oil includes information regarding the sulfur concentration in the product oil, the information regarding the operating conditions includes information regarding the hydrogen partial pressure, information regarding the catalyst filling amount, and information regarding the supply amount of the feedstock oil; The deterioration function is a function represented by the following formula 2, which is an information processing method. Φ = ΦCΦM Formula 2 In the formula 2, Φ is the deterioration degree of the catalyst, ΦC is a coke deterioration function represented by the following formula 3, and ΦM is a metal deterioration function. ΦC = exp(−Dt) Formula 3 In the formula 3, D is a deterioration coefficient due to coke of the active species of the catalyst, which is calculated from the following formula 4, and t is the number of days elapsed since the reaction (days). 【Number 1】 In the formula 4, α is a catalyst constant (a constant representing the deterioration rate due to coke of the catalyst), SF is the sulfur concentration (mass%) in the feedstock oil at any time t days after the reaction, SP is the sulfur concentration (mass%) in the product oil at any time t days after the reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue oil, LHSV is the liquid hourly space velocity (h−1) at any time t days after the reaction, PB is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) at any time t days after the reaction, 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)), TB is the reference reaction temperature (K), and TSOR is the required temperature on the 0th day (K). α, PB, a, Ec, TB, and TSOR are constants determined according to the catalyst used. The constants are obtained while performing the reaction in a full-scale unit or are obtained in advance on a bench scale based on the full-scale operating conditions. Claim 2: Regarding the hydrotreating reaction of a feedstock oil containing atmospheric distillation residue oil, an information acquisition step of acquiring information regarding the feedstock oil, information regarding the produced oil, and information regarding the operating conditions when a predetermined time has elapsed since the start of the reaction; A deterioration degree calculation step of calculating the deterioration degree of the catalyst by a deterioration function based on the acquired information regarding the feedstock oil, the information regarding the produced oil, and the information regarding the operating conditions; A reaction temperature calculation step of calculating a reaction temperature necessary to satisfy the information regarding the feedstock oil, the information regarding the produced oil, and the operating conditions based on the deterioration degree of the catalyst, the information processing method comprising: The information regarding the feedstock oil includes information regarding the sulfur concentration in the feedstock oil, the information regarding the produced oil includes information regarding the sulfur concentration in the produced oil, and the information regarding the operating conditions includes information regarding the hydrogen partial pressure, information regarding the catalyst filling amount, information regarding the supply amount of the feedstock oil, and information regarding the supply amount of hydrogen; The deterioration function is a function represented by the following formula 2, the information processing method. Φ = ΦCΦM Formula 2 In the formula 2, Φ is the deterioration degree of the catalyst, ΦC is a coke deterioration function represented by the following formula 10, and ΦM is a metal deterioration function. ΦC = exp(−D't) Formula 10 In the formula 10, D' is the deterioration coefficient of coke of the active species of the catalyst and is calculated from the following formula 11, and t is the number of days elapsed since the reaction (days). 【Number 2】 In the above formula (11), α' is a catalyst constant (a constant representing the deterioration rate of the coke of the catalyst), SF is the sulfur concentration (mass %) in the feedstock oil at the end of an arbitrary reaction day t, SP 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 atmospheric distillation residue oil, LHSV is the liquid hourly space velocity (h-1) at the end of an arbitrary reaction day t, PB 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, GB is the reference hydrogen / feedstock oil ratio (Nm3 / kL), G is the hydrogen / feedstock oil ratio (Nm3 / 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)), TB is the reference reaction temperature (K), and TSOR is the required temperature on day 0 (K). α', PB, a, GB, b, Ec, TB, and TSOR are constants determined according to the catalyst to be used. The constants are determined while conducting the reaction in an actual machine, or are determined in advance on a bench scale based on the actual machine operating conditions.

