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

Abstract

To provide, regarding hydrotreating reaction of raw oil including reduced-pressure distillation gas oil, an information processing method capable of estimating a reaction temperature required to achieve a predetermined reaction condition, a reaction temperature calculation device capable of estimating the reaction temperature, a reaction temperature calculation program for forcing a computer to function as the reaction temperature calculation device, and a non-temporary readable recording medium for the computer that stores the program.SOLUTION: An information processing method includes: an information acquisition step to acquire information on raw oil including reduced-pressure distillation gas 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: None

Description

Technical Field

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

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. On the other hand, a method of subjecting the atmospheric distillation residue oil to vacuum distillation to separate it into vacuum distillation light oil and vacuum distillation residue oil, reducing the sulfur content by hydrotreating the vacuum distillation light oil, and mixing the hydrotreated vacuum distillation light oil and the vacuum distillation residue is known as indirect desulfurization.

[0003] In the hydrotreating of vacuum distillation light 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. Therefore, in order to keep the sulfur content in the produced oil below a certain level, the operation must be carried out at an increased reaction temperature in response to 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 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 there is a surplus 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 hydrotreating 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 hydrotreating catalyst. Therefore, a method for estimating the optimal reaction temperature while considering the decrease in the activity of the hydrotreating catalyst is desired.

[0008] The present invention has been made in view of the above circumstances, and relates to an information processing method for estimating the reaction temperature necessary to achieve predetermined reaction conditions in the hydrotreating reaction of a feedstock oil containing vacuum distillation light 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.

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 vacuum distillation light oil obtained by vacuum distilling atmospheric distillation residual oil, an information acquisition step of acquiring 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; a degree of deterioration calculation step of calculating the degree of deterioration of the catalyst by a deterioration function based on the acquired information on the feedstock oil, the information on the product oil, and the information on the operating conditions; and a reaction temperature calculation step of calculating the reaction temperature necessary to satisfy the information on the feedstock oil, the information on the product oil, and the operating conditions based on the degree of deterioration of the catalyst. An information processing method comprising: [2] The deterioration function is a coke deterioration function regarding the deterioration of the catalyst due to the deposition of coke, and is composed of a readily deactivating active species deterioration function regarding the deterioration of the readily deactivating active species of the catalyst and a hardly deactivating active species deterioration function regarding the deterioration of the hardly deactivating active species of the catalyst. The information processing method according to [1]. [3] The information on the feedstock oil includes information on the sulfur concentration in the feedstock oil, and the information on the product oil includes information on the sulfur concentration in the product oil. The information processing method according to [1] or [2]. [4] The information on 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 information processing method according to any one of [1] to [3]. [5] Regarding the hydrotreating reaction of a feedstock oil containing vacuum distillation light oil obtained by vacuum distilling atmospheric distillation residual oil, 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; 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, a calculation unit that calculates the degree of deterioration of the catalyst by a deterioration function, and based on the calculated degree of deterioration of the catalyst, calculates the reaction temperature necessary to satisfy the information on the feedstock oil, the information on the product oil, and the operating conditions. A reaction temperature calculation device comprising: [6] The reaction temperature calculation device described in [5], wherein the deterioration function is a coke deterioration function relating to catalyst deterioration due to coke deposition, and is composed of an easily deactivated active species deterioration function relating to deterioration of easily deactivated active species of the catalyst and a hardly deactivated active species deterioration function relating to deterioration of hardly deactivated active species of the catalyst. [7] The reaction temperature calculation device described in [5] or [6], wherein the information about the feedstock oil includes information about the sulfur concentration in the feedstock oil, and the information about the produced oil includes information about the sulfur concentration in the produced oil. [8] The reaction temperature calculation device according to any one of [5] to [7], wherein the information on the operating conditions includes information on the hydrogen partial pressure, information on the catalyst loading amount, and information on the feedstock supply amount. [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 computer-readable recording medium storing the program described in [9]. [Effects of the Invention]

[0010] According to the present invention, there are provided an information processing method capable of estimating a reaction temperature required to achieve predetermined reaction conditions for a hydrotreating reaction of feedstock oil containing vacuum distillation gas oil, a reaction temperature calculation device capable of estimating the reaction temperature, a reaction temperature calculation program for causing a computer to function as the reaction temperature calculation device, and a non-transitory computer-readable recording medium storing the program. [Brief explanation of the drawings]

[0011]

Figure 1

Figure 2

Figure 3

Figure 4

[0012] The following describes in detail the embodiments of the present invention. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to these contents and can be modified and implemented within the scope of its gist.

[0013] <Information processing method> The information processing method of this embodiment relates to a hydrotreating reaction of a feedstock containing vacuum distillation gas oil obtained by vacuum distillation of atmospheric distillation residue oil. The method includes: an information acquisition step (S1 in FIG. 1) for acquiring information about the feedstock, information about the product oil, and information about the operating conditions at a predetermined time after the start of the reaction; a deterioration degree calculation step (S2 in FIG. 1) for calculating the deterioration level of the catalyst using a deterioration function based on the acquired information about the feedstock, information about the product oil, and information about the operating conditions; and a reaction temperature calculation step (S3 in FIG. 1) for calculating the reaction temperature required to satisfy the information about the feedstock, information about the product oil, and the operating conditions based on the deterioration level of the catalyst. Each step will be described below. Note that each step shown below is executed, for example, by the reaction temperature calculation device 1 of this 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 Steps> The information acquisition step of this embodiment is a step of acquiring information about the feedstock oil, information about the product oil, and information about the operating conditions when a predetermined time has elapsed since the start of the reaction. The predetermined time after the start of the reaction refers to, for example, any t days having elapsed since the start of the reaction. t may be an integer or a decimal; for example, if t is 0.5, it means that 12 hours have elapsed since the start of the reaction. Furthermore, the time when t days have elapsed may be in the past, present, or future from the time when the information processing method of this embodiment is implemented. For example, if the information processing method of this embodiment is implemented two days after the start of the reaction and t is 4, the reaction temperature two days later (in the future) will be estimated.

[0015] (Information about raw material oil) An example of the information about the feedstock oil is information about the composition of the feedstock oil. An example of the information about the composition of the feedstock oil is information about the sulfur concentration in the feedstock oil.

[0016] Information on the sulfur concentration in the feedstock oil can be obtained by sulfur concentration measurement methods known in the art, such as ultraviolet fluorescence spectroscopy and wavelength dispersive X-ray fluorescence spectroscopy. 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 to be used can be used.

[0017] (Information about the produced oil) Examples of the information about the product oil include information about the composition of the product oil, and information about the sulfur concentration in the product oil.

[0018] Information regarding the sulfur concentration in the product oil can be obtained in the same manner as in the case of the feedstock oil described above. In this embodiment, the information regarding the sulfur concentration in the product oil is preferably a set value. That is, the sulfur concentration of the target product oil can be used.

[0019] (Information about operating conditions) Examples of information about operating conditions include information about hydrogen partial pressure, information about catalyst loading, information about the feedstock feed rate, and information about the hydrogen feed rate. For example, the information about operating conditions is at least one of information about hydrogen partial pressure, information about catalyst loading, information about the feedstock feed rate, and information about the hydrogen feed rate. In particular, the information about operating conditions preferably includes information about hydrogen partial pressure, information about catalyst loading, and information about the feedstock feed rate, and more preferably includes all of information about hydrogen partial pressure, information about catalyst loading, information about the feedstock feed rate, and information about the hydrogen feed rate. The operating conditions also include time information, such as the elapse of any t days since the start of the reaction.

[0020] The information on the hydrogen partial pressure, the catalyst loading amount, the feedstock feed rate, and the hydrogen feed rate can be determined by methods known in the art. The information on the hydrogen partial pressure, the catalyst loading amount, the feedstock feed rate, and the hydrogen feed rate can be controlled in the hydrotreating reaction of feedstocks containing vacuum distillation gas oil. The information on the operating conditions is preferably a set value. That is, the planned operating conditions are used.

[0021] <Deterioration level calculation step> The deterioration level calculation step of this embodiment is a step of calculating the deterioration level of the catalyst using a deterioration function based on the acquired information on the feedstock oil, information on the refined oil, and information on the operating conditions.

[0022] <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

[0023] 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.

