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

Abstract

To provide an information processing method configured to estimate naphtha gain in a predetermined reaction condition regarding hydrogenation treatment reaction of raw oil containing atmospheric distillation gas oil, a naphtha gain calculation apparatus for estimating naphtha gain, a naphtha gain calculation program, and a computer non-transitory readable recording medium.SOLUTION: An information processing method includes: an information acquisition step of acquiring information on raw oil containing atmospheric distillation gas oil to be obtained a predetermined time after the start of reaction, information on generated oil, and information on an operation condition; a deterioration calculation step of calculating a degree of deterioration of a catalyst with a deterioration function based on the acquired information; a reaction temperature calculation step of calculating information on the raw oil, information on the generated oil, and a reaction temperature required for satisfying the operation condition, based on the degree of deterioration of the catalyst; and a naphtha gain calculation step of calculating naphtha gain based on the reaction temperature and the degree of deterioration of the catalyst.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] Diesel base stocks are produced by hydrotreating atmospheric distillation gas oil obtained by atmospheric distillation of crude oil, which is then contacted with a hydrotreating catalyst in the presence of hydrogen.

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

[0004] Furthermore, in the hydrotreating of atmospheric distillation gas oil, light fractions such as naphtha are produced as by-products, and it is necessary to control these light fractions. The yield of light fractions such as naphtha varies over time depending on the cracking activity of the hydrotreating catalyst and the reaction temperature.

[0005] In a hydrotreating unit for atmospheric distillation gas oil, there is an upper limit to the extraction capacity of the light fractions such as naphtha, and if the extraction of the light fractions such as naphtha becomes a bottleneck, the throughput of the gas oil fraction will be restricted. Therefore, a method for accurately estimating the yield of light fractions such as naphtha 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 fractions such as naphtha, and actual data from past operations is used.

[0009] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide an information processing method capable of estimating a naphtha yield under predetermined reaction conditions for a hydrotreating reaction of feedstock oil including atmospheric distillation gas oil, a naphtha yield calculation device capable of estimating the naphtha yield, a naphtha yield calculation program for causing a computer to function as the naphtha 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] With regard to the hydrotreating reaction of a feedstock oil containing atmospheric distillation gas 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 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 necessary 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 naphtha yield calculation step of calculating the naphtha yield 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, information relating to the feedstock oil supply amount, and information relating to the hydrogen supply amount. [5] A naphtha 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 when a predetermined time has elapsed since the start of the hydrotreating reaction of the feedstock oil containing atmospheric distillation gas oil; and an acquisition unit that calculates the degree of deterioration of the desulfurization reaction and the degree of deterioration of the cracking reaction of the catalyst using a deterioration function based on the information about the feedstock oil, the information about the product oil, and the information about the operating conditions acquired by the acquisition unit; and a calculation unit that calculates the reaction temperature required to satisfy the information about the feedstock oil, the information about the product oil, and the operating conditions based on the calculated degree of deterioration of the desulfurization reaction of the catalyst; and calculates the naphtha yield based on the calculated reaction temperature and the degree of deterioration of the cracking reaction of the catalyst. [6] The naphtha yield calculation device according to [5], wherein 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 deactivation of easily deactivated active species of the catalyst and a hardly deactivated active species deactivation function relating to deactivation of hardly deactivated active species of the catalyst. [7] The naphtha yield calculation device according to [5] or [6], wherein the information about the feed oil includes information about the sulfur concentration in the feed oil, and the information about the product oil includes information about the sulfur concentration in the product oil. [8] The naphtha yield calculation device 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, information on the feedstock supply amount, and information on the hydrogen supply amount. [9] A naphtha yield calculation program for causing a computer to function as the naphtha yield calculation device according to any one of [5] to [8].

