Information processing method, cracked light oil yield calculation device, cracked light oil yield calculation program, and non-transitory computer readable recording medium

Abstract

To provide: an information processing method capable of estimating a decomposition light oil acquisition amount under prescribed reaction conditions, in a hydrogen treatment reaction of raw material oil including a reduced pressure distillation light oil; a decomposition light oil acquisition amount calculation device capable of estimating the decomposition light oil acquisition amount; a decomposition light oil acquisition amount calculation program; and a computer-readable non-temporary recording medium.SOLUTION: There is provided an information processing method comprising: an information acquisition step of acquiring information related to raw material oil including reduced pressure distillation light oil as of when a prescribed period passes since start of a reaction, information related to product oil, and information related to operation conditions; a deterioration degree calculation step of, on the basis of the acquired information, by a deterioration function, calculating a deterioration degree of a catalyst; a reaction temperature calculation step of, on the basis of the deterioration degree of the catalyst, calculating a reaction temperature required for satisfying the information related to the raw material oil, the information related to the product oil, and the operation conditions; and a decomposition light oil acquisition amount calculation step of calculating a decomposition light oil acquisition amount on the basis of the reaction temperature and the deterioration degree of the catalyst.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an information processing method, a cracked light oil yield calculation device, a cracked light oil yield calculation program, and a non-transitory computer-readable recording medium. [Background technology]

[0002] Atmospheric residue oil, obtained by atmospheric distillation of crude oil, contains a high concentration of sulfur. The method of reducing the sulfur content of atmospheric residue oil by hydrotreating it is known as direct desulfurization. On the other hand, the method of reducing the sulfur content by vacuum distilling atmospheric residue oil and separating it into vacuum gas oil and vacuum residue oil, hydrotreating the vacuum gas oil to reduce the sulfur content, and then blending the hydrotreated vacuum gas oil and the vacuum residue is known as indirect desulfurization.

[0003] In the hydrotreatment of vacuum distillate gas oil, coke is produced as a by-product, and the activity of the hydrotreatment catalyst decreases over time due to the coke deposits on the catalyst. Therefore, in order to maintain the sulfur content of the product oil below a certain level, the reaction temperature must be increased to counteract the decrease in activity of the hydrotreatment catalyst.

[0004] On the other hand, in the hydrotreating of vacuum distillation gas oil, light fractions including naphtha, kerosene, and diesel (hereinafter abbreviated as "cracked light oil") are produced as by-products, and production control is required to balance this cracked light oil with the residual heavy oil. The yield of cracked light oil varies over time depending on changes in the cracking activity of the hydrotreating catalyst, reaction temperature, etc.

[0005] The supply of cracked light oil may increase due to changes in the product supply and demand environment. Accordingly, in a vacuum gas oil hydrotreating unit, it becomes necessary to significantly change the yield of the cracked light oil according to the supply and demand situation. Therefore, a method for accurately estimating the yield of cracked light oil is desired.

[0006] In the field of crude oil refining, various methods for accurately estimating various conditions have been studied. For example, Patent Document 1 discloses a method for estimating the reaction temperature required after switching from information on the properties of the atmospheric distillation light oil and operating conditions before switching to a feedstock containing atmospheric distillation light oil with different properties in the hydrotreatment of the feedstock containing atmospheric distillation light oil, and information on the properties of the atmospheric distillation light oil after switching and operating conditions other than the reaction temperature. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 10-60455 Summary of the Invention [Problem to be solved by the invention]

[0008] On the other hand, currently, there is no method for estimating the yield of light cracked oil, and actual data from past operations is used.

[0009] The present invention has been made in consideration of the above circumstances, and aims to provide an information processing method capable of estimating the yield of cracked light oil under specified reaction conditions in relation to the hydrotreating reaction of feedstock oil containing vacuum distillation light oil obtained by vacuum distillation of atmospheric distillation residual oil, a cracked light oil yield calculation device capable of estimating the yield of cracked light oil, a cracked light oil yield calculation program for causing a computer to function as the cracked light oil yield calculation device, and a non-transitory computer-readable recording medium storing the program. [Means for solving the problem]

[0010] In order 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 distillation of atmospheric distillation residual oil, an information acquisition step of acquiring information on the feedstock oil at a predetermined time after the start of the reaction, information on the product oil, and information on the operating conditions; a deterioration degree calculation step of calculating the deterioration degree of the desulfurization reaction and the deterioration degree of the cracking reaction of the catalyst using a deterioration function based on the acquired information on the feedstock oil, information on the product oil, and information on the operating conditions; a reaction temperature calculation step of calculating the reaction temperature required to satisfy the information on the feedstock oil, information on the product oil, and the operating conditions based on the deterioration degree of the desulfurization reaction of the catalyst; and a cracked light oil yield calculation step of calculating the yield of the cracked light oil based on the reaction temperature and the deterioration degree of the cracking reaction of the catalyst. [2] The information processing method described in [1], wherein the deterioration function is a coke deterioration function relating to the deterioration of the catalyst due to coke deposition, and is composed of a readily deactivated active species deterioration function relating to the deterioration of the easily deactivated active species of the catalyst and a refractory deactivation active species deterioration function relating to the deterioration of the refractory deactivation active species of the catalyst. [3] The information processing method according to [1] or [2], 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. [4] The information processing method according to any one of [1] to [3], wherein the information relating to the operating conditions includes information relating to the hydrogen partial pressure, information relating to the catalyst loading amount, and information relating to the feedstock supply amount. [5] A cracked light oil yield calculation device including: an acquisition unit that acquires information about the feedstock oil, information about the product oil, and information about the operating conditions at a predetermined time after the start of the reaction, regarding the hydrotreating reaction of the feedstock oil including vacuum distillation light oil obtained by vacuum distillation of atmospheric distillation residual oil; and an acquisition unit that acquires information about the feedstock oil, information about the product oil, and information about the operating conditions acquired by the acquisition unit, calculates the degree of deterioration of the desulfurization reaction and the degree of deterioration of the cracking reaction of the catalyst using a degradation function, and calculates the information about the feedstock oil, information about the product oil, and the reaction temperature required to satisfy the operating conditions based on the calculated degree of deterioration of the desulfurization reaction of the catalyst, and calculates the amount of cracked light oil obtained based on the calculated reaction temperature and the degree of deterioration of the cracking reaction of the catalyst. [6] The deactivation function is a coke deactivation function relating to catalyst deactivation due to coke deposition, and is composed of an easily deactivated active species deactivation function relating to the deactivation of easily deactivated active species of the catalyst and a hardly deactivated active species deactivation function relating to the deactivation of hardly deactivated active species of the catalyst. [5] The cracked light oil yield calculation device described in [5]. [7] 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. [5] or [6] The cracked light oil yield calculation device described in [5] or [6]. [8] The apparatus for calculating yield of cracked light oil according to any one of [5] to [7], wherein the information on the operating conditions includes information on hydrogen partial pressure, information on catalyst loading amount, and information on feedstock oil supply amount. [9] A program for calculating a yield of light cracked oil for causing a computer to function as the device for calculating a yield of light cracked oil 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]

[0011] According to the present invention, there are provided an information processing method capable of calculating the yield of cracked light oil under specified reaction conditions for the hydrotreating reaction of feedstock oil containing vacuum distillation light oil obtained by vacuum distillation of atmospheric distillation residual oil, a cracked light oil yield calculation device capable of calculating the yield of cracked light oil, a cracked light oil yield calculation program for causing a computer to function as the cracked light oil yield calculation device, and a non-transitory computer-readable recording medium storing the program. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is a flowchart of an information processing method according to an embodiment. [Figure 2] 1 is a block diagram showing the configuration of a cracked light oil yield calculation device according to an embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0013] 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.

[0014] <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 reaction has started; a deterioration calculation step (S2 in FIG. 1) for calculating the deterioration level of the catalyst desulfurization reaction and the deterioration level of the cracking reaction using a deterioration function based on the acquired information about the feedstock, information about the product oil, and information about the operating conditions; 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 desulfurization reaction; and a cracked light oil yield calculation step (S4 in FIG. 1) for calculating the cracked light oil yield based on the reaction temperature and the deterioration level of the cracking reaction of the catalyst. Each step will be described below. Each of the steps described below is executed, for example, by the cracked light oil yield calculation device 1 of this embodiment. For example, S1 is executed by the acquisition unit 11, and S2, S3, and S4 are executed by the calculation unit 13 in the computer main body 12.

[0015] <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.

[0016] (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.

[0017] 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.

[0018] (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.

[0019] 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.

[0020] (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 preferably 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 an arbitrary t days after the start of the reaction. The operating conditions may also include information about the actually measured yield of cracked light oil.

[0021] 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.

[0022] <Deterioration level calculation step> The deterioration degree calculation step in this embodiment is a step of calculating the deterioration degree of the desulfurization reaction and the deterioration degree of the cracking reaction of the catalyst using a deterioration function based on the acquired information about the raw material oil, information about the product oil, and information about the operating conditions. The step of calculating the degradation degree of the desulfurization reaction will be described below. The step of calculating the degradation degree of the decomposition reaction will be described later.

[0023] <Deterioration of desulfurization reaction> The deterioration degree of the desulfurization reaction 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 desulfurization reaction 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 desulfurization reaction of the catalyst after t days of reaction. t is the temperature T SOR is the reaction rate constant of the desulfurization reaction at

[0024] In this embodiment, the degree of deterioration of the desulfurization reaction of the catalyst can be calculated using the desulfurization reaction deterioration function based on the acquired information on the feedstock oil, information on the product oil, and information on the operating conditions.

[0025] <Degradation function 1 of desulfurization reaction> The desulfurization reaction deterioration function is a function for calculating the deterioration degree of the desulfurization reaction of the catalyst. In this embodiment, the desulfurization reaction deterioration function is preferably a coke deterioration function relating to the deterioration of the desulfurization reaction of the catalyst due to coke deposition. The coke deterioration function is not particularly limited as long as it is a function capable of calculating the deterioration degree of the coke deterioration of the catalyst. For example, the desulfurization reaction deterioration function 1 expressed by the following formula 2 can be mentioned as an example.

[0026] Φ=exp(-Dt) Equation 2 In the above formula 2, D is the deterioration coefficient of the active species of the desulfurization reaction of the catalyst, and t is the number of days elapsed since the reaction began.

[0027] D can be calculated using the following formula 3. Formula 3 below is an equation that can calculate the deterioration coefficient of the active species in the desulfurization reaction 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.

[0028]

number

[0029] 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.

[0030] 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.

[0031] 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

[0032] In the above formula 3, T SOR represents the initial activity of the catalyst for desulfurization, and α represents the deterioration rate of the catalyst for desulfurization. SOR The larger the value of α, the greater the deterioration of the catalyst's desulfurization reaction, and this deterioration behavior is reflected in the value of D.

[0033] In the above formula 3, (1 / S P n-1 -1 / S F n-1The 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 described 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.

[0034] 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).

[0035] 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 desulfurization reaction 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.