[0024] <Degradation function 1> The deterioration function is a function for calculating the deterioration level of a catalyst. In this embodiment, the deterioration function is preferably a coke deterioration function relating to catalyst deterioration due to coke deposition. The coke deterioration function is not particularly limited as long as it is a function capable of calculating the deterioration level relating to coke deterioration of a catalyst. For example, deterioration function 1 expressed by the following formula 2 can be mentioned as an example.

[0025] Φ=exp(-Dt) Equation 2 In the above formula 2, D is the deterioration coefficient of the active species of the catalyst, and t is the number of days elapsed since the reaction began.

[0026] D can be calculated by the following formula 3. The following formula 3 is an equation that can calculate the deterioration coefficient of the active species of the catalyst using specific parameters, and was first discovered by the inventors of the present application based on the operating results of an actual machine, etc.

[0027]

number

[0028] In this specification, the term "required temperature" refers to the reaction temperature required to achieve a predetermined reaction condition. That is, the required temperature on day 0 is the temperature at which the reaction starts. F , S P , LHSV, and the reaction temperature required to achieve the reaction conditions of P.

[0029] In this specification, the term "reference hydrogen partial pressure" refers to the standard pressure under actual reaction conditions. It is calculated as the average value of the reaction pressures used to determine the hydrogen partial pressure coefficient a, which will be described later.

[0030] In this specification, the "reference reaction temperature" refers to the T obtained under the standard operating conditions that may be actually used. SOR means the average value of

[0031] In the above formula 3, T SOR represents the initial activity of the catalyst, and α represents the deactivation rate of the catalyst. SOR The larger the value of α, the greater the catalyst deterioration, and this deterioration behavior is reflected in the value of D.

[0032] In the above formula 3, (1 / S P n-1 -1 / S F n-1 The term expressed as )LHSV is the desulfurization reaction rate constant, and as mentioned above, S P , S F When the LHSV is set as a set value and the operation is performed under certain conditions, it becomes a constant. B / P) a The term expressed by is a term that indicates the hydrogen partial pressure dependency, and as mentioned above, when P is set to a set value and operation is performed under constant conditions, it becomes a constant. In the above equation 3, exp[Ec / R(1 / T B -1 / T SOR )] is a term that indicates temperature dependency and is a constant.

[0033] In the formula 3, S F , S P , LHSV, and P are values substituted based on the information about the feed oil, the information about the product oil, and the information about the operating conditions acquired in the information acquisition step described above. Note that LHSV can be calculated by dividing the feed oil supply rate (volume / h) by the catalyst loading amount (volume).

[0034] As mentioned above, S F , LHSV, and P are controllable parameters. P is the sulfur concentration of the target product oil. F , S P The depletion coefficient of the active species of the catalyst can be calculated under the reaction conditions of , LHSV, and P. The method for determining n, which is the reaction order of the hydrotreating reaction of feedstock oil containing vacuum distillation gas oil, will be described later.

[0035] (How to determine basic degradation parameters) In the above formula 3, α, P B ,a,Ec,T B , T SOR is a constant. Hereinafter, these parameters will be collectively referred to as "basic deterioration parameter 1." The basic deterioration parameter 1 is a parameter determined depending on the catalyst used, and may be determined while performing a reaction in an actual reactor, or may be determined in advance on a bench scale based on the operating conditions of the actual reactor. In this embodiment, it is preferable to determine the parameter in advance on a bench scale based on the operating conditions of the actual reactor. The basic degradation parameter P B ,a,Ec,T B Here is an example of how to calculate P. The method of calculating P is based on the catalyst deterioration behavior (change in reaction rate constant) analyzed from data obtained from the above-mentioned reaction in the actual equipment or from bench-scale reaction under the actual equipment operating conditions. B ,a,Ec,T B (How to find α, T SORTwo examples are shown for how to obtain SOR it, but the present invention is not limited thereto. The first example is a method of obtaining from the deterioration behavior of the catalyst (change in reaction rate constant) analyzed from the data obtained from the reaction in the actual machine described above or the reaction on a bench scale based on the actual machine operation conditions (α and T SOR obtaining method 1), and the second example is a method of obtaining from the reaction temperature profile analyzed from the data obtained from the reaction in the actual machine described above or the reaction on a bench scale based on the actual machine operation conditions (α and T

[0036] (P B , a, Ec, T B obtaining method) 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 actual machine described above or the reaction on a bench scale based on 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 4. Φ’ = k t ’ / k0’ Formula 4 In the above formula 4, k0’ is the reaction rate constant of the catalyst at the time when 0 days have passed since the start of the reaction (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 passed. Note that k0’, k t ’ is the reaction rate constant at the temperature T SOR ’ described later.

[0037] Similar to the above formula 1, the above formula 4 is a deterioration function based on the reaction rate constant. The reaction rate constant is expressed by the Arrhenius formula of the following formula 5.

[0038]

Equation

[0039] Temperature T at the start of the reaction SORThe reaction rate constant k0 at ' is k t In order to obtain an activity equivalent to the reaction rate constant k0' after t days of reaction, the reaction temperature must be set to T t ', the following formula 6 is derived from formula 4 and formula 5. Note that, since the reaction in this embodiment is a hydrotreating reaction of feed oil containing vacuum distillation gas oil, the activation energy E is set to the desulfurization activation energy Ea (kJ / mol).

[0040]

number

[0041] (Ec and T B (How to find) The LHSV, hydrogen partial pressure, hydrogen / feed oil ratio, and sulfur concentration in the feed oil are constant, and the sulfur concentration in the produced oil is set to a constant value S Pn The reaction is carried out for a certain period of time so that the sulfur concentration in the produced oil becomes S Pn To achieve this, the reaction temperature is increased while the reaction is carried out. If the reaction time is plotted on the horizontal axis and the measured reaction temperature on the vertical axis, and a regression line is drawn, y = a n x+b n (0 n ) is obtained. a n and b n is a value that reflects the catalyst deterioration behavior. n is T in the above formula 6 SOR In the above formula 6, T SOR ' to b n Substituting, T t By substituting the measured reaction temperature into ', the degree of deterioration Φ' after any reaction time t days has elapsed can be obtained. The activation energy Ea of desulfurization can be determined by the method described below. By plotting the logarithm of Φ' on the vertical axis and the reaction time on the horizontal axis, and drawing a regression line, y = -a n ’ x(|-a​n ’ |=a n ’ is obtained. A straight line represented by a n ’ represents the deterioration rate of the catalyst.

[0042] For n types of sulfur concentrations S Pn perform the same reaction, and in the same way, n a's n , b n are obtained, and in the same method as above, n a's n ’ are obtained. n is an integer of 3 or more. The larger the number of n, the higher the accuracy of Ec that can be obtained. On the other hand, if the number of n is too large, it takes time to obtain Ec and it is not efficient. In this embodiment, n is preferably 3 to 20, and more preferably 3 to 10. The n a's n ’ and b n thus obtained are respectively substituted into the following formula 7. Formula 7 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.

[0043] ln(a n ’ ) = ln(A) - (Ec / Rb n ) Formula 7 In the above formula 7, 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)).

[0044] For the combination of n a's n ’ and b n , plot ln(a n ’ ) on the vertical axis and 1 / b n on the horizontal axis, 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.

[0045] Also, by averaging n b's n T can be obtained. B It can be obtained.

[0046] Ec and T B Regarding the LHSV, hydrogen partial pressure, hydrogen / feedstock oil ratio, and sulfur concentration in the feedstock oil for obtaining Ec and T, it is preferable to set conditions in accordance with actual operating conditions. As such LHSV, for example, it is 0.5 to 2.5 h -1 and as the hydrogen partial pressure, for example, it is 3 to 7 MPa, as the hydrogen / feedstock oil ratio, for example, it is 100 to 400 [Nm 3 / kL], and as the sulfur concentration in the feedstock oil, for example, it is 0.5 to 3.0 mass%. n types of sulfur concentrations S Pn are also preferably set to conditions in accordance with actual operating conditions. Such S Pn is, for example, 0.3 mass% or less. As the reaction period, for example, it is 100 to 1500 days.