[10] A non-transitory computer-readable recording medium storing the program described in [9]. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide an information processing method capable of calculating a naphtha yield under predetermined reaction conditions for a hydrotreating reaction of feedstock oil containing atmospheric distillation gas oil, a naphtha yield calculation device capable of calculating the naphtha yield, a naphtha yield calculation program for causing a computer to function as the naphtha 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] FIG. 1 is a configuration block diagram of a naphtha 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 includes the following steps: 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 after a predetermined time has elapsed since the start of the hydrotreating reaction of a feedstock containing atmospheric distillation gas oil; a deterioration calculation step (S2 in FIG. 1) for calculating the deterioration level of the desulfurization reaction and the deterioration level of the cracking reaction of the catalyst using a deterioration function based on the acquired information about the feedstock, information about the product oil, and information about the operating conditions; 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 desulfurization reaction of the catalyst; and a naphtha yield calculation step (S4 in FIG. 1) for calculating the naphtha yield based on the reaction temperature and the deterioration level of the cracking reaction of the catalyst. Each step will be described below. Note that each step shown below is executed, for example, by the naphtha 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, and preferably all of these. The operating conditions also include time information, such as the time when any t days have elapsed since the start of the reaction. The operating conditions may also include information about the actually measured naphtha yield.

[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 including atmospheric 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 feedstock 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, G、 and the reaction temperature required to achieve the reaction conditions 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 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.

[0033] 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.

[0034] In the above formula 3, (1 / S P n-1 -1 / S F n-1 The term expressed as )LHSV is the desulfurization reaction rate constant, and as mentioned above, S P , S F When the LHSV is set as a set value and the operation is performed under certain conditions, it becomes a constant. B / P) aThe term expressed by (G) is a term that indicates the hydrogen partial pressure dependency, and as described above, when P is set as a set value and operation is performed under constant conditions, it becomes a constant. B / G) b The term expressed by is a term that indicates the hydrogen / feed oil ratio dependency, and as mentioned above, when G is set as 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.

[0035] In the formula 3, S F , S P , LHSV, P, and G are values substituted based on the information on the feed oil, information on the product oil, and 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 rate (volume). G is the hydrogen supply rate (Nm 3 / hour) by the feed rate of the raw oil (kL / hour).

[0036] As mentioned above, S F , LHSV, P, and G 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, P, and G. The method for determining n, which is the reaction order of the hydrotreating reaction of feedstock oil containing atmospheric distillation gas oil, will be described later.

[0037] (How to calculate basic degradation parameters) In the above formula 3, α, P B , a, G B ,b,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, G B ,b,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, G B ,b,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).

[0038] (P B , a, G B ,b,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

[0039] 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.

[0040]

number

[0041] 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 atmospheric distillation gas oil, the activation energy E is set to the desulfurization activation energy Ea (kJ / mol).

[0042]

number

[0043] (Ec and T B (How to find) The LHSV, hydrogen partial pressure, hydrogen / feed oil ratio, and sulfur concentration in the feed oil are constant, and the sulfur concentration in the produced oil is set to a constant value S Pn The reaction is carried out for a certain period of time so that the sulfur concentration in the produced oil becomes S Pn To achieve this, the reaction temperature is increased while the reaction is carried out. If the reaction time is plotted on the horizontal axis and the measured reaction temperature on the vertical axis, and a regression line is drawn, y = a n x+b n (0 n ) is obtained. a n and b n is a value that reflects the catalyst deterioration behavior. n is T in the above formula 6 SOR In the above formula 6, T SOR ' to b n Substituting, T t By substituting the measured reaction temperature into ', the 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 ’ ) is obtained. a n ’ represents the deterioration rate of the desulfurization reaction of the catalyst.

[0044] 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 ’ where 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.

[0045] 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)).

[0046] n a n ’ and b n For the combination of ln(a n ’ ) on the vertical axis, and 1 / b n On the horizontal axis, a regression line is drawn and its slope is calculated. Since this slope is Ec / R, the activation energy of coke deterioration, Ec, can be calculated by subtracting R from the slope.

[0047] Also, n b n By averaging T B can be obtained.

[0048] 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, 0.3 to 2.0 h -1 The hydrogen partial pressure is, for example, 3 to 7 MPa, and the hydrogen / feedstock ratio is, for example, 100 to 700 [Nm 3 / kL], and the sulfur concentration in the feed oil is, for example, 0.5 to 2.0 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, 0.001 mass % or less. The reaction period is, for example, 30 to 1600 days.