3. Regarding the hydrotreating reaction of a feedstock oil containing atmospheric distillation residue oil, an information acquisition step of acquiring information regarding the feedstock oil, information regarding the product oil, and information regarding the operating conditions when a predetermined time has elapsed since the start of the reaction; A deterioration degree calculation step of calculating the deterioration degree of the catalyst by a deterioration function based on the acquired information regarding the feedstock oil, the information regarding the product oil, and the information regarding the operating conditions; A reaction temperature calculation step of calculating the reaction temperature necessary to satisfy the information regarding the feedstock oil, the information regarding the product oil, and the operating conditions based on the deterioration degree of the catalyst, which is an information processing method including: The information regarding the feedstock oil includes information regarding the sulfur concentration in the feedstock oil, the information regarding the product oil includes information regarding the sulfur concentration in the product oil, and the information regarding the operating conditions includes information regarding the hydrogen partial pressure, information regarding the catalyst filling amount, and information regarding the supply amount of the feedstock oil. The deterioration function is a function represented by the following formula (2), which is an information processing method. Φ = ΦCΦM Formula 2 In the above formula (2), Φ is the deterioration degree of the catalyst, ΦC is a coke deterioration function represented by the following formula (13), and ΦM is a metal deterioration function. ΦC = k1 × exp(−D1t) + k2 × exp(−D2t) Equation 13 In Equation 13 above, k1 is the active site coefficient of the easily deactivated active species of the catalyst, k2 is the active site coefficient of the hardly deactivated active species of the catalyst, and the active site coefficient represents the relative reaction rate constant of both active species. D1 is the deterioration coefficient due to coke of the easily deactivated active species of the catalyst and is calculated from Equation 14 below, D2 is the deterioration coefficient due to coke of the hardly deactivated active species of the catalyst and is calculated from Equation 15 below, t is the number of days elapsed since the start of the reaction (days), k1 + k2 = 1, and k1 and k2 are obtained while conducting the reaction in a real machine or are obtained in advance on a bench scale based on the real machine operating conditions. 【Number 3】 【Number 4】 In Equation 14 and Equation 15 above, SF is the sulfur concentration (mass %) in the feedstock oil at the time when an arbitrary reaction has elapsed for t days, SP is the sulfur concentration (mass %) in the product oil at the time when an arbitrary reaction has elapsed for t days, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric residue, LHSV is the liquid hourly space velocity (h−1) at the time when an arbitrary reaction has elapsed for t days, PB is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) at the time when an arbitrary reaction has elapsed for t days, 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)), TB is the reference reaction temperature (K), and TSOR is the required temperature on day 0 (K). In Equation 14, α1 is the catalyst constant of the easily deactivated active site (a constant representing the deterioration rate due to coke of the catalyst), and in Equation 15, α2 is the catalyst constant of the hardly deactivated active site (a constant representing the deterioration rate due to coke of the catalyst). α1, α2, PB, a, Ec, TB, and TSOR are constants determined according to the catalyst used. The above constants are obtained while conducting the reaction in a real machine or are obtained in advance on a bench scale based on the real machine operating conditions.

4. Regarding the hydrotreating reaction of a feedstock oil containing atmospheric residue, an information acquisition step of acquiring information regarding the feedstock oil, information regarding the product oil, and information regarding the operating conditions when a predetermined time has elapsed since the start of the reaction; A degree of deterioration calculation step of calculating the degree of deterioration of the catalyst by a deterioration function based on the acquired information regarding the feedstock oil, the information regarding the product oil, and the information regarding the operating conditions; A reaction temperature calculation step of calculating the information on the feedstock oil, the information on the product oil, and the reaction temperature required to satisfy the operating conditions based on the degree of deterioration of the catalyst, and an information processing method including the same. The information on the feedstock oil includes information on the sulfur concentration in the feedstock oil, the information on the product oil includes information on the sulfur concentration in the product oil, and the information on the operating conditions includes information on the hydrogen partial pressure, the catalyst filling amount, the feedstock oil supply amount, and the hydrogen supply amount. The deterioration function is a function represented by the following formula 2, and an