[0036] (How to calculate basic degradation parameters) In the above formula 3, α, P B ,a,Ec,T B , T SORis 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 deterioration behavior of the catalyst desulfurization reaction (changes in the reaction rate constant of the desulfurization reaction) analyzed from data obtained from the reaction in the actual plant described above or from bench-scale reactions based on the operating conditions of the actual plant. B ,a,Ec,T B (How to find α, T SOR Two examples of how to determine α and T are shown below, but the present invention is not limited to these. The first example is a method of determining α and T from the deterioration behavior of the desulfurization reaction of the catalyst (changes in the reaction rate constant of the desulfurization reaction) analyzed from data obtained from the reaction in the above-mentioned actual equipment or from a bench-scale reaction based on the operating conditions of the actual equipment. SOR The second example is a method to determine α and T from the reaction temperature profile analyzed from the data obtained from the reaction in the actual equipment or the bench-scale reaction based on the actual equipment operating conditions. SOR This is how to find it 2).

[0037] (P B ,a,Ec,T B (How to find) The method for determining the basic deterioration parameters in this embodiment is based on the deterioration behavior of the desulfurization reaction of the catalyst analyzed from data obtained from the above-mentioned reaction in an actual plant or a bench-scale reaction under actual plant operating conditions. The deterioration behavior (degree of deterioration) of the desulfurization reaction of this catalyst can be expressed by the following equation 4, based on the same concept as equation 1. Φ'=k t ' / k0' expression 4 In the above formula 4, k0' is the reaction rate constant of the desulfurization reaction 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 desulfurization reaction of the catalyst after t days of reaction. t ' is the temperature T SOR ' is the reaction rate constant of the desulfurization reaction at

[0038] The above-mentioned formula 4 is a deterioration function based on the reaction rate constant of the desulfurization reaction, similar to the above-mentioned formula 1. The reaction rate constant is expressed by the Arrhenius equation shown in the following formula 5.

[0039]

number

[0040] Temperature T at the start of reaction SOR The reaction rate constant k0 of the desulfurization reaction in ' is k t In order to obtain an activity equivalent to the reaction rate constant k0' of the desulfurization reaction 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).

[0041]

number

[0042] (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 SPn 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 degradation degree Φ' of the desulfurization reaction after t days of reaction 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 '.) A straight line represented by a n ' represents the deterioration rate of the desulfurization reaction of the catalyst.

[0043] n types of sulfur concentration S Pn The same reaction is carried out for n a n , b n Then, using the same method as above, find n a n n is an integer of 3 or more. The larger the value of n, the more accurate Ec can be obtained. On the other hand, if the value of n is too large, it takes a long time to obtain Ec, which is not efficient. In this embodiment, n is preferably 3 to 20, and more preferably 3 to 10. The n a's obtained in this way n ' and b n are substituted into the following formula 7. The following formula 7 is an equation that can calculate the activation energy of coke and the reference reaction temperature, and was first discovered by the inventors of the present application based on the operating results of an actual machine, etc.

[0044] ln(a n ​')=ln(A)-(Ec / Rb n ) Equation 7 In Equation 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)).

[0045] n a n ' and b n For the combination of ln(a n ') on the vertical axis, and 1 / b n Plot the horizontal axis, draw a regression line, and determine its slope. Since this slope is Ec / R, the activation energy of coke deterioration, Ec, can be calculated by subtracting R from the slope.

[0046] Also, n b n By averaging T B can be obtained.

[0047] Ec and T B In determining the above, it is preferable that the LHSV, hydrogen partial pressure, hydrogen / feed oil ratio, and sulfur concentration in the feed oil are conditions that correspond to the operating conditions of the actual plant. Such LHSV is, for example, 0.5 to 2.5 h -1 The hydrogen partial pressure is, for example, 3 to 7 MPa, and the hydrogen / feedstock ratio is, for example, 100 to 400 [Nm 3 / kL], and the sulfur concentration in the feed oil is, for example, 0.5 to 3.0 mass %. n types of sulfur concentration S Pn Similarly, it is preferable to set the conditions for S to match the actual operating conditions. Pn The content is, for example, 0.3 mass % or less. The reaction period is, for example, 100 to 1500 days.

[0048] (P B and how to find a) Under the conditions of constant LHSV, hydrogen / feed oil ratio, sulfur concentration in feed oil, and sulfur concentration in produced oil, the hydrogen partial pressure P mThe reaction is carried out for a certain period of time under the conditions. Because the catalyst deteriorates during the reaction, the reaction temperature is increased to maintain a constant sulfur concentration in the resulting oil. If the reaction time is plotted on the horizontal axis and the measured reaction temperature on the vertical axis, a regression line is drawn, which gives y=a m x+b m (0 m ) is obtained. On this line, b m is T in the above formula 6 SOR In the above formula 6, T SOR ' to b m Substituting, T t By substituting the actual reaction temperature into ', the degradation degree Φ' of the desulfurization reaction after any reaction time t days has elapsed can be obtained. By plotting the reaction time on the horizontal axis and the logarithm of Φ' on the vertical axis and drawing a regression line, y = -a m 'x(|―a m '|=a m '.) A straight line represented by a m ' represents the deterioration rate of the desulfurization reaction of the catalyst.

[0049] 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 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.

[0050] ln(a m ')=-aln(P m )+B1 formula 8 In the formula 8, B1 can be 0. ​

[0051] 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.

[0052] In addition, the m hydrogen partial pressures P m By averaging P B can be obtained.

[0053] a and P B In determining the above, it is preferable that the LHSV, hydrogen / feed oil ratio, 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 -1 The hydrogen / feedstock ratio is, for example, 100 to 400 [Nm 3 / kL], the sulfur concentration in the feed 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. m types of hydrogen partial pressure P m Similarly, it is preferable to set the conditions for P to match the actual operating conditions. m The pressure is, for example, 3 to 7 MPa. The reaction period is, for example, 50 to 600 days.

[0054] (α and T SOR How to find 1) In an actual plant or on a bench scale, the reaction is carried out for a certain period of time so that the LHSV, hydrogen partial pressure, hydrogen / feed oil ratio, sulfur concentration in the feed oil, and sulfur concentration in the product oil are the assumed operating conditions of the actual plant. Because the catalyst deteriorates during the reaction, the reaction temperature is increased during operation. The assumed operating conditions of the actual plant are (Ec and T B (How to find P B The operating conditions explained in (2) above are an example. 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 α x+b αA straight line expressed as a is obtained. α is a value correlated to α in the above formula 3, and b α is T in the above formula 3 SOR In the above formula 6, T SOR ' to b α Substituting, T t By substituting the actual reaction temperature into ', the degradation degree Φ' of the desulfurization reaction after any reaction time t days has elapsed can be obtained. By plotting the reaction time on the horizontal axis and the logarithm of Φ' on the vertical axis and drawing a regression line, y = -a α 'x(|-a α '|=a α ') is obtained. a α ' represents the deterioration rate of the desulfurization reaction of the catalyst.

[0055] The operating condition is S P , S F , LHSV, P, and P obtained by the above method B ,a,Ec,T B、 T SOR (i.e., b α ) into the above formula 3 to find D. Substituting the found D into the above formula 2 gives Φ. In this case, Φ is a function of α. If the reaction time is plotted on the horizontal axis and the logarithm of Φ on the vertical axis, and a regression line is drawn by changing α so that 0<α, then y=-α α ”x(|-a α ”|=a α For each value of α, multiple lines expressed as α " and the above-mentioned a α The value of α when ' is equal to α can be used as α in the above formula 3.

[0056] (α and T SOR How to find 2) (α and T SOR Carry out the same reaction as in 1) above, and find y=a α x+b α Obtain a line represented by b α T in the above formula 3 SOR The operating condition is S P , S F, LHSV, P, and P obtained by the above method B ,a,Ec,T B、 T SOR (i.e., b α ) into the above formula 3 to find D. Substituting the found D into the above formula 2 gives Φ. In this case, Φ is a function of α. Substituting the found Φ into Φ' in the above formula 6, T SOR (i.e., b α ) in the above formula 6 SOR ' and T t ', T t ' is a function of α. The measured reaction temperature T obs T for t ' ratio (T t ' / T obs ) becomes 1 can be used as the α in the above formula 3. Similarly, N reaction temperatures T obs T for t ' ratio (T t ' / T obs ) and the value of α when their average is closest to 1 is preferably used as α in the above formula 3. N is an integer of 10 or more, preferably 10 to 500, and more preferably 50 to 200.

[0057] (Modification of the degradation function 1 of the desulfurization reaction) A modified example of the degradation function 1 of the desulfurization reaction will be described below. As the degradation function 1 of the desulfurization reaction, the degradation function 1-1 of the desulfurization reaction expressed by the following formula 9 may be used.

[0058] Φ=exp(-D't) Equation 9 In the above formula 9, D' is the deterioration coefficient of the active species of the desulfurization reaction of the catalyst, and t is the number of days elapsed since the reaction began.

[0059] D' can be calculated using the following formula 10.

[0060]

number

[0061] 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).

[0062] In this specification, the "reference hydrogen / feed oil ratio" refers to a standard hydrogen / feed oil ratio under actual reaction conditions. It is calculated as the average value of the hydrogen / feed oil ratios used to determine the hydrogen / feed oil ratio coefficient b, which will be described later.

[0063] 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.

[0064] P B ,a,Ec,TB , T SOR can be calculated in the same way as in the formula 3. B , b, and α' are calculated as follows.

[0065] G B , b is P B ,a,Ec,T B , T SOR Similarly to G, G is a parameter determined depending on the catalyst used, and may be determined while carrying out a reaction in an actual machine, or may be determined in advance on a bench scale based on the operating conditions of the actual machine. In this embodiment, it is preferable to determine G in advance on a bench scale based on the operating conditions of the actual machine. B We will explain how to calculate b.

[0066] (G B , how to find b) The method for determining the basic deterioration parameters in this embodiment is based on the deterioration behavior of the desulfurization reaction of the catalyst analyzed from data obtained from the reaction in the above-mentioned actual machine or from a bench-scale reaction based on the operating conditions of the actual machine.

[0067] Under the conditions of constant LHSV, hydrogen partial pressure, sulfur concentration in feed oil, and sulfur concentration in the produced oil, the hydrogen / feed oil ratio G h The reaction is carried out for a certain period of time under the conditions. Because the catalyst deteriorates during the reaction, the reaction temperature is increased to maintain a constant sulfur concentration in the resulting oil. If the reaction time is plotted on the horizontal axis and the measured reaction temperature on the vertical axis, a regression line is drawn, which gives y=a h x+b h (0 h ) is obtained. On this line, b h is T in the above formula 6 SOR In the above formula 6, T SOR ' to b h Substituting, T t By substituting the actual reaction temperature into ', the degradation degree Φ' of the desulfurization reaction after any reaction time t days has elapsed can be obtained. By plotting the reaction time on the horizontal axis and the logarithm of Φ' on the vertical axis and drawing a regression line, y = -a h 'x(|―a h ​'|=a h '.) A straight line represented by a h ' represents the deterioration rate of the desulfurization reaction of the catalyst.

[0068] h types of hydrogen / feed oil ratio G h The same reaction is carried out for h a h , b h Then, using the same method as above, find h a h 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.

[0069] ln(a h ')=-bln(G h )+B3 Equation 11 In the formula 11, B3 can be 0.

[0070] 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.

[0071] In addition, the above h types of hydrogen / feed oil ratio G h By averaging, G B can be obtained.