[0049] (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 m 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 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 ’ ) is obtained. a m ’ represents the deterioration rate of the desulfurization reaction of the catalyst.

[0050] m types of hydrogen partial pressure P m The same reaction is carried out for m a m , b m Then, using the same method as above, m a m ’ where m is an integer of 3 or more. The larger the value of m, the more accurate a can be obtained. On the other hand, if the value of m is too large, it takes a long time to obtain a, which is not efficient. In this embodiment, m is preferably 3 to 20, and more preferably 3 to 10. The m a obtained in this way m ​' and P m are substituted into the following formula 8. The following formula 8 is an equation that can calculate the hydrogen partial pressure coefficient and the reference hydrogen partial pressure, and was first discovered by the inventors of the present application based on the operating results of an actual machine, etc.

[0051] ln(a m ’ )=-aln(P m )+B1 formula 8 In the formula 8, B1 can be 0.

[0052] 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.

[0053] In addition, the partial pressure P m By averaging P B can be obtained.

[0054] 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, 0.3 to 2.0 h -1 The hydrogen / feedstock ratio is, for example, 100 to 700 [Nm 3 / kL], the sulfur concentration in the feed oil is, for example, 0.5 to 2.0 mass %, and the sulfur concentration in the product oil is, for example, 0.001 mass % or less. m hydrogen partial pressures P m Similarly, it is preferable to set the conditions for P to match the actual operating conditions. m The reaction pressure is, for example, 3 to 7 MPa. The reaction period is, for example, 30 to 1600 days.

[0055] (G B , how to find b) 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 measured 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 ’ ) is obtained. a h ’ represents the deterioration rate of the desulfurization reaction of the catalyst.

[0056] 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 equation 9. The following equation 9 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.

[0057] ln(a h ')=-bln(G h )+B2 Equation 9 In the formula 9, B2 can be 0.

[0058] 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.

[0059] In addition, the above h types of hydrogen / feed oil ratio G h By averaging, G B can be obtained.

[0060] 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, 0.3 to 2.0 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 2.0 mass %, and the sulfur concentration in the product oil is, for example, 0.001 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 700 [Nm 3 / kL]. The reaction period is, for example, 30 to 1600 days.

[0061] (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 and how to find a), (G 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 α A 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.

[0062] The operating condition is S P , S F , LHSV, P, G and P obtained by the above method B , a, G B ,b,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 ” ) are obtained for each value of α. α ” and the above-mentioned a α ’ The value of α when these values are equal can be used as α in the above formula 3.

[0063] (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, G B ,b,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 ’ Substituting into, 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.

[0064] <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 10, 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.

[0065] Φ=k1×exp(-D1t)+k2×exp(-D2t) Equation 10 In Equation 10, 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, 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.

[0066] As described above, in the hydrotreating reaction of atmospheric distillation gas oil, catalyst deterioration occurs due to coke deposition, and therefore, in order to maintain the sulfur content in 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 atmospheric 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.

[0067] In other words, the profile of reaction temperature versus reaction time suggests that in the hydrotreating reaction of atmospheric 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.

[0068] 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.

[0069] In the formula 10, 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.

[0070] D1 can be calculated using the following formula 11, and D2 can be calculated using the following formula 12.

[0071]

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[0072]

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[0073] In the formula 11 and the formula 12, 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 the feedstock oil containing atmospheric 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 any reaction t days have passed, a is the hydrogen partial pressure coefficient, and G B is the standard hydrogen / feed oil ratio (Nm 3 / kL), G is the hydrogen / feed oil ratio (Nm3 / kL), b is the hydrogen / feed oil ratio coefficient, Ec is the activation energy of coke degradation (kJ / mol), R is the gas constant: 0.00831 (kJ / (mol K)), and T B is the reference reaction temperature (K), and T SOR is the required temperature (K) on day 0. In the above formula 11, 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 the above formula 12, 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).