[0047] (Method for obtaining P B and a) With the LHSV, hydrogen / feedstock oil ratio, sulfur concentration in the feedstock oil, and sulfur concentration in the product oil being set to certain conditions, under the condition of hydrogen partial pressure P m , 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 certain 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 this is obtained. b m in this straight line becomes T SOR ' in the above formula 6. In the above formula 6, 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 (|―am ’ |=a m ’ ) is obtained. a m ’ represents the catalyst deterioration rate.

[0048] m types of hydrogen partial pressure P m The same reaction is carried out for m a m , b m Then, using the same method as above, m a m ’ where m is an integer of 3 or more. The larger the value of m, the more accurate a can be obtained. On the other hand, if the value of m is too large, it takes a long time to obtain a, which is not efficient. In this embodiment, m is preferably 3 to 20, and more preferably 3 to 10. The m a obtained in this way m ' and P m are substituted into the following formula 8. The following formula 8 is an equation that can calculate the hydrogen partial pressure coefficient and the reference hydrogen partial pressure, and was first discovered by the inventors of the present application based on the operating results of an actual machine, etc.

[0049] ln(a m ’ )=-aln(P m )+B1 formula 8 In the formula 8, B1 can be 0.

[0050] m a m ' and P m For the combination of ln(a m ’ ) on the vertical axis, and ln(P m ) on the horizontal axis, draw a regression line, and determine its slope. This slope is the hydrogen partial pressure coefficient a.

[0051] In addition, the m hydrogen partial pressures P m By averaging P B can be obtained.

[0052] a and P BIn determining [parameters], it is preferable that the LHSV, hydrogen / feedstock oil ratio, sulfur concentration in the feedstock oil, and sulfur concentration in the product oil be conditions in accordance with actual operating conditions. Such LHSV is, for example, 0.5 to 2.5 h -1 -1, and the hydrogen / feedstock oil ratio is, for example, 100 to 400 [Nm 3 / kL], the sulfur concentration in the feedstock oil is, for example, 0.5 to 3.0 mass%, and the sulfur concentration in the product oil is, for example, 0.3 mass% or less. The hydrogen partial pressures P of m types m are likewise preferably conditions in accordance with actual operating conditions. Such P m is, for example, 3 to 7 MPa. The reaction period is, for example, 50 to 600 days.

[0053] (Method for obtaining α and T SOR -1) In a full-scale unit or bench scale, perform the reaction for a certain period so as to achieve the LHSV, hydrogen partial pressure, hydrogen / feedstock oil ratio, sulfur concentration in the feedstock oil, and sulfur concentration in the product oil under the assumed actual operating conditions. Since the catalyst deteriorates due to the reaction, operate while increasing the reaction temperature. The assumed actual operating conditions are, for example, the operating conditions described in (Method for obtaining Ec and T B ), (Method for obtaining P B and a). Plot the measured reaction temperature on the vertical axis and the reaction time on the horizontal axis, and draw a regression line, then a straight line represented by y = a α x + b α is obtained. The a in this straight line α is a value correlated with α in the above formula 3, and b α is T in the above formula 3 SOR . In the above formula 6, 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 elapsed is obtained. 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 α ’ x (|-a α ’ | = a α ’Let it be so. A straight line represented by ) is obtained. a α ’ represents the deterioration rate of the catalyst.

[0054] 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 (That is, b α ) is substituted into the above formula 3 to obtain D. When the obtained D is substituted into the above formula 2, Φ is obtained. In this case, Φ is a function of α. 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 0 < α. Then, y = -a α ” x (|-a α ” | = a α ” ). A plurality of straight lines represented by are obtained for each value of α. a in each straight line α ” and the above a α ’ When they become equal values, α can be set as α in the above formula 3.

[0055] (Method for obtaining α and T SOR Method 2) (Method for obtaining α and T SOR Method 1) Perform the same reaction, and obtain a straight line represented by y = ax + b α and set b α as T in the above formula 3 α Let it be so. S which is the operating condition SOR , S P , LHSV, P, and P obtained by the above method F , a, Ec, T B T B、 T SOR (That is, b α ) is substituted into the above formula 3 to obtain D. When the obtained D is substituted into the above formula 2, Φ is obtained. In this case, Φ is a function of α. Substitute the obtained Φ into Φ' of the above formula 6, and substitute T SOR (That is, b α ) into T of the above formula 6 SOR ’Substitute it into T t When arranging for T t ’, T obs ’ becomes a function of α. The ratio of T t ’ to the measured reaction temperature T t ’ / T obs ) can be set as α in the above formula 3 when it becomes 1. Similarly, for N reaction temperatures T obs , the ratio of T t ’ to T t ’ / T obs ) is calculated, and it is preferable to set α in the above formula 3 as the α when the average of these is closest to 1. N is an integer of 10 or more, preferably 10 to 500, and more preferably 50 to 200.

[0056] (Modified example of deterioration function 1) A modified example of deterioration function 1 will be described below. As deterioration function 1, deterioration function 1-1 represented by the following formula 9 may be used.

[0057] Φ = exp(-D’t) Formula 9 In the above formula 9, D’ is the deterioration coefficient of the active species of the catalyst, and t is the number of days of reaction progress (days).

[0058] D’ can be obtained by the following formula 10.

[0059] [Number] In the above formula 10, α’ is a catalyst constant (a constant representing the deterioration rate of the catalyst), S F is the sulfur concentration (mass%) in the feedstock oil at any reaction time t days, S P is the sulfur concentration (mass%) in the product oil at any reaction time t days, n is the reaction order of the hydrotreating reaction of the feedstock oil containing vacuum gas oil, LHSV is the liquid hourly space velocity (h -1 ) at any reaction time t days, P B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) at any reaction time t days, a is the hydrogen partial pressure coefficient, G B is the reference hydrogen / feedstock oil ratio (Nm 3 / kL), G is the hydrogen / feed oil ratio (Nm 3 / kL), b is the hydrogen / feed oil ratio coefficient, Ec is the activation energy of coke degradation (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol K)), and T B is the reference reaction temperature (K), and T SOR is the required temperature (K) on day 0.

[0060] S in the formula 10 F , S P , LHSV, and P are the same as those in the above-mentioned formula 3. In the above-mentioned formula 10, G is a value substituted based on the information on the feedstock oil and the information on the operating conditions acquired in the above-mentioned information acquisition step. Specifically, G is the hydrogen supply amount (Nm 3 / hour) by the feed rate of the raw oil (kL / hour).

[0061] In this specification, the "reference hydrogen / feedstock ratio" refers to a standard hydrogen / feedstock ratio under actual reaction conditions. It is calculated as the average value of the hydrogen / feedstock ratios used to determine the hydrogen / feedstock ratio coefficient b, which will be described later.

[0062] In the formula 10, (G B / G) b The term expressed by is a term that indicates dependency on the hydrogen / feed oil ratio, and as described above, when G is set as a set value and operation is performed under constant conditions, it becomes a constant.

[0063] P B ,a,Ec,T B , T SOR can be calculated in the same way as in the formula 3. B , b, and α' are calculated as follows.

[0064] G B , b is P B ,a,Ec,T B , T SORSimilarly, 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 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, G B , and how to obtain b will be described.

[0065] (G B , 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 operating conditions.

[0066] Set LHSV, hydrogen partial pressure, sulfur concentration in the feedstock oil, and sulfur concentration in the product oil as constant conditions, and carry out the reaction for a certain period under the condition of the hydrogen / feedstock oil ratio G h . 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 h x + b h (0 < a h .). A straight line represented by this is obtained. b h in this straight line becomes T SOR ' in the above formula 6. In the above formula 6, substituting b SOR for T h ' and substituting the measured reaction temperature for T t ’ , the degree of deterioration Φ' at an arbitrary reaction time t days elapsed 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 h ’ x (|―a h ’ | = a h ’ .). A straight line represented by this is obtained. a h ’ represents the deterioration rate of the catalyst.

[0067] h types of hydrogen / feedstock oil ratio G hThe same reaction is carried out for h a h , b h Then, using the same method as above, find h a h ’ where h is an integer of 3 or more. The larger the value of h, the more accurate b can be obtained. On the other hand, if the value of h is too large, it takes a long time to obtain b, which is not efficient. In this embodiment, h is preferably 3 to 20, and more preferably 3 to 10. The h a obtained in this way h ' and G h are substituted into the following formula 11. The following formula 11 is an equation that can calculate the hydrogen / feed oil ratio coefficient and the reference hydrogen / feed oil ratio, and was first discovered by the inventors of the present application based on the operating results of an actual plant, etc.