[0072] 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 -1 The 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.

[0073] In addition, α' is calculated in the same manner as in the section on the deterioration function of the desulfurization reaction 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).

[0074] <Degradation function of desulfurization reaction 2> In this embodiment, the coke deterioration function relating to the deterioration of the desulfurization reaction of the catalyst 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 in the desulfurization reaction of the catalyst and a less easily deactivated active species deterioration function relating to the deterioration of less easily deactivated active species in the desulfurization reaction of the catalyst.

[0075] Φ=k1×exp(-D1t)+k2×exp(-D2t) Equation 12 In Equation 12, k1 is the activity site coefficient of the easily deactivated active species in the desulfurization reaction of the catalyst, k2 is the activity site coefficient of the resistant to deactivation active species in the desulfurization reaction of the catalyst, and the activity site coefficients represent the relative reaction rate constants of the desulfurization reaction of both active species. D1 is the deterioration coefficient of the easily deactivated active species in the desulfurization reaction of the catalyst, D2 is the deterioration coefficient of the resistant to deactivation active species in the desulfurization reaction of the catalyst, t is the number of days elapsed since the reaction began, and k1 + k2 = 1.

[0076] 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.

[0077] 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.

[0078] 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 for the desulfurization reaction, which are deactivated in the early stage of the reaction, and active species that are difficult to deactivate for the desulfurization reaction, which are deactivated from the middle stage of the reaction onwards. As a result, they found that deactivation function 2 makes it possible to calculate the degree of deactivation of the catalyst's desulfurization reaction more accurately than deactivation function 1. The easily deactivated active species for the desulfurization reaction are active species that mainly lose activity in the early stage of the reaction, and the difficult to deactivate active species for the desulfurization reaction are active species that lose activity from the middle stage of the reaction onwards.

[0079] In the formula 12, k1 represents the active site coefficient of the active species that is easily deactivated in the desulfurization reaction of the catalyst, and k2 represents the active site coefficient of the active species that is difficult to deactivate in the desulfurization reaction of the catalyst. k1 and k2 are constants specific to the catalyst, and their calculation methods will be described later.

[0080] D1 can be calculated using the following formula 13, and D2 can be calculated using the following formula 14.

[0081]

number

[0082]

number

[0083] In the formula 13 and the formula 14, S F is the sulfur concentration (mass%) in the feed oil after any reaction time t days, and S P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of feedstock oil containing vacuum distillation gas oil, and LHSV is the liquid hourly space velocity (h -1 ) and P B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, Ec is the activation energy of coke degradation (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol K)), and T B is the reference reaction temperature (K), and T SOR is the required temperature (K) on day 0. In the above formula 13, α1 is the catalytic constant of the easily deactivated active site for the desulfurization reaction (a constant representing the degradation rate of the desulfurization reaction of the catalyst), and in the above formula 14, α2 is the catalytic constant of the hardly deactivated active site for the desulfurization reaction (a constant representing the degradation rate of the desulfurization reaction of the catalyst).

[0084] In the formula 13 and the formula 14, S F , S P , LHSV, and P are values ​​substituted based on the information on the feed oil, the information on the product oil, and the information on the operating conditions acquired in the information acquisition step, as in the explanation of the above-mentioned formula 3. Note that the LHSV can be calculated by dividing the feed oil supply rate (volume / h) by the catalyst loading amount (volume).

[0085] As mentioned above, S F , LHSV, and P are controllable parameters. P is the sulfur concentration of the target product oil. That is, according to the above formulas 13 and 14, the above S F , S PThe deactivation coefficient of the easily deactivated active species in the desulfurization reaction of the catalyst and the deactivation coefficient of the less easily deactivated active species in the desulfurization reaction 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.

[0086] (How to calculate basic degradation parameters) In the formula 13 and the formula 14, α1, α2, P B ,a,Ec,T B , T SOR is a constant, as in the above-mentioned formula 3, and these parameters are collectively referred to as "basic deterioration parameter 2." The basic deterioration parameter 2 is a parameter determined depending on the catalyst used, and may be determined while carrying out a reaction in an actual machine, or may be determined in advance on a bench scale based on the operating conditions of the actual machine. In this embodiment, it is preferable to determine it in advance on a bench scale based on the operating conditions of the actual machine. In the above-mentioned formulas 13 and 14, P B ,a,Ec,T B can be calculated in the same manner as in Equation 3 above. On the other hand, α1, α2, T SOR can be calculated by the following two methods: In addition, the coefficient k1 of the number of active sites of the easily deactivated active species in the desulfurization reaction of the catalyst and the coefficient k2 of the number of active sites of the hardly deactivated active species in the desulfurization reaction of the catalyst in the above formula 12 can also be calculated at the same time as follows.

[0087] (α1, α 2、 T SOR , k1, and k2 calculation method 1) In an actual plant or on a bench scale, the reaction is carried out for a certain period of time so that the LHSV, hydrogen partial pressure, hydrogen / feed oil ratio, sulfur concentration in the feed oil, and sulfur concentration in the product oil are the expected operating conditions of the actual plant. Because the catalyst deteriorates during the reaction, the reaction temperature is increased during operation. The reaction time is plotted on the horizontal axis and the reaction temperature on the vertical axis. When drawing a regression line for these plots, as mentioned above, the initial reaction time (x1 to x n ) is a straight line expressed as y=a1x+b1, which correlates with the rapid rise in reaction temperature, and the line expressed as y=a1x+b1 after the middle stage of the reaction (x n+1 ~x m) Two straight lines are obtained, which are expressed as y = a2x + b2, which correlate with the gradual increase in reaction temperature. In the above equation, a1 > a2 > 0, and b1 <b2であり、x1<x n <x n+1 <x m x n , x m means the reaction time relative to the n(m)th plot from the start of the reaction.

[0088] 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 active species that are easily deactivated in the desulfurization reaction of the catalyst exist, and (x ip , y ip ) is considered to have two active species: one that is easily deactivated in the desulfurization reaction of the catalyst and one that is difficult to deactivate in the desulfurization reaction of the catalyst.

[0089] In the formula 6, T SOR ' is assigned to b1, and T t By substituting the reaction temperature into ', the degradation degree Φ' of the desulfurization reaction 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 values ​​of x1 to x ip If we draw a regression line up to y = -a1'x (|-a1'| = a1'), we get a line expressed as y = -a1'x (|-a1'| = a1'). ip ~x m If we draw a regression line from α1 to α2, we obtain a line expressed as y=-a2'x-b2' (|-a2'|=a2' and |-b2'|=b2'). a1' is a value correlated with α1, a2' is a value correlated with α2, and b2' is a value correlated with k2.

[0090] k2 can be found by substituting b2' obtained from the regression line described above into the following formula 15. Since k1 is k1+k2=1, it can be found from k1=1-k2. k2=exp(-b2') Equation 15

[0091] 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 For each value of α1, multiple straight lines expressed as α1 The α1 when the above-mentioned a1' is equal to " can be set as the α1 in the above-mentioned formula 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 For each value of α2, multiple straight lines expressed as α2 The α2 when the above-mentioned a2' is equal to " can be set as the α2 in the above-mentioned formula 14.

[0092] (α1, α 2、 T SOR 2) How to calculate k1 and k2 (α1, α 2、 T SOR , k1, and k2. 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 ' and T t ', 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 ' 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 ' 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. x ip ~x m The measured reaction temperature T obs T for t ' ratio (T t ' / T obs ) is 1, the combination of α2 and k2 can be determined, 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 determined, and this k1 can be used as k1 in the above formula 13. Similarly,obs T for t ' ratio (T t ' / T obs ) and use α2 and k2 when their average is closest to 1 as α2 and k2 in the formula 14. Also, use k1 calculated from the obtained k2 as k1 in the formula 13. L is an integer of 10 or more, preferably 10 to 500, and more preferably 50 to 200.

[0093] In this way, α1, α 2、 T SOR , k1, and k2, it is necessary to obtain y=a1x+b1 and y=a2x+b2. For example, y=a1x+b1 and y=a2x+b2 can be obtained as follows.

[0094] 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.

[0095] 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 coefficient of y = a'x + b' becomes 0.5 or greater.

[0096] (Modification of the degradation function 2 of the desulfurization reaction) A modified example of the degradation function 2 of the desulfurization reaction will be described below. As the degradation function 2 of the desulfurization reaction, a degradation function 2-1 of the desulfurization reaction expressed by the following formula 16 may be used.

[0097] 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 that is easily deactivated in the desulfurization reaction of the catalyst, and D2' is the deterioration coefficient of the active species that is difficult to deactivate in the desulfurization reaction of the catalyst.

[0098] D1' can be calculated using the following formula 17, and D2' can be calculated using the following formula 18.

[0099]

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[0100]

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[0101] In the formula 17 and the formula 18, S F , S P ,n,LHSV,P B ,P,a,Ec,R,T B , T SOR is the same as the formula 13 and the formula 14, and G B , G, and b are the same as in Equation 10, and in Equation 17, α1' is the catalytic constant of the easily deactivated active site in the desulfurization reaction (a constant representing the degradation rate of the desulfurization reaction of the catalyst), and in Equation 18, α2' is the catalytic constant of the hardly deactivated active site in the desulfurization reaction (a constant representing the degradation rate of the desulfurization reaction of the catalyst).

[0102] P B ,a,Ec,T B , T SOR can be calculated in the same manner as described in the above formulas 13 and 14, and G B , b can be calculated in the same manner as described in Equation 10 above.

[0103] In addition, α1' and α2' can be calculated in the same manner as for calculating α1 and α2 described in the desulfurization reaction deterioration function 2, except that Equation 16 is used instead of Equation 12, Equation 17 is used instead of Equation 13, and Equation 18 is used instead of Equation 14.

[0104] <Reaction temperature calculation step> The reaction temperature calculation step of this embodiment is a 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 desulfurization reaction of the catalyst. The reaction temperature is preferably calculated using a desulfurization rate equation based on the Arrhenius equation.

[0105] <Degradation rate equation for desulfurization reaction> The deterioration rate equation for the desulfurization reaction is based on the Arrhenius equation expressed by the above-mentioned equation 5. Similar to the calculation method for the above-mentioned equation 6, the following equation 19 is derived from the above-mentioned equations 1 and 5.

[0106]

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[0107]

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[0108] 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.

[0109] (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.

[0110] 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.

[0111]

number

[0112] The same reaction is carried out for x types of LHSV(x), and x plots of the above are obtained. Based on the obtained plots, a regression line is drawn through the origin to obtain a line expressed as y=cx. y is ((1 / (n-1))((1 / S P n-1 )-(1 / S F n-1 ))), where x is 1 / LHSV and c is k. Calculate the correlation function using Excel or similar software and find the n that makes the correlation coefficient closest to 1. The resulting n is the reaction order. Note that n should be calculated to the first decimal place.

[0113] The above x is an integer of 3 or more. The larger the number of x, the more accurate n can be obtained. On the other hand, if the number of x is too large, it takes a long time to obtain n, which is not efficient. In this embodiment, x is preferably 3 to 20, and more preferably 3 to 10.