[0074] In the formula 11 and the formula 12, S F , S P , LHSV, P, and G 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 Equation 3 above. Note that LHSV can be calculated by dividing the feed oil supply rate (volume / h) by the catalyst loading rate (volume). G is the hydrogen supply rate (Nm 3 / hour) by the feed rate of the raw oil (kL / hour).

[0075] As mentioned above, S F , LHSV, P, and G are controllable parameters. P is the sulfur concentration of the target product oil. That is, according to the above formulas 11 and 12, the above S F , S P The 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 atmospheric distillation gas oil, will be described later.

[0076] (How to calculate basic degradation parameters) In the formula 11 and the formula 12, α1, α2, P B , a, G B ,b,Ec,T B , T SORis 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 11 and 12, P B , a, G B ,b,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 activity site coefficient k1 of the active species that is easily deactivated in the desulfurization reaction of the catalyst and the activity site coefficient k2 of the active species that is difficult to deactivate in the desulfurization reaction of the catalyst in the above formula 10 can also be calculated at the same time as follows.

[0077] (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.

[0078] 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.

[0079] 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 ’ ) is obtained. Also, x ip ~x m If we draw a regression line up to y=-a2 ’ x-b2 ’ (|-a2 ’ |=a2 ’ and |-b2 ’ |=b2 ’ ) is obtained. a1 ’ is a value correlated with α1, and a2 ’ is a value correlated with α2, and b2 ’ is a value correlated to k2.

[0080] k2 is the b2 obtained from the regression line above. ’ can be calculated by substituting into the following equation 13. Since k1 is k1+k2=1, it can be calculated from k1=1-k2. k2=exp(-b2 ’ ) Equation 13

[0081] The operating condition is S P , S F , LHSV, P, G and P obtained by the above method B , a, G B ,b,Ec,T B , T SOR Substituting (b1) into the above formula 11 and formula 12 gives D1 and D2. Substituting the obtained D1, D2, k1, and k2 into the above formula 10 gives Φ. In this case, Φ is a function of α1 and α2. Plot the reaction time on the horizontal axis and the logarithm of Φ on the vertical axis, and set α2 = 0 and change α1 so that 0 < α1 to obtain x1 to x ip If we draw a regression line from y to -a α1 ” x(|-a α1 " |=a α1 ” ) are obtained for each value of α1. α1 ” and the above-mentioned a1 ’ The α1 when these values are equal can be used as the α1 in the above equation 11. Next, substitute the obtained α1 into Φ, which is a function of α1 and α2 obtained by the above method, and change α2 so that 0<α2 to obtain x ip ~x m If we draw a regression line from y to -a α2 ” xb α2 " (|-a α2 ” |=a α2 " ) are obtained for each value of α2. α2 and the above-mentioned a2 ’ The α2 when these values are equal can be used as the α2 in the above formula 12.

[0082] (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 11 and formula 12 to obtain D1 and D2. The obtained D1 and D2 are substituted into the above formula 10 to obtain Φ. In this case, Φ is a function of α1, α2, k1, and k2. The obtained Φ is substituted into Φ' in the above formula 6, and T SOR (i.e., b1) is T in the above formula 6 SOR ’ Substituting into, T t ', 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 11. 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 value of α1 when their average is closest to 1 is preferably taken as α1 in the above formula 11. 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 (Tt' / 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 12. 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 11. 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 12. Also, use k1 calculated from the obtained k2 as k1 in the formula 11. L is an integer of 10 or more, preferably 10 to 500, and more preferably 50 to 200.

[0083] 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.

[0084] 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.

[0085] The reaction time required to obtain y = a1x + b1 and y = a2x + b2 is usually 100 days or more. In general, it is sufficient to carry out the reaction until the correlation function of y = a'x + b' becomes 0.5 or greater.

[0086] <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.

[0087] <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 14 is derived from the above-mentioned equations 1 and 5.

[0088]

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[0089]

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[0090] In the above formula 15, 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 15 can be calculated as follows.

[0091] (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.

[0092] First, determine the reaction order of the desulfurization reaction of feedstock oil containing atmospheric distillation gas oil. 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 16 below, 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.