[0068] ln(a h ')=-bln(G h )+B3 Equation 11 In the formula 11, B3 can be 0.

[0069] h a h ' and G h For the combination of ln(a h ') on the vertical axis, and ln(G h ) on the horizontal axis, draw a regression line, and determine its slope. This slope is the hydrogen / feed oil ratio coefficient b.

[0070] In addition, the above h types of hydrogen / feed oil ratio G h By averaging, G B can be obtained.

[0071] b and G B In determining the above, it is preferable that the LHSV, hydrogen partial pressure, sulfur concentration in the feed oil, and sulfur concentration in the product oil are conditions that correspond to the operating conditions of the actual plant. Such LHSV is, for example, 0.5 to 2.5 h -1The hydrogen partial pressure is, for example, 3 to 7 MPa, the sulfur concentration in the feedstock oil is, for example, 0.5 to 3.0 mass %, and the sulfur concentration in the product oil is, for example, 0.3 mass % or less. h types of hydrogen / feed oil ratio G h Similarly, it is preferable to set the conditions for G according to the actual operating conditions. h For example, 100 to 400 [Nm 3 / kL]. The reaction period is, for example, 50 to 600 days.

[0072] In addition, α' is calculated in the same manner as in the degradation function 1 (α and T SOR How to find 1) and (α and T SOR This can be calculated using the same method as in 2).

[0073] <Degradation function 2> In this embodiment, the coke deterioration function relating to catalyst deterioration due to coke deposition is preferably deterioration function 2, expressed by the following equation 12, which is composed of an easily deactivated active species deterioration function relating to the deterioration of easily deactivated active species of the catalyst and a hardly deactivated active species deterioration function relating to the deterioration of hardly deactivated active species of the catalyst.

[0074] Φ=k1×exp(-D1t)+k2×exp(-D2t) Equation 12 In Equation 12, k1 is the active site coefficient of the easily deactivated active species of the catalyst, k2 is the active site coefficient of the less easily deactivated active species of the catalyst, and the active site coefficients represent the relative reaction rate constants of both active species. D1 is the deterioration coefficient of the easily deactivated active species of the catalyst, D2 is the deterioration coefficient of the less easily deactivated active species of the catalyst, t is the number of days elapsed since the reaction began, and k1 + k2 = 1.

[0075] As described above, in the hydrotreating reaction of vacuum distillation gas oil, catalyst deterioration occurs due to coke deposition, and therefore, in order to maintain the sulfur content of the product oil at a certain level or below, it is necessary to operate the reaction at an elevated temperature. In the hydrotreating reaction of vacuum distillation gas oil, the reaction temperature rises rapidly at the beginning of the reaction. This rapid rise in reaction temperature indicates rapid deterioration of the catalyst at the beginning of the reaction. On the other hand, from the middle of the reaction onwards, the reaction temperature rises slowly. This slow rise in reaction temperature indicates slow deterioration of the catalyst at the middle of the reaction onwards.

[0076] In other words, the profile of reaction temperature versus reaction time suggests that in the hydrotreating reaction of vacuum distillation gas oil, rapid catalyst deterioration occurs at the beginning of the reaction, followed by gradual catalyst deterioration from the middle stage of the reaction onwards.

[0077] Based on the above-mentioned profile of reaction temperature versus reaction time, the inventors of the present application further improved deactivation function 1 and discovered deactivation function 2 on the assumption that the catalyst contains active species that are easily deactivated in the early stage of the reaction and active species that are difficult to deactivate in the middle or later stage of the reaction. As a result, they found that deactivation function 2 makes it possible to calculate the degree of catalyst degradation more accurately than deactivation function 1. Easily deactivated active species are active species that lose activity mainly in the early stage of the reaction, and difficult to deactivate active species are active species that lose activity in the middle or later stage of the reaction.

[0078] In the formula 12, 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 determining them will be described later.

[0079] D1 can be calculated using the following formula 13, and D2 can be calculated using the following formula 14.

[0080]

number

[0081]

number

[0082] In the above formula 13 and the above formula 14, S F is the sulfur concentration (mass%) in the feedstock oil at the end of an arbitrary reaction day t, and S P is the sulfur concentration (mass%) in the product oil at the end of an arbitrary reaction day t. n is the reaction order of the hydrotreating reaction of the feedstock oil containing vacuum gas oil. LHSV is the liquid hourly space velocity (h -1 ) at the end of an arbitrary reaction day t. P B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) at the end of an arbitrary reaction day t, a is the hydrogen partial pressure coefficient, Ec is the activation energy (kJ / mol) of coke deterioration, R is the gas constant: 0.00831 (kJ / (mol·K)), and T B is the reference reaction temperature (K), and T SOR is the required temperature (K) on the 0th day. In the above formula 13, α1 is the catalyst constant of the easily deactivated active site (a constant representing the catalyst deterioration rate). In the above formula 14, α2 is the catalyst constant of the hardly deactivated active site (a constant representing the catalyst deterioration rate).

[0083] In the above formula 13 and the above formula 14, S F , S P , LHSV, and P are values substituted based on the information about the feedstock oil, the information about the product oil, and the information about the operating conditions obtained in the above-described information acquisition step in the same manner as the description of the above formula 3. Note that LHSV can be obtained by dividing the supply amount (volume / h) of the feedstock oil by the catalyst filling amount (volume).

[0084] As described above, S F , LHSV, and P are parameters that can be controlled. Also, S P is the sulfur concentration of the target product oil. That is, according to the above formula 13 and the above formula 14, the deterioration coefficients of the easily deactivated active species of the catalyst and the hardly deactivated active species of the catalyst under the reaction conditions of the above S F , S P , 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 vacuum gas oil, will be described later.

[0085] (Method for Obtaining Basic Deterioration Parameters) In the above formulas 13 and 14, α1, α2, P B , a, Ec, T B , T SOR are constants, similar to the above formula 3, and these parameters are collectively referred to as "basic deterioration parameter 2". The basic deterioration parameter 2 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 it may be obtained in advance on a bench scale based on the actual machine operating conditions. In this embodiment, it is preferable to obtain it in advance on a bench scale based on the actual machine operating conditions. In the above formulas 13 and 14, P B , a, Ec, T B can be obtained by the same method as the above formula 3. On the other hand, α1, α2, T SOR can be obtained, for example, by the following two methods. Also, the activity point number coefficient k1 of the easily deactivated active species of the catalyst and the activity point number coefficient k2 of the hardly deactivated active species of the catalyst in the above formula 12 can also be obtained as follows at the same time.

[0086] (Method for Obtaining α1, α 2、 T SOR , k1, and k2 - 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, and sulfur concentration in the product oil under the assumed actual machine operating conditions are achieved. 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, the line represented by y = a1x + b1 that correlates with the rapid increase in the reaction temperature at the initial stage of the reaction start (x1 to x n ), and the two lines represented by y = a2x + b2 that correlate with the gentle increase in the reaction temperature after the middle stage of the reaction (x n+1 to x m ) are obtained. In the above formulas, a1 > a2 > 0, b1 < b2, and x1 < x n < x n+1 < x m < xn , x m means the reaction time relative to the n(m)th plot from the start of the reaction.

[0087] The above-mentioned a1 is a value correlated with α1, b1 is a value correlated with k1+k2, and T SOR In addition, a2 is a value that correlates with α2, and b2 is a value that correlates with k2. Next, the intersection point (x ip , y ip ) is calculated. This intersection point means the inflection point of y=a1x+b1 and y=a2x+b2. That is, (x ip , y ip ), it is assumed that only the easily deactivated active species of the catalyst exist, and (x ip , y ip ) is considered to have two active species: one that is easily deactivated and one that is difficult to deactivate.

[0088] In the formula 6, T SOR ' is assigned to b1, and T t By substituting the reaction temperature into ', the degree of deterioration Φ' after any reaction time t days has elapsed can be obtained. Plot the reaction time on the horizontal axis and the logarithm of Φ' on the vertical axis, and then calculate the ratio x1 to x ip If we draw a regression line up to y=-a1 ’ x (|-a1 ’ |=a1 ’ ) is obtained. Also, x ip ~x m If we draw a regression line to y=-a2 ’ x-b2 ’ (|-a2 ’ |=a2 ’ and |-b2 ’ |=b2 ’ ) is obtained. a1 ’ is a value correlated with α1, and a2 ’ is a value correlated with α2, and b2 ’ is a value correlated to k2.