[0114] In determining n, the reaction temperature, hydrogen partial pressure, hydrogen / feedstock ratio, and sulfur concentration in the feedstock are preferably set to conditions that correspond to the operating conditions of an actual plant. Such a reaction temperature is, for example, 300 to 420°C, the hydrogen partial pressure is 3 to 7 MPa, and the hydrogen / feedstock ratio is 100 to 400 [Nm 3 / kL], and the sulfur concentration in the feed oil is 0.5 to 3.0 mass %. Similarly, it is preferable that the x types of LHSV(x) are set to conditions that correspond to the actual operating conditions. Such LHSV(x) should be set to 0.5 to 2.5 h -1 is.

[0115] When the activation energy E in the Arrhenius equation expressed by the above formula 5 is set as the activation energy Ea of desulfurization and the natural logarithm of both sides is taken, the following formula 22 is obtained.

[0116]

number

[0117] 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.

[0118] 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.

[0119] 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 time to obtain Ea, which is not efficient. In this embodiment, y is preferably 3 to 20, and more preferably 3 to 10.

[0120] 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.

[0121] 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.

[0122] Actual reaction temperature T obs The reaction temperature T obtained by the information processing method of this embodiment t is the ratio of T t / T obs is preferably 0.97 to 1.03, and more preferably 0.985 to 1.015, in °C. t / T obs If is within the above range, it can be determined that the reaction temperature can be estimated with high accuracy.

[0123] <Steps for calculating the amount of cracked light oil> In the present embodiment, the step of calculating the yield of cracked light oil is carried out at the reaction temperature T t The yield of cracked light oil is calculated based on the degree of deterioration of the cracking reaction of the catalyst and the rate of degradation of the cracking reaction of the catalyst. The yield of cracked light oil is preferably calculated using a cracked light oil yield calculation function based on a first-order cracking reaction rate equation.

[0124] <Light cracked oil yield calculation function> The function for calculating the yield of cracked light oil is expressed by the following formula 23.

[0125]

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[0126] In the above-mentioned formula 23, LHSV is a value substituted based on the information on 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). Φ C and k C0(Tt) The method for calculating this will be described later.

[0127] The degradation degree of the decomposition reaction in the above formula 23 is expressed by the following formula 24. Φ C =k Ct(T0) / k C0(T0) formula 24 In the formula 24, k C0(T0) is the reaction rate constant of the decomposition reaction of the catalyst (fresh catalyst) at the beginning of the reaction (i.e., at the start of the reaction), and k Ct(T0) is the reaction rate constant of the catalyst decomposition reaction after t days of reaction. Ct(T0) , k C0(T0) is the temperature T SOR is the reaction rate constant for the decomposition reaction at

[0128] The above-mentioned formula 23 is derived based on the premise that the cracking reaction of vacuum distillation gas oil is a first-order reaction and that only cracked light oil is produced by the cracking reaction. The method for deriving the above-mentioned formula 23 will be explained below.

[0129] The decomposition reaction rate equation is expressed as Equation 25 below. k Ct(Tt) =ln(C F / C P )×LHSV Equation 25 In the formula 25, k Ct(Tt) is the reaction temperature T calculated in the above reaction temperature calculation step after any reaction t days have passed. t The reaction rate constant (h -1 ) and C F is the vacuum distillation diesel concentration (mass%) in the feedstock oil after any reaction time t days, and C P is the vacuum distillation gas oil concentration (mass%) in the produced oil after t days of reaction, and LHSV is the liquid hourly space velocity (h -1 )

[0130] C F / C P is dimensionless, so C F If is set to 1, the conversion rate C of the decomposition reaction after any reaction time t days has elapsed t (%) is C t =(1-C P ) × 100. Therefore, C P is C P =1-C t As mentioned above, based on the assumption that only light cracked oil is produced by the cracking reaction, the conversion rate C t (%) is also the amount of cracked light oil obtained (mass %). Substituting these values ​​into the above formula 25, the following formula 26 is obtained.

[0131]

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[0132]

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[0133] Φ C =k Ct(Tt) / k C0(Tt) formula 28 In the formula 28, k C0(Tt) is the reaction rate constant of the decomposition reaction of the catalyst (fresh catalyst) at the beginning of the reaction (i.e., at the start of the reaction), and k Ct(Tt) is the reaction rate constant of the catalyst decomposition reaction after t days of reaction. Ct(Tt) , k C0(Tt) is the reaction temperature T calculated in the reaction temperature calculation step above after t days of reaction. t is the reaction rate constant for the decomposition reaction at

[0134] From the above formula 28, k Ct(Tt) =Φ C ×k C0(Tt) By substituting this value into the above-mentioned equation 27, the above-mentioned equation 23 is derived.

[0135] Next, Φ C , k C0(Tt) Explain how to find it.

[0136] (k C0(Tt) (How to find) k C0(Tt) is a parameter (constant) determined depending on the catalyst used, and may be determined while carrying out 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 it in advance on a bench scale based on the operating conditions of the actual reactor. k C0(Tt) can be calculated by the following formula 29. The following formula 29 is based on the Arrhenius equation expressed by the formula 5 above.

[0137]

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[0138] k C0(T0) is the reaction temperature T of the fresh catalyst SOR Since this is the reaction rate constant of the decomposition reaction in the above formula 26, it can be calculated by the following formula 30.

[0139]

number

[0140] That is, k C0(T0) is a bench scale reaction using fresh catalyst at the reaction temperature of T SOR The hydrotreating reaction is carried out at the LSHV, which is the operating condition of the actual plant, and the yield of light cracked oil is measured, and the yield can be calculated from the above formula (30).

[0141] On the above bench scale, k C0(T0) When calculating the above, it is preferable that the hydrogen partial pressure, hydrogen / feed oil ratio, LHSV, and sulfur concentration in the feed oil are 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 -1The sulfur concentration in the feed oil is 0.5 to 3.0 mass %.

[0142] k C0(T0) can be calculated while the reaction is running in the actual equipment as follows: int Reaction temperature T int The amount of cracked light oil obtained and the LHSV can be calculated by substituting them into the above formula 30. int The time is preferably 20 days or less, and more preferably 10 days or less. int When T is equal to or less than the upper limit, a value very close to the reaction rate constant of the decomposition of the fresh catalyst can be obtained. int is a value calculated from the deterioration degree of the desulfurization reaction by the reaction temperature calculation step described above.

[0143] Activation energy of decomposition E D can be found as follows:

[0144] The activation energy E in the Arrhenius equation represented by Equation 5 is the decomposition activation energy E D Taking the natural logarithm of both sides gives us the following equation (31).

[0145]

number

[0146] The activation energy of decomposition can be determined by carrying out the reaction in an actual plant, or based on the operating conditions of the actual plant. This may be determined in advance on a bench scale based on the above equation. The hydrogen partial pressure, hydrogen / feedstock ratio, LHSV, and sulfur concentration in the feedstock are kept constant, and the reaction is carried out at a reaction temperature of T(y'), and the amount of cracked light oil obtained in the product oil is measured. The obtained amount of cracked light oil and LHSV are substituted into equation 26 to determine the reaction rate constant k. The obtained reaction rate constant is substituted into equation 31, and the result (lnk) on the left side of the equation is plotted on the vertical axis and 1 / T (1 / T(y')) on the horizontal axis.

[0147] The same reaction is carried out for y' kinds of reaction temperatures T(y'), and y' plots are obtained. A regression line is drawn from the obtained plots, and its slope is calculated. This slope is E D / R, so by subtracting R from the slope, the activation energy of decomposition, E D can be obtained.

[0148] The above y' is an integer equal to or greater than 3. The larger the number of y', the more accurate the E D On the other hand, if the number of y' is too large, E D In this embodiment, y' is preferably 3 to 20, and more preferably 3 to 10.

[0149] E D In determining the above, it is preferable that the hydrogen partial pressure, hydrogen / feed oil ratio, LHSV, and sulfur concentration in the feed oil are 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.

[0150] The k obtained in this way C0(T0) , the activation energy of decomposition E D , T SOR , the reaction temperature T calculated in the reaction temperature calculation step described above t By substituting into the above equation 29, k C0(Tt) Ask for.

[0151] <How to determine the degradation level of decomposition reaction> When the desulfurization reaction activity of the catalyst decreases, the cracking reaction activity also decreases. Therefore, it is thought that there is a correlation between the degree of deterioration of the desulfurization reaction and the degree of deterioration of the cracking reaction. The inventors of the present application focused on this correlation and calculated the degree of deterioration of the cracking reaction ΦC It has been found for the first time that the degradation degree Φ of the desulfurization reaction can be calculated based on the degradation function Φ of the desulfurization reaction described above. Hereinafter, the degradation degree Φ of the decomposition reaction based on the degradation function 1 (or 1-1) of the desulfurization reaction and the degradation function 2 (or 2-1) of the desulfurization reaction will be referred to as the degradation function Φ of the decomposition reaction. C We will explain how to find each of these.

[0152] (Method 1 for determining the degree of degradation of decomposition reactions) Φ C The method for calculating Φ is based on the degradation function 1 of the desulfurization reaction. C This is a method to find Φ C can be calculated using the following equation 32.

[0153] Φ C =βΦ Equation 32 In the above formula 32, Φ C is the degradation degree of the decomposition reaction, Φ is the degradation degree of the desulfurization reaction (degradation function 1 (or 1-1) of the desulfurization reaction), and β is the degradation coefficient of the decomposition reaction (constant).

[0154] Since Φ can be calculated using the method described above, once β is determined, Φ can be calculated from C In the above formula 32, Φ at the time of reaction elapsed time 0 can be calculated. C where βΦ=1.

[0155] In an actual plant or on a bench scale, the reaction is carried out for a certain period of time so that the LHSV, hydrogen partial pressure, hydrogen / feed oil ratio, sulfur concentration in the feed oil, and sulfur concentration in the product oil are the assumed operating conditions of the actual plant. Because the catalyst deteriorates during the reaction, the reaction temperature is increased during operation. The reaction temperature at this time is calculated by the reaction temperature T calculated in the reaction temperature calculation step described above. t The assumed operating conditions of the actual plant are the conditions used to calculate the activation energy of cracking described above. The amount of cracked light oil obtained after t' days of reaction, C, is t ' was measured and the resulting C t ', k obtained by the above method C0(Tt) (k C0(Tt’) ), and LHSV are substituted into Equation 23, CAlso, using the above method, Φ is calculated after t' days of any reaction. Similarly, Φ is calculated for multiple reactions after t' days. C and Φ are calculated. Φ C For the combination of and Φ, Φ is on the x-axis, and Φ C The y-axis is used to plot the values. A regression line is drawn between these plots (where x=0 and y=0). The slope of this line is β. The number of plots used to determine β is preferably 10 to 100, and more preferably 10 to 50. Furthermore, the value of t' used to determine β is preferably after 3 days of reaction.

[0156] (Method 2 for determining the degree of degradation of decomposition reactions) Φ C The method 2 for determining Φ is based on the degradation function 2 of the desulfurization reaction. C This is a method to find Φ C can be calculated using the following equation 33.

[0157] Φ C =β1Φ1+β2Φ2 Equation 33 In the above formula 33, Φ C is the degree of deterioration of the decomposition reaction, Φ1 is k1 × exp(-D1t) in the above formula 12, Φ2 is k2 × exp(-D2t) in the above formula 12, β1 is the decomposition deterioration coefficient (constant) of the easily deactivated active species of the catalyst, and β2 is the decomposition deterioration coefficient (constant) of the hardly deactivated active species of the catalyst.