[0093]

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[0094] 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.

[0095] 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.

[0096] 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. The reaction temperature is, for example, 300 to 400°C, the hydrogen partial pressure is, for example, 3 to 7 MPa, and the hydrogen / feedstock ratio is, for example, 100 to 700 [Nm 3 / kL], and the sulfur concentration in the feed oil is, for example, 0.5 to 2.0 mass %. Similarly, it is preferable that the x types of LHSV(x) are set to conditions that correspond to the actual operating conditions. For example, LHSV(x) is set to 0.3 to 2.0 h -1 is.

[0097] 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 17 is obtained.

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[0098] 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 17, 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.

[0099] 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.

[0100] 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.

[0101] 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 700 [Nm 3 / kL] and LHSV is 0.3 to 2.0 h -1 The sulfur concentration in the feed oil is 0.5 to 2.0 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 400°C.

[0102] By substituting each parameter thus obtained into the above-mentioned formula 15, the reaction temperature T required to achieve the predetermined reaction conditions can be calculated. t can be obtained.

[0103] 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.

[0104] <Naphtha yield calculation step> In the naphtha yield calculation step of this embodiment, t The naphtha yield is calculated based on the degree of deterioration of the catalyst cracking reaction. The naphtha yield is preferably calculated using a naphtha yield calculation function based on a first-order cracking reaction rate equation.

[0105] <Naphtha yield calculation function> The naphtha yield calculation function is expressed by the following equation 18.

[0106]

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[0107] In the above-mentioned formula 18, 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 feedstock oil supply rate (volume / h) by the catalyst loading rate (volume). Φ C and k C0(Tt) The method for calculating this will be described later.

[0108] The degradation degree of the decomposition reaction in the above formula 18 is expressed by the following formula 19. Φ C =k Ct(T0) / k C0(T0) formula 19 In the formula 19, 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

[0109] The above-mentioned formula 18 is derived based on the premise that the cracking reaction of diesel is a first-order reaction and that naphtha is produced by the cracking reaction. The method for deriving the above-mentioned formula 18 will be explained below.

[0110] The decomposition reaction rate equation is expressed by the following equation 20. k Ct(Tt) =ln(CF / C P )×LHSV Equation 20 In the formula 20, 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 diesel concentration (mass%) in the feedstock oil after any reaction time t days, and C P is the diesel concentration (mass%) in the produced oil after t days of reaction, and LHSV is the liquid hourly space velocity (h -1 )

[0111] 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-Ct / 100. As mentioned above, based on the assumption that naphtha is produced by the cracking reaction, the conversion rate C t (%) is also the amount of naphtha obtained (mass%). Substituting these values into Equation 20 above, we obtain Equation 21 below.

[0112]

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[0113]

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[0114] Φ C =k Ct(Tt) / k C0(Tt) formula 23 In the formula 23, 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

[0115] From the above formula 23, k Ct(Tt) =Φ C ×k C0(Tt) By substituting this value into the above-mentioned equation 22, the above-mentioned equation 18 is derived.

[0116] Next, Φ C , k C0(Tt) We will explain how to find this.

[0117] (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 24. The following formula 24 is based on the Arrhenius equation expressed by the formula 5 above.

[0118]

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[0119] 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 21, it can be calculated by the following formula 25.

[0120]

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[0121] 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 naphtha yield is measured, and the yield can be calculated from the above formula 25.

[0122] 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 700 [Nm 3 / kL] and LHSV is 0.3 to 2.0 h -1 The sulfur concentration in the feed oil is 0.5 to 2.0 mass %.

[0123] 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 naphtha obtained and the LHSV can be calculated by substituting them into the above formula 25.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.

[0124] Activation energy of decomposition E D can be found as follows:

[0125] 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 (26).

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[0126] 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. The reaction rate constant k can be calculated 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 naphtha yield in the product oil is measured. The naphtha yield and LHSV obtained are substituted into equation 21 to calculate the reaction rate constant k. The obtained reaction rate constant is substituted into equation 26, 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.

[0127] 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.