[0089] k2 is the b2 obtained from the regression line above. ’can be calculated by substituting into the following equation 15. Since k1 is k1+k2=1, it can be calculated from k1=1-k2. k2=exp(-b2 ’ ) Equation 15

[0090] The operating condition is S P , S F , LHSV, P, and P obtained by the above method B ,a,Ec,T B , T SOR Substituting (b1) into the above formula 13 and formula 14 gives D1 and D2. Substituting the obtained D1, D2, k1, and k2 into the above formula 12 gives Φ. In this case, Φ is a function of α1 and α2. Plot the reaction time on the horizontal axis and the logarithm of Φ on the vertical axis, and set α2 = 0 and change α1 so that 0 < α1 to obtain x1 to x ip If we draw a regression line from y to -a α1 ” x(|-a α1 " |=a α1 ” ) are obtained for each value of α1. α1 ” and the above-mentioned a1 ’ The α1 when these values are equal can be used as the α1 in the above equation (13). Next, substitute the obtained α1 into Φ, which is a function of α1 and α2 obtained by the above method, and change α2 so that 0<α2 to obtain x ip ~x m If we draw a regression line from y to -a α2 ” xb α2 " (|-a α2 ” |=a α2 " ) are obtained for each value of α2. α2 ” and the above-mentioned a2 ’ The α2 when these values are equal can be used as the α2 in the above equation (14).

[0091] (α1, α2、 T SOR 2) How to calculate k1 and k2 (α1, α 2、 T SOR , k1, and k2. Carry out the same reaction as in 1) and calculate T SOR (b1) is obtained. The operating condition is S 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 formula 13 and formula 14 to obtain D1 and D2. The obtained D1 and D2 are substituted into the above formula 12 to obtain Φ. In this case, Φ is a function of α1, α2, k1, and k2. The obtained Φ is substituted into Φ' in the above formula 6, and T SOR (i.e., b1) is T in the above formula 6 SOR ’ Substituting into, T t ’ To summarize, T t ’ is a function of α1, α2, k1, and k2. If α2 is set to 0 and k2=1-k1, then T t ’ is a function of α1 and k1. x1~x ip The measured reaction temperature T obs T for t ’ The ratio (T t ’ / T obs ) is 1, and this α1 can be used as α1 in the above formula 13. Note that k1 at this time is a tentative value. Similarly, M reaction temperatures T obs T for t ’ The ratio (T t ’ / T obs ) and the α1 at which their average is closest to 1 is preferably taken as the α1 in the above formula 13. M is an integer of 10 or more, preferably 10 to 500, and more preferably 50 to 200. Using the obtained α1, let k1 = 1-k2, and T t ’ is a function of α2 and k2. xip ~x m The measured reaction temperature T at obs with respect to T t ’ The ratio of (T t ’ / T obs ) becomes 1, find the combination of α2 and k2, and these α2 and k2 can be used as α2 and k2 in the above formula 14. 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 13. Similarly, for L reaction temperatures T obs with respect to T t ’ The ratio of (T t ’ / T obs ) is calculated, and it is preferable that α2 and k2 when the average of these is closest to 1 are used as α2 and k2 in the above formula 14. Also, it is preferable that k1 obtained from the obtained k2 is used as k1 in the above formula 13. L is an integer of 10 or more, preferably 10 to 500, and more preferably 50 to 200.

[0092] 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.

[0093] Using the method described above, plot the reaction time on the horizontal axis and the reaction temperature on the vertical axis. A regression line is drawn from the start of the reaction to the end of the reaction, resulting in a line expressed as y = a'x + b'. This line does not take into account the inflection point. Remove plots from the end of the reaction in order, and adjust the y = a'x + b' so that the correlation coefficient approaches 1, to obtain y = a1'x + b1'. Similarly, remove plots from the start of the reaction in order, and adjust the y = a'x + b' so that the correlation coefficient approaches 1, to obtain y = a2'x + b2'. The lines where the average correlation coefficients of y = a1'x + b1' and y = a2'x + b2' are closest to 1 are y = a1x + b1 and y = a2x + b2. All plots should belong to either y = a1x + b1 or y = a2x + b2.

[0094] The reaction time required to obtain y = a1x + b1 and y = a2x + b2 is usually 100 days or more. In general, it is sufficient to carry out the reaction until the correlation function of y = a'x + b' becomes 0.5 or greater.

[0095] (Modification of degradation function 2) The following describes a modification of the point spread function 2. Point spread function 2-1 expressed by the following equation 16 may be used as the point spread function 1.

[0096] Φ=k1×exp(-D1't)+k2×exp(-D2't) Equation 16 In the above formula 16, k1, k2, and t are the same as those in the above formula 12, D1' is the deterioration coefficient of the active species of the catalyst that is easily deactivated, and D2' is the deterioration coefficient of the active species of the catalyst that is difficult to deactivate.

[0097] D1' can be calculated using the following formula 17, and D2' can be calculated using the following formula 18.

[0098]

number

[0099]

number

[0100] In the formulas 17 and 18, S F , S P , n, LHSV, P B , P, a, Ec, R, T B , T SOR is the same as in the formulas 13 and 14, G B , G, b are the same as in the formula 10. In the formula 17, α1’ is the catalytic constant of the deactivatable active site (a constant representing the catalyst deterioration rate). In the formula 18, α2’ is the catalytic constant of the non-deactivatable active site (a constant representing the catalyst deterioration rate).

[0101] P B , a, Ec, T B , T SOR can be obtained by the same method as described in the formulas 13 and 14, G B , b can be obtained by the same method as described in the formula 10.

[0102] 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 the formula 16 is used instead of the formula 12, the formula 17 is used instead of the formula 13, and the formula 18 is used instead of the formula 14.

[0103] ≪Reaction temperature calculation step≫ The reaction temperature calculation step of this embodiment is a step of calculating the reaction temperature necessary to satisfy the information on the feedstock 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 formula based on the Arrhenius equation.

[0104] <Deterioration rate formula> The deterioration rate formula is a formula based on the Arrhenius equation represented by the formula 5. Similar to the calculation method of the formula 6, the following formula 19 is derived from the formulas 1 and 5.

[0105]

Equation

[0106]

number

[0107] In the above formula 20, T obtained by the above method SOR , Φ, T after t days of any reaction t (K) can be obtained. The activation energy of the desulfurization reaction in the above formula 20 can be calculated as follows.

[0108] (How to calculate the activation energy of the desulfurization reaction) The activation energy of the desulfurization reaction can be determined by a method known in the art based on the Arrhenius equation represented by the above-mentioned formula 5. An example will be described below.

[0109] First, determine the reaction order of the desulfurization reaction of feedstock oil containing vacuum distillation diesel. The reaction temperature, hydrogen partial pressure, hydrogen / feedstock ratio, and sulfur concentration in the feedstock oil are kept constant, and the reaction is carried out under the conditions of LHSV(x), and the sulfur concentration in the resulting oil is measured. S in the desulfurization reaction rate equation, expressed as Equation 21 below, is F The sulfur concentration in the feed oil is expressed as S P Substitute LHSV(x) for the sulfur concentration in the resulting oil obtained in . Plot the result on the left side of the equation on the vertical axis and 1 / LHSV on the horizontal axis. In this case, the vertical axis is a function of n.

[0110]

number

[0111] 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 such as Excel to find the correlation function and determine 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.

[0112] 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.

[0113] 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, 300 to 420 °C, the hydrogen partial pressure is 3 to 7 MPa, the hydrogen / feedstock oil ratio is 100 to 400 [Nm 3 / kL], and the sulfur concentration in the feedstock oil is 0.5 to 3.0 mass%. The x types of LHSV(x) are also preferably set to conditions in accordance with the actual operating conditions. Such LHSV(x) is 0.5 to 2.5 h -1 .

[0114] Taking the activation energy E in the Arrhenius equation represented by Formula 5 as the desulfurization activation energy Ea and taking the natural logarithm of both sides, the equation represented by the following Formula 22 is obtained.