[0158] Since Φ1 and Φ2 can be obtained by the above method, once β1 and β2 are determined, Φ C In the above formula 33, Φ at the time of reaction elapsed time 0 can be calculated. C is β1Φ1+β2Φ2=1.

[0159] In an actual plant or on a bench scale, the reaction is carried out for a certain period of time so that the LHSV, hydrogen partial pressure, hydrogen / feed oil ratio, sulfur concentration in the feed oil, and sulfur concentration in the product oil are the assumed operating conditions of the actual plant. Because the catalyst deteriorates during the reaction, the reaction temperature is increased during operation. The reaction temperature at this time is calculated by the reaction temperature T calculated in the reaction temperature calculation step described above. t The amount of cracked light oil obtained after any reaction time t' is C t ' was measured and the resulting C t ', k obtained by the above method C0(Tt) (k C0(Tt’) ), and LHSV are substituted into Equation 23, C Also, using the above method, Φ1 and Φ2 are calculated after t' days of reaction. C , Φ1, Φ2 are substituted into the above formula 33. Similarly, Φ Cn , Φ 1n , Φ 2n If Equation 33 holds for each combination, then Φ Cn =β1'Φ 1n +β2'Φ 2n In this equation, Φ Cn is the dependent variable, Φ 1n、 and Φ 2n The β1' and β2' with the smallest error can be obtained by two-way linear regression with β as the independent variables. The obtained β1' can be used as β1 in the above formula 33, and the obtained β2' can be used as β2 in the above formula 33. In obtaining β1 and β2, Φ C The number of combinations of Φ1 and Φ2 is preferably 10 to 100, more preferably 10 to 50. In addition, the time t' for determining β1 and β2 is preferably 3 days or more after the reaction.

[0160] Using the β or β1 and β2 obtained by the above method, Φ is calculated from the above formula 32 or 33. C can be obtained.

[0161] The k obtained by the above method C0(Tt) , Φ calculated by the above-mentioned formula 32 or the above-mentioned formula 33C By substituting the above formula 23, the yield of light cracked oil after t days of reaction can be calculated.

[0162] Actual cracked light oil yield C obs The amount of cracked light oil obtained by the information processing method of this embodiment is C t C is the ratio of t / C obs is preferably 0.80 to 1.20, more preferably 0.85 to 1.15, in terms of mass %. t / C obs If the value is within the above range, it can be determined that the yield of cracked light oil can be estimated with high accuracy.

[0163] <<Information output step>> The method may further include an information output step (S5 in FIG. 1) of outputting information indicating the yield of the cracked light oil thus obtained. For example, S5 is executed by the output unit 14.

[0164] <Hydrotreatment reaction of feedstock oil containing vacuum distillation gas oil> The hydrotreating reaction of feedstock oil containing vacuum distillation gas oil will be outlined below. Vacuum distillation gas oil is a fraction with a boiling point range of 200 to 550°C obtained by vacuum distillation of atmospheric distillation residue. The density of vacuum distillation gas oil is 0.91 to 0.95 g / mL. The content of vacuum distillation gas oil in the feedstock oil may be, for example, 30% by volume or more, or 50% by volume or more. In addition, examples of oil types other than vacuum distillation light oil contained in the feedstock include atmospheric heavy oil obtained by atmospheric distillation of crude oil in an atmospheric distillation unit, heavy extracts which are particularly heavy oils among the oils extracted and removed by solvent extraction of lubricating base oils such as hydrocracked heavy oil, atmospheric distillation residual oil, fluid catalytic cracking residual oil, and de-sludge oil.

[0165] The hydrotreating reaction of a feedstock containing vacuum gas oil can be carried out by contacting the feedstock containing vacuum gas oil with a hydrotreating catalyst in the presence of hydrogen. The hydrotreating catalyst is not particularly limited, and any hydrotreating catalyst known in the art can be used. Various catalyst supports can be used, including, for example, silica, alumina, boria, magnesia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-boria, alumina-zirconia, alumina-titania, alumina-boria, alumina-chromia, titania-zirconia, silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, and the like, or mixtures of two or more of these. Among these inorganic oxides, preferred are alumina, silica-alumina, alumina-titania, alumina-boria, and alumina-zirconia, with alumina being particularly preferred, and gamma alumina being particularly preferred. These inorganic oxides may be used alone or in combination of two or more.

[0166] The metal contained in the support as an active component is at least one metal selected from Group 6 metals and Groups 8 to 10 metals of the periodic table, preferably molybdenum, tungsten, cobalt, and nickel. These metals are effective in the metallic state, metal oxide, or metal sulfide form. They may also be bonded to the catalyst support by ion exchange or other methods. The content of this metal component is typically within the range of approximately 10 to 25 mass% of the catalyst, calculated as oxide. If the metal content is less than 10 mass%, the absolute amount of metal acting as active sites is small, and hydrotreating activity (hereinafter simply referred to as hydrotreating activity), including desulfurization activity, is not achieved. Conversely, if the supported metal content is greater than 25 mass%, metal aggregation occurs, reducing the number of active sites and, as a result, hydrotreating activity is actually reduced. Furthermore, if necessary, phosphorus, boron, zinc, zirconia, etc. can be contained in addition to the active metals consisting of Group 6 and Group 8 metals of the periodic table. When applying the method of the present invention, there is no restriction on the form of the catalyst bed, and it can be applied to reactors with catalyst beds such as fixed beds, moving beds, and fluidized beds.

[0167] The conditions for the hydrotreating reaction of feedstock oil containing vacuum distillation gas oil are generally a reaction temperature of 300 to 420°C, preferably 340 to 400°C, a hydrogen partial pressure of 3 to 7 MPa, preferably 4 to 6 MPa, and an LHSV of 0.5 to 2.5 h. -1 , preferably 0.6 to 1.5 hours -1 The hydrogen / feed oil ratio is 100 to 400 [Nm 3 / kL], preferably 200 to 300 [Nm 3 / kL].

[0168] The sulfur concentration in the feedstock oil containing vacuum distillation gas oil is usually 0.5 to 3.0 mass %, and the sulfur concentration in the product oil is usually 0.01 to 0.3 mass %.

[0169] In this specification, the term "cracked light oil" cannot be generally defined as it differs depending on the feedstock oil, the equipment, etc., but examples include fractions with a boiling point of 343°C or less and a carbon number of 5 or more. Note that components with a boiling point of 343°C or less and a carbon number of less than 5 are gas components, so "cracked light oil" in this specification refers to, for example, fractions with a boiling point of 343°C or less. The yield of cracked light oil can be determined by a method for measuring the yield of cracked light oil known in the art, such as calculation from the proportion of fractions having a boiling point of 343°C or less using a distillation test such as ASTM D-6352.

[0170] ≪Cracked light oil yield calculation device≫ The cracked light oil yield calculation device of this embodiment includes an acquisition unit that acquires information about the feedstock, information about the product oil, and information about operating conditions a predetermined time after the start of the hydrotreating reaction of feedstock containing vacuum distillation light oil; and a calculation unit that calculates the degradation levels of the desulfurization reaction and the cracking reaction of the catalyst using a degradation function based on the information about the feedstock, information about the product oil, and information about the operating conditions acquired by the acquisition unit, calculates the information about the feedstock, information about the product oil, and the reaction temperature required to satisfy the operating conditions based on the calculated degradation level of the desulfurization reaction of the catalyst, and calculates the cracked light oil yield based on the calculated reaction temperature and the degradation level of the cracking reaction of the catalyst.

[0171] The cracked light oil yield 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 cracked light oil yield calculation device 1 may be configured using one or more information processing devices. For example, the cracked light oil yield calculation device 1 may be configured as a cluster machine, a cloud, or in any other manner. Specifically, as shown in FIG. 2, the cracked light oil yield calculation device 1 has an acquisition unit 11 and a computer main body 12 that processes information from the acquisition unit. The cracked light oil yield calculation device 1 may also have an output unit 14 that outputs information processed in the computer main body 12 to the outside. These components are realized, for example, by a hardware processor such as a CPU (Central Processing Unit) executing a program (software). 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 having a non-transitory storage medium) such as an HDD (Hard Disk Drive) 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 an HDD, flash memory, EEPROM (Electrically Erasable Programmable Read Only Memory), ROM (Read Only Memory), or RAM (Random Access Memory).

[0172] The acquisition unit 11 receives predetermined information input by a reaction operator and transmits the information acquired by this input to the computer main body 12. The information acquired by the acquisition unit 11 in this embodiment is, with respect to the hydrotreating reaction of feedstock oil containing vacuum distillation gas oil, information on the feedstock oil at a predetermined time after the start of the reaction, information on the product oil, and information on the operating conditions. The information on the feedstock oil at a predetermined time after the start of the reaction, information on the product oil, and information on the operating conditions are as described above. For example, the acquisition unit 11 executes the information acquisition step described above. The acquisition unit 11 only needs to acquire information on the feedstock oil at a predetermined time after the start of the reaction, information on the product oil, and information on the operating conditions, and the acquisition method is not particularly limited.

[0173] In this embodiment, the acquisition unit 11 is configured with a single keyboard. The specific configuration of the acquisition unit 11 is not limited, and although it is a keyboard in this embodiment, it may also be a touch panel or the like. Note that acquisition units for acquiring various types of information may be configured separately and each may be independently connected to the computer main body 12. Furthermore, the acquisition unit 11 may be configured to directly acquire each piece of information via wired or wireless communication from a computer or the like used for controlling the reactor or the like.

[0174] The computer main body 12 is, for example, a so-called computer capable of processing various types of information. The computer main body 12 includes a calculation unit 13. For example, a predetermined program is installed in the computer main body 12, and the calculation unit 13 is functionally configured by executing this program. Specifically, the calculation unit 13 calculates the deterioration degree of the catalyst desulfurization reaction and the deterioration degree of the cracking reaction using a deterioration function based on the information on the feed oil, the information on the product oil, and the information on the operating conditions acquired by the acquisition unit 11 at a predetermined time after the start of the reaction. Based on the calculated deterioration degree of the catalyst desulfurization reaction, the calculation unit 13 calculates the reaction temperature required to satisfy the information on the feed oil, the information on the product oil, and the operating conditions. Based on the calculated reaction temperature and the calculated deterioration degree of the catalyst cracking reaction, the calculation unit 13 calculates the yield of cracked light oil. The deterioration function is as described above. As described above, the reaction temperature can be determined, for example, from a deterioration rate equation. Furthermore, the yield of cracked light oil can be determined, for example, from a cracked light oil yield function. For example, the calculation unit 13 executes the deterioration degree calculation step, reaction temperature calculation step, and cracked light oil yield calculation step described above. The calculation unit 13 may include, for example, a processor such as a CPU (Central Processing Unit) or an MPU (Micro Processing Unit) and non-volatile or volatile semiconductor memory (for example, RAM (Random Access Memory), ROM (Read Only Memory), flash memory, EPROM (Erasable Programmable Read Only Memory), or EEPROM (Electrically Erasable Programmable Read Only Memory)). For example, the calculation unit 13 may be a microcontroller such as an MCU.