[0128] The above y' is an integer equal to or greater than 3. The larger the number of y', the more accurate the E DOn 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.

[0129] 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 700 [Nm 3 / kL] and LHSV is 0.3 to 2.0 h -1 The sulfur concentration in the feed oil is 0.5 to 2.0 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 400°C.

[0130] 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 24, k C0(Tt) Ask for.

[0131] <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 Φ C It was found for the first time that the degradation degree Φ of the desulfurization reaction can be calculated based on the above-mentioned degradation degree Φ of the desulfurization reaction. C We will explain how to find each of these.

[0132] (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. CThis is a method to find Φ C can be calculated using the following equation 27.

[0133] Φ C =βΦ Equation 27 In the above formula 27, Φ C is the degradation degree of the decomposition reaction, Φ is the degradation degree of the desulfurization reaction (degradation function 1 of the desulfurization reaction), and β is the degradation coefficient of the decomposition reaction (constant).

[0134] Since Φ can be calculated using the method described above, once β is determined, Φ can be calculated from C In the above formula 27, Φ at the time of reaction elapsed time 0 can be calculated. C where βΦ=1.

[0135] 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 for the actual plant are the conditions used to calculate the activation energy of the cracking process mentioned above. The amount of naphtha obtained after t' days of reaction, C, is t’ Measure the resulting C t’ , k obtained by the above method C0(Tt) (k C0(Tt’) ), and LHSV are substituted into Equation 18, C Also, 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.

[0136] (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 28.

[0137] Φ C =β1Φ1+β2Φ2 Equation 28 In the above formula 28, Φ C is the degree of deterioration of the decomposition reaction, Φ1 is k1 × exp(-D1t) in equation 10, Φ2 is k2 × exp(-D2t) in equation 10, 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.

[0138] Since Φ1 and Φ2 can be obtained by the above method, once β1 and β2 are determined, Φ C In the above formula 28, Φ at the time of reaction elapsed time 0 can be calculated. C is β1Φ1+β2Φ2=1.

[0139] 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 naphtha obtained after any reaction t' days has elapsed is C t’ Measure the resulting C t’ , k obtained by the above method C0(Tt) (k C0(Tt’) ), and LHSV are substituted into Equation 18, 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 28. Similarly, Φ Cn , Φ1n , Φ 2n If Equation 28 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 28, and the obtained β2' can be used as β2 in the above formula 28. 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.

[0140] Using the β or β1 and β2 obtained by the above method, Φ is calculated from the above formula 27 or 28. C can be obtained.

[0141] The k obtained by the above method C0(Tt) , Φ calculated by the above-mentioned formula 27 or the above-mentioned formula 28 C By substituting the above formula 18, the yield of naphtha after t days of reaction can be calculated.

[0142] Actual naphtha yield C obs The naphtha yield C obtained by the information processing method of this embodiment 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 When the amount of naphtha obtained is within the above range, it can be determined that the amount of naphtha obtained can be estimated with high accuracy.

[0143] <Information output step> The method may further include an information output step (S5 in FIG. 1) of outputting information indicating the naphtha yield thus obtained. For example, S5 is executed by the output unit 14.

[0144] <Hydrotreatment reaction of feedstock oil including atmospheric distillation gas oil> The hydrotreating reaction of feedstock oils including atmospheric distillation gas oil will be outlined below. Atmospheric distillation gas oil is a fraction with a boiling point range of 150 to 380°C obtained by atmospheric distillation of crude oil. The density of atmospheric distillation gas oil is 0.83 to 0.90 g / mL. The content of atmospheric distillation gas oil in the feedstock oil may be, for example, 50 to 100% by volume, or 80 to 100% by volume. In addition, examples of oil types contained in the feedstock other than atmospheric distillation light oil and cracked light oil include light oil fractions obtained from fluid catalytic cracking units, direct desulfurization units, indirect desulfurization units, and the like.

[0145] The hydrotreating reaction of a feedstock containing atmospheric distillation gas oil can be carried out by contacting the feedstock containing atmospheric distillation 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.

[0146] 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.