Equation

[0115] The hydrogen partial pressure, hydrogen / feed oil ratio, LHSV, and sulfur concentration in the feed oil are kept constant, and the reaction is carried out at a reaction temperature of T(y), and the sulfur concentration in the resulting oil is measured. F The sulfur concentration in the feed oil is expressed as S P The sulfur concentration in the product oil obtained in is substituted for LHSV, and the above obtained n is substituted to determine the reaction rate constant k. The obtained reaction rate constant is substituted into the above equation 22, and the result (lnk) on the left side obtained is plotted on the vertical axis and 1 / T (1 / T(y)) on the horizontal axis.

[0116] The same reaction is carried out at y different reaction temperatures T(y), and y plots like the one above are obtained. A regression line is drawn from the obtained plots, and its slope is determined. Since this slope is Ea / R, the activation energy of desulfurization, Ea, can be calculated by subtracting R from the slope.

[0117] The above y is an integer of 3 or more. The larger the number of y, the more accurate Ea can be obtained. On the other hand, if the number of y is too large, it takes a long time to obtain Ea, which is not efficient. In this embodiment, y is preferably 3 to 20, and more preferably 3 to 10.

[0118] In determining Ea, the hydrogen partial pressure, hydrogen / feed oil ratio, LHSV, and sulfur concentration in the feed oil are preferably set to conditions that correspond to the operating conditions of the actual plant. The hydrogen partial pressure is, for example, 3 to 7 MPa, and the hydrogen / feedstock ratio is 100 to 400 [Nm 3 / kL] and LHSV is 0.5 to 2.5 h -1 The sulfur concentration in the feed oil is 0.5 to 3.0 mass %. Similarly, it is preferable that the reaction temperature T(y) of the y types is set to a condition that conforms to the operating conditions of the actual equipment. Such T(y) is 300 to 420°C.

[0119] By substituting each parameter thus obtained into the above-mentioned formula 20, the reaction temperature T required to achieve the predetermined reaction conditions can be calculated. t can be obtained.

[0120] Measured reaction temperature T obs The reaction temperature T obtained by the information processing method of the present 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.

[0121] <<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.

[0122] <<Hydrogenation treatment reaction of feedstock oil containing vacuum gas oil>> An overview of the hydrogenation treatment reaction of the feedstock oil containing vacuum gas oil will be described. Vacuum gas oil is a fraction with a boiling range of 200 to 550 °C obtained by vacuum distillation of atmospheric residue oil. The density of vacuum gas oil is 0.91 to 0.95 g / mL. The content of vacuum gas oil in the feedstock oil may be, for example, 30% by volume or more, or 50% by volume or more. In addition, as oil types other than vacuum gas oil contained in the feedstock oil, there are atmospheric residue oil obtained by atmospheric distillation of crude oil in an atmospheric distillation unit, heavy extract which is a particularly heavy oil fraction among the oil fractions extracted and removed by solvent extraction of lubricating base oils such as hydrocracked heavy oil, atmospheric residue, fluid catalytic cracking residue oil, and deasphalted oil.

[0123] The hydrogenation treatment reaction of the feedstock oil containing vacuum gas oil can be carried out by contacting the feedstock oil containing vacuum gas oil with a hydrogenation treatment catalyst in the presence of hydrogen. The hydrogenation catalyst is not particularly limited, and known hydrogenation catalysts 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.

[0124] 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 10 to 25% by mass based on the catalyst and in terms of oxide conversion. If the metal content is less than 10% by mass, the absolute amount of the metal acting as the active site is small, so the hydrogenation treatment activity (hereinafter simply referred to as hydrogenation treatment 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 hydrogenation treatment 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.

[0125] As conditions in the hydrotreating reaction of a feedstock oil containing vacuum distillation light oil, generally, the reaction temperature is 300 to 420 °C, preferably 340 to 400 °C, the hydrogen partial pressure is 3 to 7 MPa, preferably 4 to 6 MPa, and the LHSV is 0.5 to 2.5 h -1 , preferably 0.6 to 1.5 h -1 and the hydrogen / feedstock oil ratio is 100 to 400 [Nm 3 / kL], preferably 200 to 300 [Nm 3 / kL].

[0126] The sulfur concentration in the feedstock oil containing vacuum distillation light oil is usually 0.5 to 3.0 mass%. Also, the sulfur concentration in the produced oil is usually 0.01 to 0.3 mass%.

[0127] ≪Reaction Temperature Calculation Device≫ The reaction temperature calculation device of the present embodiment relates to the hydrotreating reaction of a feedstock oil containing vacuum distillation light oil obtained by vacuum distilling atmospheric distillation residue oil, and includes an acquisition unit that acquires 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, and 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, calculates the degree of catalyst deterioration by a deterioration function, and based on the calculated degree of catalyst deterioration, calculates the reaction temperature required to satisfy the information on the feedstock oil, the information on the produced oil, and the operating conditions. The reaction temperature calculation device of the present embodiment may have an output unit that outputs information indicating the calculated reaction temperature.

[0128] The reaction temperature calculation device 1 of this embodiment is configured using an information processing device such as a personal computer, a server device, or a dedicated device. The reaction temperature calculation device 1 may be configured using one or more information processing devices. For example, the reaction temperature calculation device 1 may be configured as a cluster machine, a cloud, or any other configuration. The reaction temperature calculation device 1 includes, for example, an acquisition unit 11 and a computer main body 12 that processes information from the acquisition unit, as shown in FIG. 4. The reaction temperature calculation device 1 may also include an output unit 14 that outputs information processed by 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). Furthermore, some or all of these components may be realized by hardware (including 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 a combination of software and hardware. The program may be stored in advance in a storage device (a storage device with a non-transitory storage medium) such as a hard disk drive (HDD) or flash memory, or may be stored in a removable storage medium (a non-transitory storage medium) such as a DVD or CD-ROM, and installed in the storage device by inserting the storage medium into a drive device. The storage device may be configured, for example, with a HDD, flash memory, electrically erasable programmable read-only memory (EEPROM), read-only memory (ROM), or random access memory (RAM).

[0129] The acquisition unit 11 is configured to receive predetermined information input by the operator of the reaction and transmit the information thus obtained to the computer main body 12. The information acquired by the acquisition unit 11 in this embodiment includes information about the feedstock oil, information about the product oil, and information about the operating conditions regarding the hydrotreating reaction of the feedstock oil containing vacuum gas oil when a predetermined time has elapsed since the start of the reaction. The information about the feedstock oil, information about the product oil, and information about the operating conditions when a predetermined time has elapsed since the start of the reaction are as described above. For example, the acquisition unit 11 executes the above-described information acquisition step. The acquisition unit 11 may acquire information about the feedstock oil, information about the product oil, and information about the operating conditions when a predetermined time has elapsed since the start of the reaction, and the acquisition method is not particularly limited.

[0130] In this embodiment, the acquisition unit 11 is constituted by a single keyboard. The specific configuration of the acquisition unit 11 is not limited. In this embodiment, it is a keyboard, but it may also be a touch panel or the like. Note that the acquisition units for acquiring various types of 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-mentioned pieces of information from a computer or the like used for controlling the reactor or the like, either wired or wirelessly.

[0131] The computer main body 12 is, for example, a so-called computer capable of processing various 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 executing 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 obtained by the acquisition unit 11 was started, the deterioration degree of the catalyst is calculated by a deterioration function, and based on the deterioration degree of the catalyst, 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, for example, from a deterioration rate equation. For example, the arithmetic unit 13 executes the above-described deterioration degree calculation step and reaction temperature calculation step. 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.

[0132] 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.

[0133] 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 in this embodiment is configured by a display unit such as a CRT display, a liquid crystal display, or a PDP, but is not limited to this and may be configured to output to a printing unit such as a printer, or to other devices (for example, a computer used to control the hydrotreating reaction of feed oil including vacuum distillation light 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.

[0134] 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).