[0175] The calculation unit 13 may output to the output unit 14 information regarding the feedstock oil obtained as described above, information regarding the product oil, and information indicating the amount of cracked light oil obtained at the reaction temperature required to satisfy the operating conditions.

[0176] 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.

[0177] This embodiment also provides a cracked light oil yield calculation program for causing a computer to function as a cracked light oil yield calculation device, and a non-transitory computer-readable recording medium storing the program. Examples of non-transitory computer-readable recording media include magnetic tape (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).

[0178] <Method of using information processing method and device for calculating light cracked oil yield> The information processing method and cracked light oil yield calculation device of this embodiment make it possible to estimate the yield of cracked light oil at 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 cracked light oil yield calculation device of this embodiment make it possible to obtain a plot of estimated values ​​of the yield of cracked light oil over time.The following applications are possible based on the relationship between the plot and the supply-demand balance between cracked light oil and residual heavy oil in the hydrotreating treatment unit of vacuum distillation gas oil.

[0179] It can be used to estimate the reaction conditions (reaction temperature, throughput (LHSV)) required to obtain a specified yield of light cracked oil, to estimate the yield of light cracked oil under specified reaction conditions (reaction temperature, throughput (LHSV)), and to plan the production of light cracked oil and heavy oil by estimating and knowing the future yield of light cracked oil in advance. In other words, when a specified yield of light cracked oil is set for a specified operating time, the above equation 23 can be expressed as k C0(Tt) , Φ C , LHSV. k C0(Tt) , Φ C The reaction conditions for this combination make it possible to obtain the optimum yield of cracked light oil and heavy oil corresponding to the supply and demand balance. C0(Tt) , Φ C In determining the combination of P, LHSV, S, etc., the reaction conditions that can be changed are as follows: F , S P In such a utilization method, the acquisition unit 11 of the cracked light oil yield calculation device 1 acquires a predetermined cracked light oil yield, and the calculation unit 13 in the computer main body 12 calculates P, LHSV, S for achieving the predetermined cracked light oil yield based on the cracked light oil yield calculation function, the degradation rate formula of the desulfurization reaction, the degradation function, etc. F , S P Calculate the combination of [Example]

[0180] 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.

[0181] [Example] A bench-scale hydrotreating reaction was carried out by contacting a feedstock containing 100% by volume of vacuum distillation gas oil with a hydrotreating catalyst. Based on the obtained results, the deterioration function of the desulfurization reaction was calculated. In this example, the deterioration function 2 of the desulfurization reaction represented by the above-mentioned formula 12 was used. The parameters in the formulas 12 to 14 were calculated by the above-mentioned method, and the results were k1 = 0.5, k2 = 0.5, α1 = 0.04, α2 = 0.005, PB = 4.9 (MPa), a = 2.3, E C = 150 (kJ / mol), T B =673(K), T SOR =629(K), n=1.5. The reaction was carried out in an actual reactor using the same feedstock and catalyst as in the bench-scale hydrotreating reaction. F =2.03(mass%), P=5.2(MPa), LHSV=1(h -1 ), S P = 0.05 (mass%). In addition, the activation energy of desulfurization and decomposition was calculated in advance using the method described above, and Ea = 125 (kJ / mol), E D =150 (kJ / mol).

[0182] From the measured value of the amount of cracked light oil obtained after one day of reaction, k C0(T0) The result was 0.285[h -1 The actual measured value of the reaction temperature, T0, at this time was 629 (K). In the initial stage of the reaction, Φ1(k1 × exp(-D1t)) and Φ2(k2 × exp(-D2t)) calculated by the above formula 12, the actual measured value of the amount of cracked light oil obtained, C0(T0) , and Φ calculated from Equation 23 by LHSV C From this, β1 and β2 were calculated using the above formula 33, and were found to be β1=0.6 and β2=1.05. Using the above parameters, the required temperature T t From the above formula 23, (3) the amount of cracked light oil obtained C t The results are shown in Table 1.

[0183] The measured values ​​of the yield of cracked light oil in Table 1 were analyzed as follows. The product oil was distilled and separated into a fraction with a boiling point of 343°C or less and a fraction with a boiling point of more than 343°C. The fraction with a boiling point of 343°C or less was then divided by the amount (mass) of the product oil before distillation and multiplied by 100 to calculate the yield.

[0184] [Table 1]

[0185] As shown in Table 1, the yield of light cracked oil C obtained by the present invention t It was found that the yield of light cracked oil was almost the same as the measured value. [Explanation of symbols]

[0186] 1...Cracked light oil yield calculation device 11...Acquisition part 12...Calculator body 13... Arithmetic section 14. Output section

Claims

1. With respect to the hydrotreating reaction of feedstock oil including vacuum distillation gas oil obtained by vacuum distillation of atmospheric distillation residue oil, an information acquisition step of acquiring information on the feedstock oil, information on the product oil, and information on operating conditions at a predetermined time after the start of the reaction; a deterioration degree calculation step of calculating a deterioration degree of a desulfurization reaction and a deterioration degree of a cracking reaction of the catalyst using 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 information about the feed oil, information about the product oil, and a reaction temperature necessary to satisfy the operating conditions based on the degree of deterioration of the desulfurization reaction of the catalyst; and a cracked light oil yield calculation step of calculating the cracked light oil yield based on the reaction temperature and the degree of deterioration of the cracking reaction of the catalyst, the information about the feedstock oil includes information about the sulfur concentration in the feedstock oil, the information about the product oil includes information about the sulfur concentration in the product oil, and the information about the operating conditions includes information about the hydrogen partial pressure, information about the catalyst loading amount, and information about the feedstock oil supply amount; The degradation function is a function expressed by the following equation 2: The degree of deterioration of the catalytic decomposition reaction is calculated by the following formula 32: The amount of cracked light oil obtained is calculated by the following formula 23. Φ=exp(-Dt) Formula 2 In the above formula 2, Φ is the degree of deterioration of the desulfurization reaction of the catalyst, D is the deterioration coefficient of the active species of the desulfurization reaction of the catalyst and is calculated using the following formula 3, and t is the number of days elapsed since the reaction began. [Equation 1] In the above formula 3, α is the catalyst constant of the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction of the catalyst), S F is the sulfur concentration (mass%) in the feedstock oil after t days of reaction, S P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing vacuum distillation gas oil, LHSV is the liquid hourly space velocity (h −1 ) after t days of reaction, P B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, Ec is the activation energy of coke deterioration (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol·K)), T B is the reference reaction temperature (K), and T SOR is the required temperature on day 0 (K). α, P B , a, Ec, T B , and T SOR are constants determined depending on the catalyst used. These constants are determined while carrying out the reaction in an actual reactor, or are determined in advance on a bench scale based on the operating conditions of the actual reactor. Φ C = βΦ Equation 32 In the above formula 32, Φ C is the degree of deterioration of the catalytic cracking reaction, Φ is the degree of deterioration of the catalytic desulfurization reaction, and β is the cracking deterioration coefficient (constant). β is determined while performing the reaction in an actual plant, or is determined in advance on a bench scale based on the operating conditions of the actual plant. [Equation 2] In the above equation 23, C t is the yield (mass%) of cracked light oil after t days of reaction, k C0(Tt) is the reaction rate constant (h −1 ) of the cracking reaction at the reaction temperature T t calculated in the reaction temperature calculation step for the catalyst (fresh catalyst) after 0 days of reaction (at the start of the reaction), Φ C is the degree of deterioration of the catalyst cracking reaction, and LHSV is the liquid hourly space velocity (h −1 ) after t days of reaction.

2. With regard to a hydrotreating reaction of a feedstock oil including a vacuum distillation gas oil obtained by vacuum distillation of atmospheric distillation residual oil, an information acquisition step of acquiring information on the feedstock oil, information on the product oil, and information on operating conditions at a predetermined time after the start of the reaction; a deterioration degree calculation step of calculating a deterioration degree of a desulfurization reaction and a deterioration degree of a cracking reaction of the catalyst using 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 information about the feed oil, information about the product oil, and a reaction temperature necessary to satisfy the operating conditions based on the degree of deterioration of the desulfurization reaction of the catalyst; and a cracked light oil yield calculation step of calculating the cracked light oil yield based on the reaction temperature and the degree of deterioration of the cracking reaction of the catalyst, the information on the feed oil includes information on the sulfur concentration in the feed oil, the information on the product oil includes information on the sulfur concentration in the product oil, and the information on the operating conditions includes information on the hydrogen partial pressure, information on the hydrogen supply amount, information on the catalyst loading amount, and information on the feed oil supply amount; The degradation function is a function expressed by the following equation 9: The degree of deterioration of the catalytic decomposition reaction is calculated by the following formula 32: The amount of cracked light oil obtained is calculated by the following formula 23. Φ=exp(-D't) Equation 9 In the above formula 9, Φ is the degree of deterioration of the desulfurization reaction of the catalyst, D′ is the deterioration coefficient of the active species of the desulfurization reaction of the catalyst and is calculated using the following formula 10, and t is the number of days elapsed since the reaction began. [Equation 3] In the above formula 10, α' is the catalyst constant of the desulfurization reaction (a constant representing the degradation rate of the desulfurization reaction of the catalyst), S F is the sulfur concentration (mass%) in the feed oil after t days of reaction, S P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feed oil containing vacuum distillation gas oil, LHSV is the liquid hourly space velocity (h -1 ) after t days of reaction, P B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, G B is the reference hydrogen / feed oil ratio (Nm 3 / kL), and 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 deterioration (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol·K)), T B is the reference reaction temperature (K), and T SOR is the required temperature on day 0 (K). α', P B , a, G B , b, Ec, T B , and T SOR are constants determined depending on the catalyst used. The constants are determined while performing the reaction in an actual plant, or are determined in advance on a bench scale based on the operating conditions of the actual plant. Φ C = βΦ Equation 32 In the above formula 32, Φ C is the degree of deterioration of the catalytic cracking reaction, Φ is the degree of deterioration of the catalytic desulfurization reaction, and β is the cracking deterioration coefficient (constant). β is determined while performing the reaction in an actual plant, or is determined in advance on a bench scale based on the operating conditions of the actual plant. [Equation 4] In the above equation 23, C t is the yield (mass%) of cracked light oil after t days of reaction, k C0(Tt) is the reaction rate constant (h −1 ) of the cracking reaction at the reaction temperature T t calculated in the reaction temperature calculation step for the catalyst (fresh catalyst) after 0 days of reaction (at the start of the reaction), Φ C is the degree of deterioration of the catalyst cracking reaction, and LHSV is the liquid hourly space velocity (h −1 ) after t days of reaction.