information processing method. Φ = ΦCΦM Formula 2 In the formula 2, Φ is the degree of deterioration of the catalyst, ΦC is the coke deterioration function represented by the following formula 17, and ΦM is the metal deterioration function. ΦC = k1×exp(−D1't) + k2×exp(−D2't) Formula 17 In the formula 17, k1 is the active site coefficient of the easily deactivated active species of the catalyst, k2 is the active site coefficient of the hardly deactivated active species of the catalyst, and the active site coefficient represents the relative reaction rate constant of both active species. D1' is the coke deterioration coefficient of the easily deactivated active species of the catalyst and is calculated from the following formula 18, D2' is the coke deterioration 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 reaction (days), k1 + k2 = 1, and k1 and k2 are obtained while performing the reaction in an actual machine or are obtained in advance on a bench scale based on the actual machine operating conditions. 【Number 5】 【Number 6】 In the above formulas 18 and 19, SF is the sulfur concentration (mass %) in the feedstock oil at the end of an arbitrary reaction time t, SP is the sulfur concentration (mass %) in the product oil at the end of an arbitrary reaction time t, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric distillation residue, LHSV is the liquid hourly space velocity (h-1) at the end of an arbitrary reaction time t, PB is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) at the end of an arbitrary reaction time t, a is the hydrogen partial pressure coefficient, GB is the reference hydrogen / feedstock oil ratio (Nm3 / kL), G is the hydrogen / feedstock oil ratio (Nm3 / kL) at the end of an arbitrary reaction time 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)), TB is the reference reaction temperature (K), and TSOR is the required temperature on day 0 (K). In the above formula 18, α1' is the catalyst constant of the easily deactivated active site (a constant representing the deterioration rate due to coke on the catalyst), and in the above formula 19, α2' is the catalyst constant of the hardly deactivated active site (a constant representing the deterioration rate due to coke on the catalyst). α1', α2', PB, a, GB, b, Ec, TB, and TSOR are constants determined according to the catalyst used. The above constants are determined while performing the reaction in a full-scale unit or determined in advance on a bench scale based on the full-scale operation conditions.

5. A reaction temperature calculation device for a hydrotreating reaction of a feedstock oil containing atmospheric distillation residue, comprising: an acquisition unit that acquires information on the feedstock oil, information on the product oil, and information on the operating conditions when a predetermined time has elapsed since the start of the reaction; and a calculation unit that calculates the degree of catalyst deterioration by a deterioration function based on the information on the feedstock oil, the information on the product oil, and the information on the operating conditions acquired by the acquisition unit, and calculates a reaction temperature necessary to satisfy the information on the feedstock oil, the information on the product oil, and the operating conditions based on the calculated degree of catalyst deterioration. The information on the feedstock oil includes information on the sulfur concentration in the feedstock oil, the information on the product oil includes information on the sulfur concentration in the product oil, and the information on the operating conditions includes information on the hydrogen partial pressure, information on the catalyst filling amount, and information on the supply amount of the feedstock oil. The reaction temperature calculation device, wherein the deterioration function is a function represented by the following formula 2. Φ = Φ C Φ M Formula 2 In Formula 2 above, Φ is the degree of catalyst deterioration, Φ C is the coke deterioration function represented by the following formula 3, and Φ M is the metal deterioration function. Φ C = exp(−Dt) Formula 3 In Formula 3 above, D is the deterioration coefficient due to coke of the active species of the catalyst, which is calculated from the following formula 4, and t is the number of days elapsed since the start of the reaction (days). 【Number 7】 In Formula 4 above, α is a catalyst constant (a constant representing the deterioration rate due to coke of the catalyst), S F is the sulfur concentration (mass %) in the feedstock oil at any time t days after the start of the reaction, S P is the sulfur concentration (mass %) in the product oil at any time t days after the start of the reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric residue, LHSV is the liquid hourly space velocity (h −1 ) at any time t days after the start of the reaction, P B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) at any time t days after the start of the reaction, a is the hydrogen partial pressure coefficient, E c 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), and T SOR is the required temperature (K) on the 0th day. α, P B, a, E c, T B, and T SOR are constants determined according to the catalyst to be used. The constants are determined while conducting the reaction in an actual machine or determined in advance on a bench scale based on the actual machine operating conditions.