[0135] <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 vacuum distillation gas oil. 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:

[0136] 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 said 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. Further, when the estimated reaction temperature is not below the equipment set temperature, the information processing method shown in S4-1 to 4-3 of FIG. 2 may be performed. The information processing method shown in S4-1 to 4-3 of FIG. 2 includes an information acquisition step (S4-1 of FIG. 2) for acquiring information regarding the target reaction temperature, a deterioration degree calculation step (S4-2 of FIG. 2) for calculating the deterioration degree of the catalyst by a deterioration function based on the acquired target reaction temperature, and a reaction condition calculation step (S4-3 of FIG. 2) 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 (S4-4 of FIG. 2) 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 deterioration function 1, substitute the target reaction temperature into T in the formula 19 to obtain Φ. Substitute the obtained Φ into the formula 2 to obtain D. Substitute the obtained D into the formula 3 to find the combination of S, S, LHSV, and P such that the equation of the formula 3 holds. Also, in the above combination, for example, taking S, S as set values, P and LHSV may be obtained. Also, as the deterioration function, any of the deterioration function 1, deterioration function 1-1, deterioration function 2, and deterioration function 2-1 may be used. Incidentally, 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. Incidentally, the target temperature may be stored in advance in the calculation unit 13 in the computer main body 12. t Substitute the target reaction temperature into it to obtain Φ. Substitute the obtained Φ into the formula 2 to obtain D. Substitute the obtained D into the formula 3 so that the equation of the formula 3 holds, and find the combination of S P , S F , LHSV, and P. P , S F As set values, P and LHSV may be obtained. Also, as the deterioration function, any of the deterioration function 1, deterioration function 1-1, deterioration function 2, and deterioration function 2-1 may be used. Incidentally, 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. Incidentally, the target temperature may be stored in advance in the calculation unit 13 in the computer main body 12.

[0137] A second application method is to estimate reaction conditions (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 represented by S1A to 3A in FIG. 3 includes an information acquisition step (S1A in FIG. 3) for acquiring information about a target reaction temperature for a predetermined operation time, a deterioration calculation step (S2A in FIG. 3) for calculating a catalyst deterioration level using a deterioration function based on the acquired target reaction temperature, and a reaction condition calculation step (S3A in FIG. 3) for calculating information about the feed oil, information about the product oil, and information about the operation conditions required to achieve the target reaction temperature based on the deterioration level. The method may further include an information output step (S4A in FIG. 3) for outputting the information about the feed oil, information about the product oil, and information about the operation conditions obtained in this manner. Specifically, for example, when deterioration function 1 is used, T in Equation 19 is t The target reaction temperature after the specified operation time t days has elapsed is substituted into the above equation to obtain Φ. The obtained Φ is substituted into the above equation 2 to obtain D. The obtained D is substituted into the above equation 3 to obtain S so that the equality of the above equation 3 is established. P , S F , LHSV, and P. In the above combination, for example, S P , S F may be used as set values to calculate P and LHSV. As the degradation function, any of degradation function 1, degradation function 1-1, degradation function 2, and degradation function 2-1 may be used. Note that each of the above steps is executed, for example, by the reaction temperature calculation device 1 of this 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 for a predetermined operation time may be stored in advance in the calculation unit 13 in the computer main body 12. [Example]

[0138] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0139] [Example] A hydrotreating reaction was carried out on a bench scale by bringing a feedstock oil containing 70% by volume of vacuum gas oil into contact with a hydrotreating catalyst. Based on the obtained results, a deterioration function was calculated. In this example, the deterioration function 2 represented by the above formula 12 was used. When the parameters in the above formulas 12 to 14 were determined by the above-described method, k1 = 0.9, k2 = 0.1, α1 = 0.001, α2 = 0.0005, P B = 4.9 (MPa), a = 0.6, Ec = 150 (kJ / mol), T B = 673 (K), T SOR = 630 (K), n = 1.5.

[0140] Using the same feedstock oil and hydrotreating catalyst as those in the hydrotreating reaction carried out on a bench scale, the reaction was carried out on a full-scale unit. As the operating conditions in the above formulas 13 and 14, S F = 2.62 (mass%), P = 6.0 (MPa), LHSV = 0.485 (h -1 ), S P = 0.07 (mass%). Also, when the activation energy for desulfurization was determined in advance by the above-described method, Ea = 125 (kJ / mol). These basic deterioration parameters and reaction conditions were substituted into the above formulas 13 and 14 to obtain D1 and D2 at an arbitrary reaction time of t days. The obtained D1, D2 and the reaction elapsed days t were substituted into the above formula 12 to obtain Φ. The obtained Φ, Ea, T SOR were substituted into the above formula 20 to obtain the required temperature T t at an arbitrary reaction time of t days. Table 1 shows the measured values of the reaction temperatures at t = 251 days, 514 days, and 1164 days, and 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.

[0141]

Table 1

[0142] As shown in Table 1, the required temperature T tIt was found that it was almost equivalent to the measured value of the reaction temperature.

Explanation of symbols

[0143] 1 ··· Reaction temperature calculation device 11 ··· Acquisition unit 12 ··· Computer main body 13 ··· Calculation unit 14 ··· Output unit

Claims

1. Regarding the hydrotreating reaction of a feedstock oil containing vacuum gas oil obtained by vacuum distillation of 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 degradation degree calculation step of calculating the degradation degree of the catalyst by a degradation 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 degradation degree of the catalyst, which is an information processing method including: The information regarding the feedstock oil is information regarding the sulfur concentration in the feedstock oil, the information regarding the product oil is information regarding the sulfur concentration in the product oil, and the information regarding the operating conditions is information regarding the hydrogen partial pressure, the catalyst filling amount, and the feedstock oil supply amount; The degradation function is a function represented by the following formula 2, an information processing method. Φ = exp(−Dt) Formula 2 In the above formula 2, Φ is the degradation degree of the catalyst, D is the degradation coefficient of the active species of the catalyst and is calculated from the following formula 3, and t is the number of days elapsed since the reaction (days). 【Number 1】 In the above formula 3, α is a catalyst constant (a constant representing the degradation 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 vacuum gas 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 degradation (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 conducting the reaction in a real machine or are obtained in advance on a bench scale based on the real machine operating conditions. Regarding the hydrotreating reaction of a feedstock oil containing vacuum distillate light oil obtained by vacuum distilling an 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 degradation degree calculation step of calculating the degradation degree of the catalyst by a degradation 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 degradation degree of the catalyst, the information processing method comprising: The information regarding the feedstock oil is information regarding the sulfur concentration in the feedstock oil, the information regarding the product oil is information regarding the sulfur concentration in the product oil, and the information regarding the operating conditions is information regarding the hydrogen partial pressure, information regarding the catalyst filling amount, information regarding the feedstock oil supply amount, and information regarding the hydrogen supply amount; The degradation function is a function represented by the following formula 9, the information processing method. Φ = exp(−D't) Formula 9 In the above formula 9, Φ is the degradation degree of the catalyst, D' is the degradation coefficient of the active species of the catalyst and is calculated from the following formula 10, and t is the number of days elapsed since the start of the reaction (days). 【Number 2】 In the above formula (10), α' is a catalyst constant (a constant representing the deterioration rate of the catalyst), SF is the sulfur concentration (% by mass) in the feedstock oil at the end of an arbitrary reaction time t, SP is the sulfur concentration (% by 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 vacuum gas oil, 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 the 0th day (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 a full-scale unit or determined in advance in a bench-scale unit based on the full-scale operating conditions.