3. With regard to the hydrotreating reaction of feedstock oil including vacuum distillation light oil obtained by vacuum distillation of atmospheric distillation residual oil, an information acquisition step of acquiring information on the feedstock oil, information on the product oil, and information on operating conditions at a predetermined time after the start of the reaction; a deterioration degree calculation step of calculating a deterioration degree of a desulfurization reaction and a deterioration degree of a cracking reaction of the catalyst using 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 information about the feed oil, information about the product oil, and a reaction temperature necessary to satisfy the operating conditions based on the degree of deterioration of the desulfurization reaction of the catalyst; and a cracked light oil yield calculation step of calculating the cracked light oil yield based on the reaction temperature and the degree of deterioration of the cracking reaction of the catalyst, the information about the feedstock oil includes information about the sulfur concentration in the feedstock oil, the information about the product oil includes information about the sulfur concentration in the product oil, and the information about the operating conditions includes information about the hydrogen partial pressure, information about the catalyst loading amount, and information about the feedstock oil supply amount; The degradation function is a function expressed by the following equation 12: The degree of deterioration of the catalytic decomposition reaction is calculated by the following formula 33: The amount of cracked light oil obtained is calculated by the following formula 23. Φ=k 1 ×exp(-D 1 t)+k 2 ×exp(-D 2 t) Equation 12 In the above formula (12), k1 is the active site coefficient of the easily deactivated active species in the desulfurization reaction of the catalyst, k2 is the active site coefficient of the resistant to deactivation active species in the desulfurization reaction of the catalyst, and the active site coefficients represent the relative reaction rate constants of the desulfurization reaction of both active species. D1 is the deterioration coefficient of the easily deactivated active species in the desulfurization reaction of the catalyst and is calculated from the following formula (13), D2 is the deterioration coefficient of the resistant to deactivation active species in the desulfurization reaction of the catalyst and is calculated from the following formula (14), t is the number of days elapsed since the reaction began (days), k1 + k2 = 1, and k1 and k2 are determined during the reaction in an actual system or are determined in advance on a bench scale based on the operating conditions of the actual system. [Equation 5] [Equation 6] In the above formulas 13 and 14, S F is the sulfur concentration (mass%) in the feedstock oil after t days of reaction, S P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing vacuum distillation gas oil, LHSV is the liquid hourly space velocity (h −1 ) after t days of reaction, P B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, Ec is the activation energy of coke deterioration (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol·K)), T B is the reference reaction temperature (K), and T SOR is the required temperature on day 0 (K). In the above formula 13, α 1 is the catalytic constant of the easily deactivated active site for the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction of the catalyst), and in the above formula 14, α 2 is the catalytic constant of the hardly deactivated active site for the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction of the catalyst). α 1 , α 2 , P B , a, Ec, T B , and T SOR are constants determined depending on the catalyst used. The above constants are determined while performing the reaction in an actual plant, or are determined in advance on a bench scale based on the operating conditions of the actual plant. Φ C = β 1 Φ 1 + β 2 Φ 2 Equation 33 In the above formula 33, Φ C is the degree of deterioration of the catalyst decomposition reaction, Φ 1 is k 1 ×exp(-D 1 t) in the above formula 12, Φ 2 is k 2 ×exp(-D 2 t) in the above formula 12, β 1 is the decomposition deterioration coefficient (constant) of the easily deactivated active species of the catalyst, and β 2 is the decomposition deterioration coefficient (constant) of the hardly deactivated active species of the catalyst. β 1 and β 2 are determined while performing the reaction in an actual plant, or are determined in advance on a bench scale based on the operating conditions of the actual plant. [Equation 7] In the above equation 23, C t is the yield (mass%) of cracked light oil after t days of reaction, k C0(Tt) is the reaction rate constant (h −1 ) of the cracking reaction at the reaction temperature T t calculated in the reaction temperature calculation step for the catalyst (fresh catalyst) after 0 days of reaction (at the start of the reaction), Φ C is the degree of deterioration of the catalyst cracking reaction, and LHSV is the liquid hourly space velocity (h −1 ) after t days of reaction.

4. With regard to a hydrotreating reaction of a feedstock oil containing vacuum distillation light oil obtained by vacuum distillation of atmospheric distillation residual oil, an information acquisition step of acquiring information on the feedstock oil, information on the product oil, and information on operating conditions at a predetermined time after the start of the reaction; a deterioration degree calculation step of calculating a deterioration degree of a desulfurization reaction and a deterioration degree of a cracking reaction of the catalyst using 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 information about the feed oil, information about the product oil, and a reaction temperature necessary to satisfy the operating conditions based on the degree of deterioration of the desulfurization reaction of the catalyst; and a cracked light oil yield calculation step of calculating the cracked light oil yield based on the reaction temperature and the degree of deterioration of the cracking reaction of the catalyst, the information on the feed oil includes information on the sulfur concentration in the feed oil, the information on the product oil includes information on the sulfur concentration in the product oil, and the information on the operating conditions includes information on the hydrogen partial pressure, information on the hydrogen supply amount, information on the catalyst loading amount, and information on the feed oil supply amount; The degradation function is a function expressed by the following equation 16: The degree of deterioration of the catalytic decomposition reaction is calculated by the following formula 33: The amount of cracked light oil obtained is calculated by the following formula 23. Φ=k 1 × exp (-D 1 't) + k 2 × exp (-D 2 't) Equation 16 In Equation 16, k1 is the active site coefficient of the easily deactivated active species in the desulfurization reaction of the catalyst, k2 is the active site coefficient of the resistant to deactivation active species in the desulfurization reaction of the catalyst, and the active site coefficients represent the relative reaction rate constants of the desulfurization reaction of both active species. D1' is the deterioration coefficient of the easily deactivated active species in the desulfurization reaction of the catalyst and is calculated from Equation 17 below, D2' is the deterioration coefficient of the resistant to deactivation active species in the desulfurization reaction of the catalyst and is calculated from Equation 18 below, t is the number of days elapsed since the reaction began (days), k1 + k2 = 1, and k1 and k2 are determined during the reaction in an actual system or are determined in advance on a bench scale based on the operating conditions of the actual system. [Equation 8] [Equation 9] In the above formulas 17 and 18, S F is the sulfur concentration (mass%) in the feed oil after t days of reaction, S P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feed oil containing vacuum distillation gas oil, LHSV is the liquid hourly space velocity (h -1 ) after t days of reaction, P B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, G B is the reference hydrogen / feed oil ratio (Nm 3 / kL), G is the hydrogen / feed oil ratio (Nm 3 / kL) after t days of reaction, b is the hydrogen / feed oil ratio coefficient, Ec is the activation energy of coke deterioration (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 on day 0 (K). In Equation 17, α 1 ' is the catalytic constant of the easily deactivated active site for the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction of the catalyst), and in Equation 18, α 2 ' is the catalytic constant of the hardly deactivated active site for the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction of the catalyst). α 1 ', α 2 ', P B , a, G B , b, Ec, T B , and T SOR are constants determined depending on the catalyst used. The above constants are determined while performing the reaction in an actual plant, or are determined in advance on a bench scale based on the operating conditions of the actual plant. Φ C = β 1 Φ 1 + β 2 Φ 2 Equation 33 In the above formula 33, Φ C is the degree of deterioration of the catalyst decomposition reaction, Φ 1 is k 1 ×exp(-D 1 't) in the above formula 16, Φ 2 is k 2 ×exp(-D 2 't) in the above formula 16, β 1 is the decomposition deterioration coefficient (constant) of the catalyst's easily deactivated active species, and β 2 is the decomposition deterioration coefficient (constant) of the catalyst's less easily deactivated active species. β 1 and β 2 are determined while carrying out the reaction in an actual plant, or are determined in advance on a bench scale based on the actual plant operating conditions. [Equation 10] In the above equation 23, C t is the yield (mass%) of cracked light oil after t days of reaction, k C0(Tt) is the reaction rate constant (h −1 ) of the cracking reaction at the reaction temperature T t calculated in the reaction temperature calculation step for the catalyst (fresh catalyst) after 0 days of reaction (at the start of the reaction), Φ C is the degree of deterioration of the catalyst cracking reaction, and LHSV is the liquid hourly space velocity (h −1 ) after t days of reaction.

5. 1. A cracked light oil yield calculation device comprising: an acquisition unit that acquires information about the feedstock, information about the product oil, and information about operating conditions at a predetermined time after the start of a hydrotreating reaction of a feedstock including vacuum distillation light oil obtained by vacuum distillation of atmospheric distillation residual oil; and a calculation unit that calculates a deterioration level of a desulfurization reaction and a deterioration level of a cracking reaction of a catalyst using a deterioration function based on the information about the feedstock, information about the product oil, and information about the operating conditions acquired by the acquisition unit, calculates a reaction temperature required to satisfy the information about the feedstock, information about the product oil, and the operating conditions based on the calculated deterioration level of the desulfurization reaction of the catalyst, and calculates a cracked light oil yield based on the calculated reaction temperature and the deterioration level of the cracking reaction of the catalyst. the information about the feedstock oil includes information about the sulfur concentration in the feedstock oil, the information about the product oil includes information about the sulfur concentration in the product oil, and the information about the operating conditions includes information about the hydrogen partial pressure, information about the catalyst loading amount, and information about the feedstock oil supply amount; The degradation function is a function expressed by the following equation 2: The degree of deterioration of the catalytic decomposition reaction is calculated by the following formula 32: The yield of cracked light oil is calculated by the following formula 23: Φ=exp(-Dt) Formula 2 In the above formula 2, Φ is the degree of deterioration of the desulfurization reaction of the catalyst, D is the deterioration coefficient of the active species of the desulfurization reaction of the catalyst and is calculated using the following formula 3, and t is the number of days elapsed since the reaction began. [0011] In the above formula 3, α is the catalyst constant of the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction of the catalyst), S F is the sulfur concentration (mass%) in the feedstock oil after t days of reaction, S P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing vacuum distillation gas oil, LHSV is the liquid hourly space velocity (h −1 ) after t days of reaction, P B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, Ec is the activation energy of coke deterioration (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol·K)), T B is the reference reaction temperature (K), and T SOR is the required temperature on day 0 (K). α, P B , a, Ec, T B , and T SOR are constants determined depending on the catalyst used. These constants are determined while carrying out the reaction in an actual reactor, or are determined in advance on a bench scale based on the operating conditions of the actual reactor. Φ C = βΦ Equation 32 In the above formula 32, Φ C is the degree of deterioration of the catalytic cracking reaction, Φ is the degree of deterioration of the catalytic desulfurization reaction, and β is the cracking deterioration coefficient (constant). β is determined while performing the reaction in an actual plant, or is determined in advance on a bench scale based on the operating conditions of the actual plant. [0012] In the above equation 23, C t is the yield (mass%) of cracked light oil after t days of reaction, k C0(Tt) is the reaction rate constant (h −1 ) of the cracking reaction at the calculated reaction temperature T t of the catalyst (fresh catalyst) after 0 days of reaction (at the start of the reaction), Φ C is the degree of deterioration of the catalyst cracking reaction, and LHSV is the liquid hourly space velocity (h −1 ) after t days of reaction.