6. A reaction temperature calculation device for a hydrotreating reaction of a feedstock oil containing atmospheric residue, comprising: an acquisition unit that acquires information on the feedstock oil, information on the product oil, and information on the operating conditions when a predetermined time has elapsed since the start of the reaction; and an arithmetic unit that calculates the degree of catalyst deterioration using a deterioration function based on the information on the feedstock oil, the information on the product oil, and the information on the operating conditions acquired by the acquisition unit, and calculates the reaction temperature required to satisfy the information on the feedstock oil, the information on the product oil, and the operating conditions based on the calculated degree of catalyst deterioration. The information on the feedstock oil includes information on the sulfur concentration in the feedstock oil, the information on the product oil includes information on the sulfur concentration in the product oil, and the information on the operating conditions includes information on the hydrogen partial pressure, information on the catalyst filling amount, information on the supply amount of the feedstock oil, and information on the supply amount of hydrogen. The reaction temperature calculation device, wherein the deterioration function is a function represented by the following formula 2. Φ = ΦCΦM Formula 2 In Formula 2, Φ is the degree of catalyst deterioration, ΦC is the coke deterioration function represented by the following formula 10, and ΦM is the metal deterioration function. ΦC = exp(−D't) Formula 10 In Formula 10, D' is the deterioration coefficient of coke of the active species of the catalyst, which is calculated from the following formula 11, and t is the number of days elapsed since the start of the reaction (days). 【Number 8】 In Formula 11, α' is a catalyst constant (a constant representing the coke deterioration rate of the catalyst), SF is the sulfur concentration (mass%) in the feedstock oil at any time t days after the reaction, SP is the sulfur concentration (mass%) in the product oil at any time t days after the reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric residue oil, LHSV is the liquid hourly space velocity (h−1) at any time t days after the reaction, PB is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) at any time t days after the reaction, a is the hydrogen partial pressure coefficient, GB is the reference hydrogen / feedstock oil ratio (Nm3 / kL), G is the hydrogen / feedstock oil ratio (Nm3 / kL) at any time t days after the reaction, 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)), TB is the reference reaction temperature (K), and TSOR is the required temperature on the 0th day (K). α', PB, a, GB, b, Ec, TB, and TSOR are constants determined according to the catalyst used. The constants are determined while performing the reaction in a full-scale unit or determined in advance on a bench scale based on the full-scale operation conditions. **Claim 7**: A reaction temperature calculation device for a hydrotreating reaction of a feedstock oil containing atmospheric residue oil, comprising: an acquisition unit that acquires information on the feedstock oil, information on the product oil, and information on the operating conditions when a predetermined time has elapsed since the start of the reaction; and a calculation unit that calculates the degree of catalyst deterioration by a deterioration function based on the information on the feedstock oil, the information on the product oil, and the information on the operating conditions acquired by the acquisition unit, and calculates the reaction temperature required to satisfy the information on the feedstock oil, the information on the product oil, and the operating conditions based on the calculated degree of catalyst deterioration. The information regarding the raw material oil includes information on the sulfur concentration in the raw material oil, the information regarding the produced oil includes information on the sulfur concentration in the produced oil, and the information regarding the operating conditions includes information on the hydrogen partial pressure, information on the catalyst filling amount, and information on the supply amount of the raw material oil. The deterioration function is a function represented by the following formula 2, and it is a reaction temperature calculation device. Φ = ΦCΦM Formula 2 In the formula 2, Φ is the degree of catalyst deterioration, ΦC is a coke deterioration function represented by the following formula 13, and ΦM is a metal deterioration function. ΦC = k1×exp(−D1t) + k2×exp(−D2t) Formula 13 In the formula 13, k1 is the active site coefficient of the easily deactivated active species of the catalyst, k2 is the active site coefficient of the hardly deactivated active species of the catalyst, and the active site coefficient represents the relative reaction rate constant of both active species. D1 is the deterioration coefficient due to coke of the easily deactivated active species of the catalyst and is calculated from the following formula 14, D2 is the deterioration coefficient due to coke of the hardly deactivated active species of the catalyst and is calculated from the following formula 15, t is the number of days elapsed since the reaction (days), k1 + k2 = 1, and k1 and k2 are obtained while performing the reaction in an actual machine or are obtained in advance on a bench scale based on the actual machine operating conditions. 【Number 9】 【Number 10】 In the above formula (14) and formula (15), SF is the sulfur concentration (% by mass) in the feedstock oil at the end of an arbitrary reaction day t, SP is the sulfur concentration (% by 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 atmospheric residue, LHSV is the liquid hourly space velocity (h-1) at the end of an arbitrary reaction day t, PB 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)), TB is the reference reaction temperature (K), and TSOR is the required temperature (K) on the 0th day. 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 due to coke), and 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 due to coke). α1, α2, PB, a, Ec, TB, and TSOR are constants determined according to the catalyst used. The above constants are determined while performing the reaction in a real machine or determined in advance on a bench scale based on the real machine operating conditions.