3. Regarding the hydrotreating reaction of a feedstock oil containing vacuum gas oil obtained by vacuum distillation of atmospheric residue oil, an information acquisition step of acquiring 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; A deterioration degree calculation step 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 product oil, and the information on the operating conditions; A reaction temperature calculation step of calculating 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 deterioration degree of the catalyst, the information processing method comprising: The information on the feedstock oil is information on the sulfur concentration in the feedstock oil, the information on the product oil is information on the sulfur concentration in the product oil, and the information on the operating conditions is information on the hydrogen partial pressure, information on the catalyst filling amount, and information on the supply amount of the feedstock oil; The deterioration function is a function represented by the following formula (12), the information processing method. Φ = k1 × exp(−D1t) + k2 × exp(−D2t) Formula (12) In the above formula (12), 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 degradation coefficient of the easily deactivated active species of the catalyst and is calculated from the following formula (13), D2 is the degradation coefficient of the hardly deactivated active species of the catalyst and is calculated from the following formula (14), 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 the above formula (13) and the above formula (14), 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 vacuum gas oil, 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 degradation (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). In the above formula (13), α1 is the catalyst constant of the easily deactivated active site (a constant representing the catalyst degradation rate), and in the above formula (14), α2 is the catalyst constant of the hardly deactivated active site (a constant representing the catalyst degradation rate). α1, α2, PB, a, Ec, TB, and TSOR are constants determined according to the catalyst to be 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 vacuum gas oil obtained by vacuum distillation of atmospheric 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 degradation degree calculation step of calculating the degradation degree of the catalyst by a degradation 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 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 degree of deterioration of the catalyst, and an information processing method comprising: The information on the feedstock oil is information on the sulfur concentration in the feedstock oil, the information on the product oil is information on the sulfur concentration in the product oil, and the information on the operating conditions is 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 16, and an information processing method. Φ = k1 × exp(−D1't) + k2 × exp(−D2't) Formula 16 In the formula 16, k1 is the activity site coefficient of the easily deactivated active species of the catalyst, k2 is the activity site coefficient of the hardly deactivated active species of the catalyst, and the activity site coefficient represents the relative reaction rate constant of both active species. D1' is the deterioration coefficient of the easily deactivated active species of the catalyst and is calculated from the following formula 17, D2' is the deterioration coefficient of the hardly deactivated active species of the catalyst and is calculated from the following formula 18, 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 formula (17) and the above formula (18), 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 vacuum gas oil, 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 the 0th day (K). In the above formula (17), α1' is the catalyst constant of the easily deactivated active site (a constant representing the catalyst deterioration rate), and in the above formula (18), α2' is the catalyst constant of the hardly deactivated active site (a constant representing the catalyst deterioration rate). α1', α2', PB, a, GB, b, Ec, TB, and TSOR are constants determined according to the catalyst to be 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. Regarding the hydrotreating reaction of a feedstock oil containing vacuum gas oil obtained by vacuum distillation of atmospheric residue oil, an acquisition unit that acquires 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; Based on the information regarding the feedstock oil, the information regarding the product oil, and the information regarding the operating conditions acquired by the acquisition unit, a calculation unit that calculates the degree of catalyst deterioration using a deterioration function and calculates 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 calculated degree of catalyst deterioration; A reaction temperature calculation device, The information regarding the feedstock oil is information regarding the sulfur concentration in the feedstock oil, the information regarding the product oil is information regarding the sulfur concentration in the product oil, and the information regarding the operating conditions is information regarding the hydrogen partial pressure, information regarding the catalyst filling amount, and information regarding 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 = exp(−Dt) Formula 2 In Formula 2, Φ is the degree of catalyst deterioration, D is the deterioration coefficient of the active species of the catalyst, which is calculated from the following formula 3, and t is the number of days elapsed since the start of the reaction (days). 【Number 7】 In Formula 3, α is a catalyst constant (a constant representing the deterioration rate of the catalyst), 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 vacuum gas oil, 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 (K) on the 0th day. α, PB, a, Ec, TB, and TSOR are constants determined according to the catalyst to be used. The constants are determined while performing the reaction in an actual machine or are determined in advance on a bench scale based on the actual machine operating conditions.

6. Regarding the hydrotreating reaction of a feedstock oil containing vacuum gas oil obtained by vacuum distillation of atmospheric residue oil, an acquisition unit that acquires 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; Based on the information regarding the feedstock oil, the information regarding the product oil, and the information regarding the operating conditions acquired by the acquisition unit, a calculation unit that calculates the degree of catalyst deterioration using a deterioration function and calculates 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 calculated degree of catalyst deterioration. A reaction temperature calculation device comprising: The information regarding the feedstock oil is information regarding the sulfur concentration in the feedstock oil, the information regarding the product oil is information regarding the sulfur concentration in the product oil, and the information regarding the operating conditions is 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 reaction temperature calculation device, wherein the deterioration function is a function represented by the following formula 9. Φ = exp(−D't) Formula 9 In the above formula (9), Φ is the degree of catalyst deterioration, D' is the deterioration coefficient of the active species of the catalyst, which is calculated from the following formula (10), and t is the number of days elapsed since the start of the reaction (days). 【Number 8】 In the above formula (10), α' is a catalyst constant (a constant representing the catalyst deterioration rate), SF is the sulfur concentration (mass%) in the feedstock oil at any time t days after the start of the reaction, SP 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 vacuum gas oil, LHSV is the liquid hourly space velocity (h-1) at any time t days after the start of the reaction, PB 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, 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 start of 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 (K) on the 0th day. α', PB, a, GB, b, Ec, TB, and TSOR are constants determined according to the catalyst used. The constants are determined while conducting the reaction in a full-scale unit or determined in advance in a bench-scale unit based on the full-scale operating conditions. **Claim 7**: Regarding the hydrotreating reaction of a feedstock oil containing vacuum gas oil obtained by vacuum distillation of atmospheric residue oil, 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; A reaction temperature calculation device including: 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 on the feedstock oil is information on the sulfur concentration in the feedstock oil, the information on the product oil is information on the sulfur concentration in the product oil, and the information on the operating conditions is 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, wherein the deterioration function is a function represented by the following formula (12). Φ = k1 × exp(−D1t) + k2 × exp(−D2t) Equation 12 In the above Equation 12, 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 degradation coefficient of the easily deactivated active species of the catalyst and is calculated from the following Equation 13, D2 is the degradation coefficient of the hardly deactivated active species of the catalyst and is calculated from the following Equation 14, t is the number of days elapsed since the start of 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 at a bench scale based on the actual machine operating conditions. 【Number 9】 【Number 10】 In the above Equation 13 and Equation 14, SF is the sulfur concentration (mass %) in the feedstock oil at the elapse of any reaction t days, SP is the sulfur concentration (mass %) in the product oil at the elapse of any reaction t days, n is the reaction order of the hydrotreating reaction of the feedstock oil containing vacuum gas oil, LHSV is the liquid hourly space velocity (h−1) at the elapse of any reaction t days, PB is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) at the elapse of any reaction t days, a is the hydrogen partial pressure coefficient, Ec is the activation energy of coke degradation (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol·K)), TB is the reference reaction temperature (K), and TSOR is the required temperature on day 0 (K). In the above Equation 13, α1 is the catalyst constant of the easily deactivated active site (a constant representing the degradation rate of the catalyst), and in the above Equation 14, α2 is the catalyst constant of the hardly deactivated active site (a constant representing the degradation rate 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 performing the reaction in an actual machine or are obtained in advance at a bench scale based on the actual machine operating conditions.

8. Regarding the hydrotreating reaction of a feedstock oil containing vacuum gas oil obtained by vacuum distillation of atmospheric residue oil, an acquisition unit that acquires 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 Based on the information on the feedstock oil, the information on the product oil, and the information on the operating conditions obtained by the acquisition unit, a deterioration function is used to calculate the degree of catalyst deterioration. Based on the calculated degree of catalyst deterioration, an arithmetic unit calculates the reaction temperature required to satisfy the information on the feedstock oil, the information on the product oil, and the operating conditions. A reaction temperature calculation device includes: The information on the feedstock oil is information on the sulfur concentration in the feedstock oil. The information on the product oil is information on the sulfur concentration in the product oil. The information on the operating conditions is information on the hydrogen partial pressure, information on the catalyst filling amount, information on the feedstock oil supply amount, and information on the hydrogen supply amount. The deterioration function is a function represented by the following formula 16. A reaction temperature calculation device. Φ = k1 × exp(−D1't) + k2 × exp(−D2't) Formula 16 In Formula 16, 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 of the easily deactivated active species of the catalyst and is calculated from the following formula 17. D2' is the deterioration coefficient of the hardly deactivated active species of the catalyst and is calculated from the following formula 18. t is the number of days elapsed since the reaction (days). k1 + k2 = 1. 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 11】 【Number 12】 In the above formulas 17 and 18, 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 vacuum gas oil, 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 17, α1' is the catalyst constant of the easily deactivated active site (a constant representing the catalyst deterioration rate), and in the above formula 18, α2' is the catalyst constant of the hardly deactivated active site (a constant representing the catalyst deterioration rate). α1', α2', PB, a, GB, b, Ec, TB, and TSOR are constants determined according to the catalyst to be used. The above constants are determined while performing the reaction in a full-scale unit or 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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