6. A cracked light oil yield calculation device comprising: an acquisition unit that acquires information about the feedstock oil, information about the product oil, and information about operating conditions at a predetermined time after the start of the reaction, regarding a hydrotreating reaction of feedstock oil including vacuum distillation light oil obtained by vacuum distillation of atmospheric distillation residual oil; and a calculation unit that calculates the degree of degradation of the desulfurization reaction and the degree of degradation of the cracking reaction of the catalyst using a degradation function based on the information about the feedstock oil, information about the product oil, and information about the operating conditions acquired by the acquisition unit, calculates the information about the feedstock oil, information about the product oil, and the reaction temperature required to satisfy the operating conditions based on the calculated degree of degradation of the desulfurization reaction of the catalyst, and calculates the amount of cracked light oil yield based on the calculated reaction temperature and the degree of degradation of the cracking reaction of the catalyst, the information on the feed oil includes information on the sulfur concentration in the feed oil, the information on the product oil includes information on the sulfur concentration in the product oil, and the information on the operating conditions includes information on the hydrogen partial pressure, information on the hydrogen supply amount, information on the catalyst loading amount, and information on the feed oil supply amount; The degradation function is a function expressed by the following equation 9: The degree of deterioration of the catalytic decomposition reaction is calculated by the following formula 32: The yield of cracked light oil is calculated by the following formula 23: Φ=exp(-D't) Equation 9 In the above formula 9, Φ is the degree of deterioration of the desulfurization reaction of the catalyst, D′ is the deterioration coefficient of the active species of the desulfurization reaction of the catalyst and is calculated using the following formula 10, and t is the number of days elapsed since the reaction began. [0013] In the above formula 10, α' is the catalyst constant of the desulfurization reaction (a constant representing the degradation rate of the desulfurization reaction of the catalyst), S F is the sulfur concentration (mass%) in the feed oil after t days of reaction, S P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feed oil containing vacuum distillation gas oil, LHSV is the liquid hourly space velocity (h -1 ) after t days of reaction, P B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, G B is the reference hydrogen / feed oil ratio (Nm 3 / kL), and 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 deterioration (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol·K)), T B is the reference reaction temperature (K), and T SOR is the required temperature on day 0 (K). α', P B , a, G B , b, Ec, T B , and T SOR are constants determined depending on the catalyst used. The constants are determined while performing the reaction in an actual plant, or are determined in advance on a bench scale based on the operating conditions of the actual plant. Φ C = βΦ Equation 32 In the above formula 32, Φ C is the degree of deterioration of the catalytic cracking reaction, Φ is the degree of deterioration of the catalytic desulfurization reaction, and β is the cracking deterioration coefficient (constant). β is determined while performing the reaction in an actual plant, or is determined in advance on a bench scale based on the operating conditions of the actual plant. [0014] In the above equation 23, C t is the yield (mass%) of cracked light oil after t days of reaction, k C0(Tt) is the reaction rate constant (h −1 ) of the cracking reaction at the calculated reaction temperature T t of the catalyst (fresh catalyst) after 0 days of reaction (at the start of the reaction), Φ C is the degree of deterioration of the catalyst cracking reaction, and LHSV is the liquid hourly space velocity (h −1 ) after t days of reaction.

7. A cracked light oil yield calculation device comprising: an acquisition unit that acquires information about the feedstock oil, information about the product oil, and information about operating conditions at a predetermined time after the start of the reaction, regarding a hydrotreating reaction of feedstock oil including vacuum distillation light oil obtained by vacuum distillation of atmospheric distillation residual oil; and a calculation unit that calculates the degree of degradation of the desulfurization reaction and the degree of degradation of the cracking reaction of the catalyst using a degradation function based on the information about the feedstock oil, information about the product oil, and information about the operating conditions acquired by the acquisition unit, calculates the information about the feedstock oil, information about the product oil, and the reaction temperature required to satisfy the operating conditions based on the calculated degree of degradation of the desulfurization reaction of the catalyst, and calculates the amount of cracked light oil yield based on the calculated reaction temperature and the degree of degradation of the cracking reaction of the catalyst, the information about the feedstock oil includes information about the sulfur concentration in the feedstock oil, the information about the product oil includes information about the sulfur concentration in the product oil, and the information about the operating conditions includes information about the hydrogen partial pressure, information about the catalyst loading amount, and information about the feedstock oil supply amount; The degradation function is a function expressed by the following equation 12: The degree of deterioration of the catalytic decomposition reaction is calculated by the following formula 33: The yield of cracked light oil is calculated by the following formula 23: Φ=k 1 ×exp(-D 1 t)+k 2 ×exp(-D 2 t) Equation 12 In the above formula (12), k1 is the active site coefficient of the easily deactivated active species in the desulfurization reaction of the catalyst, k2 is the active site coefficient of the resistant to deactivation active species in the desulfurization reaction of the catalyst, and the active site coefficients represent the relative reaction rate constants of the desulfurization reaction of both active species. D1 is the deterioration coefficient of the easily deactivated active species in the desulfurization reaction of the catalyst and is calculated from the following formula (13), D2 is the deterioration coefficient of the resistant to deactivation active species in the desulfurization reaction of the catalyst and is calculated from the following formula (14), t is the number of days elapsed since the reaction began (days), k1 + k2 = 1, and k1 and k2 are determined during the reaction in an actual system or are determined in advance on a bench scale based on the operating conditions of the actual system. [Equation 15] [0016] In the above formulas 13 and 14, S F is the sulfur concentration (mass%) in the feedstock oil after t days of reaction, S P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feedstock oil containing vacuum distillation gas oil, LHSV is the liquid hourly space velocity (h −1 ) after t days of reaction, P B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, Ec is the activation energy of coke deterioration (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol·K)), T B is the reference reaction temperature (K), and T SOR is the required temperature on day 0 (K). In the above formula 13, α 1 is the catalytic constant of the easily deactivated active site for the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction of the catalyst), and in the above formula 14, α 2 is the catalytic constant of the hardly deactivated active site for the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction of the catalyst). α 1 , α 2 , P B , a, Ec, T B , and T SOR are constants determined depending on the catalyst used. The above constants are determined while performing the reaction in an actual plant, or are determined in advance on a bench scale based on the operating conditions of the actual plant. Φ C = β 1 Φ 1 + β 2 Φ 2 Equation 33 In the above formula 33, Φ C is the degree of deterioration of the catalyst decomposition reaction, Φ 1 is k 1 ×exp(-D 1 t) in the above formula 12, Φ 2 is k 2 ×exp(-D 2 t) in the above formula 12, β 1 is the decomposition deterioration coefficient (constant) of the easily deactivated active species of the catalyst, and β 2 is the decomposition deterioration coefficient (constant) of the hardly deactivated active species of the catalyst. β 1 and β 2 are determined while performing the reaction in an actual plant, or are determined in advance on a bench scale based on the operating conditions of the actual plant. [Equation 17] In the above equation 23, C t is the yield (mass%) of cracked light oil after t days of reaction, k C0(Tt) is the reaction rate constant (h −1 ) of the cracking reaction at the calculated reaction temperature T t of the catalyst (fresh catalyst) after 0 days of reaction (at the start of the reaction), Φ C is the degree of deterioration of the catalyst cracking reaction, and LHSV is the liquid hourly space velocity (h −1 ) after t days of reaction.

8. A cracked light oil yield calculation device comprising: an acquisition unit that acquires information about the feedstock oil, information about the product oil, and information about operating conditions at a predetermined time after the start of the reaction, regarding a hydrotreating reaction of feedstock oil including vacuum distillation light oil obtained by vacuum distillation of atmospheric distillation residual oil; and a calculation unit that calculates the degree of degradation of the desulfurization reaction and the degree of degradation of the cracking reaction of the catalyst using a degradation function based on the information about the feedstock oil, information about the product oil, and information about the operating conditions acquired by the acquisition unit, calculates the information about the feedstock oil, information about the product oil, and the reaction temperature required to satisfy the operating conditions based on the calculated degree of degradation of the desulfurization reaction of the catalyst, and calculates the amount of cracked light oil yield based on the calculated reaction temperature and the degree of degradation of the cracking reaction of the catalyst, the information on the feed oil includes information on the sulfur concentration in the feed oil, the information on the product oil includes information on the sulfur concentration in the product oil, and the information on the operating conditions includes information on the hydrogen partial pressure, information on the hydrogen supply amount, information on the catalyst loading amount, and information on the feed oil supply amount; The degradation function is a function expressed by the following equation 16: The degree of deterioration of the catalytic decomposition reaction is calculated by the following formula 33: The yield of cracked light oil is calculated by the following formula 23: Φ=k 1 × exp (-D 1 't) + k 2 × exp (-D 2 't) Equation 16 In Equation 16, k1 is the active site coefficient of the easily deactivated active species in the desulfurization reaction of the catalyst, k2 is the active site coefficient of the resistant to deactivation active species in the desulfurization reaction of the catalyst, and the active site coefficients represent the relative reaction rate constants of the desulfurization reaction of both active species. D1' is the deterioration coefficient of the easily deactivated active species in the desulfurization reaction of the catalyst and is calculated from Equation 17 below, D2' is the deterioration coefficient of the resistant to deactivation active species in the desulfurization reaction of the catalyst and is calculated from Equation 18 below, t is the number of days elapsed since the reaction began (days), k1 + k2 = 1, and k1 and k2 are determined during the reaction in an actual system or are determined in advance on a bench scale based on the operating conditions of the actual system. [Equation 18] [Equation 19] In the above formulas 17 and 18, S F is the sulfur concentration (mass%) in the feed oil after t days of reaction, S P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feed oil containing vacuum distillation gas oil, LHSV is the liquid hourly space velocity (h -1 ) after t days of reaction, P B is the reference hydrogen partial pressure (MPa), P is the hydrogen partial pressure (MPa) after t days of reaction, a is the hydrogen partial pressure coefficient, G B is the reference hydrogen / feed oil ratio (Nm 3 / kL), G is the hydrogen / feed oil ratio (Nm 3 / kL) after t days of reaction, b is the hydrogen / feed oil ratio coefficient, Ec is the activation energy of coke deterioration (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 on day 0 (K). In Equation 17, α 1 ' is the catalytic constant of the easily deactivated active site for the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction of the catalyst), and in Equation 18, α 2 ' is the catalytic constant of the hardly deactivated active site for the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction of the catalyst). α 1 ', α 2 ', P B , a, G B , b, Ec, T B , and T SOR are constants determined depending on the catalyst used. The above constants are determined while performing the reaction in an actual plant, or are determined in advance on a bench scale based on the operating conditions of the actual plant. Φ C = β 1 Φ 1 + β 2 Φ 2 Equation 33 In the above formula 33, Φ C is the degree of deterioration of the catalyst decomposition reaction, Φ 1 is k 1 ×exp(-D 1 't) in the above formula 16, Φ 2 is k 2 ×exp(-D 2 't) in the above formula 16, β 1 is the decomposition deterioration coefficient (constant) of the catalyst's easily deactivated active species, and β 2 is the decomposition deterioration coefficient (constant) of the catalyst's less easily deactivated active species. β 1 and β 2 are determined while carrying out the reaction in an actual plant, or are determined in advance on a bench scale based on the actual plant operating conditions. [Equation 20] In the above equation 23, C t is the yield (mass%) of cracked light oil after t days of reaction, k C0(Tt) is the reaction rate constant (h −1 ) of the cracking reaction at the calculated reaction temperature T t of the catalyst (fresh catalyst) after 0 days of reaction (at the start of the reaction), Φ C is the degree of deterioration of the catalyst cracking reaction, and LHSV is the liquid hourly space velocity (h −1 ) after t days of reaction.

9. A cracked light oil yield calculation program for causing a computer to function as the cracked light oil yield calculation device according to any one of claims 5 to 8.

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

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