8. A reaction temperature calculation device for a hydrotreating reaction of a feedstock oil containing atmospheric residue, comprising: an acquisition unit that acquires information on the feedstock oil, information on the product oil, and information on the operating conditions when a predetermined time has elapsed since the start of the reaction; and a calculation unit that calculates the degree of catalyst deterioration using a deterioration function based on the information on the feedstock oil, the information on the product oil, and the information on the operating conditions acquired by the acquisition unit, and calculates the reaction temperature required to satisfy the information on the feedstock oil, the information on the product oil, and the operating conditions based on the calculated degree of catalyst deterioration. The information on the feedstock oil includes information on the sulfur concentration in the feedstock oil, the information on the product oil includes information on the sulfur concentration in the product oil, and the information on the operating conditions includes information on the hydrogen partial pressure, information on the catalyst filling amount, information on the supply amount of the feedstock oil, and information on the supply amount of hydrogen. The deterioration function is a function represented by the following formula (2), and is a reaction temperature calculation device. Φ = ΦCΦM Formula 2 In the above formula (2), Φ is the degree of catalyst deterioration, ΦC is a coke deterioration function represented by the following formula (17), and ΦM is a metal deterioration function. ΦC = k1 × exp(−D1't) + k2 × exp(−D2't) Equation 17 In Equation 17 above, k1 is the active site coefficient of the easily deactivated active species of the catalyst, k2 is the active site coefficient of the difficult-to-deactivate active species of the catalyst, and the active site coefficient represents the relative reaction rate constant of both active species. D1' is the coke deterioration coefficient of the easily deactivated active species of the catalyst and is calculated from the following Equation 18, D2' is the coke deterioration coefficient of the difficult-to-deactivate active species of the catalyst and is calculated from the following Equation 19, t is the number of days elapsed in the reaction (days), k1 + k2 = 1, and k1 and k2 are determined while conducting the reaction in a full-scale unit or are determined in advance at the bench scale based on the full-scale operating conditions. 【Number 11】 【Number 12】 In Equation 18 and Equation 19 above, SF is the sulfur concentration (mass%) in the feedstock oil at the elapsed time of any reaction t days, SP is the sulfur concentration (mass%) in the product oil at the elapsed time of any reaction t days, n is the reaction order of the hydrotreating reaction of the feedstock oil containing atmospheric residue, LHSV is the liquid hourly space velocity (h−1) at the elapsed time of any reaction t days, PB is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) at the elapsed time of any reaction t days, a is the hydrogen partial pressure coefficient, GB is the reference hydrogen / feedstock oil ratio (Nm3 / kL), G is the hydrogen / feedstock oil ratio (Nm3 / kL) at the elapsed time of any reaction t days, 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)), TB is the reference reaction temperature (K), and TSOR is the required temperature on day 0 (K). In Equation 18, α1' is the catalyst constant of the easily deactivated active site (a constant representing the deterioration rate due to coke of the catalyst), and in Equation 19, α2' is the catalyst constant of the difficult-to-deactivate active site (a constant representing the deterioration rate due to coke of the catalyst). α1', α2', PB, a, GB, b, Ec, TB, and TSOR are constants determined according to the catalyst used. The above constants are determined while conducting the reaction in a full-scale unit or are determined in advance at the bench scale based on the full-scale operating conditions.

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

10. A non-transitory readable recording medium of a computer storing the program according to Claim 9

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