[0147] The conditions for the hydrotreating reaction of feedstock oil containing atmospheric distillation gas oil are generally a reaction temperature of 300 to 400°C, preferably 330 to 400°C, a hydrogen partial pressure of 3 to 7 MPa, preferably 4 to 7 MPa, and an LHSV of 0.3 to 2.0 hr. -1 , preferably 0.5 to 1.5 hours -1 The hydrogen / feed oil ratio is 100 to 700 (Nm 3 / kL), preferably 200 to 500 (Nm 3 / kL).

[0148] The sulfur concentration in the feedstock oil containing atmospheric distillation gas oil is usually 0.5 to 2.0 mass %, and the sulfur concentration in the product oil is 0.001 mass % or less.

[0149] In this specification, "naphtha" refers to a component having a boiling point range of 175°C or less and having 5 to 10 carbon atoms, which is obtained by cracking in a hydrotreating reaction. The yield of naphtha can be determined by a method for measuring the yield of naphtha known in the art, for example, by calculation from the proportion of fractions at 175°C or less in a distillation test such as ASTM D-6730.

[0150] <Naphtha yield calculation device> The naphtha yield calculation device of this embodiment includes an acquisition unit that acquires information about the feedstock oil, information about the product oil, and information about operating conditions when a predetermined time has elapsed since the start of the reaction, regarding the hydrotreating reaction of feedstock oil containing atmospheric distillation gas oil; and a calculation unit that calculates a catalyst degradation level 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 a reaction temperature necessary to satisfy the operating conditions based on the calculated catalyst degradation level, and calculates the naphtha yield based on the calculated reaction temperature and the catalyst degradation level.

[0151] The naphtha 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 naphtha yield calculation device 1 may be configured using one or more information processing devices. For example, the naphtha 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 naphtha yield calculation device 1 includes an acquisition unit 11 and a computer main body 12 that processes information from the acquisition unit. The naphtha yield calculation device 1 may also include an output unit 14 that outputs information processed in the computer main body 12 to the outside. These components are implemented, 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).

[0152] 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 atmospheric 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.

[0153] 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.

[0154] 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 catalyst deterioration level 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 catalyst deterioration level, 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. The naphtha yield is calculated based on the reaction temperature and the catalyst deterioration level. The deterioration function is as described above. As described above, the reaction temperature can be calculated, for example, from a deterioration rate equation. The naphtha yield can be calculated, for example, from a naphtha yield function. For example, the calculation unit 13 executes the deterioration level calculation step, the reaction temperature calculation step, and the naphtha 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.

[0155] The calculation unit 13 may output to the output unit 14 the information on the feed oil obtained as described above, the information on the product oil, and information indicating the naphtha yield at the reaction temperature required to satisfy the operating conditions.

[0156] The output unit 14 receives the calculation results (reaction temperatures) output by the computer main body 12 (more specifically, the calculation unit 13) and outputs the received calculation results to the outside. The output unit 14 of this embodiment is configured by a display unit such as a CRT display, a liquid crystal display, or a PDP, but is not limited to this and may be configured to output to a printing unit such as a printer, or to other devices (for example, a computer used to control the hydrotreating reaction of feedstock oil including atmospheric 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.

[0157] Furthermore, in this embodiment, there are provided a naphtha yield calculation program for causing a computer to function as a naphtha yield calculation device, and a non-transitory computer-readable recording medium storing the program. Examples of non-transitory computer-readable recording media include magnetic tapes (digital data storage (DSS) and the like), magnetic disks (hard disk drives (HDD), flexible disks (FD), and the like), optical disks (compact disks (CD), digital versatile disks (DVD), Blu-ray disks (BD), and the like), magneto-optical disks (MO), and flash memories (solid state drives (SSD), memory cards, USB memories, and the like).

[0158] <Method of using information processing method and naphtha yield calculation device> The information processing method and naphtha yield calculation device of this embodiment can estimate the naphtha yield at the reaction temperature required to achieve predetermined reaction conditions for the hydrotreating reaction of feedstock oil containing atmospheric distillation gas oil.The information processing method and naphtha yield calculation device of this embodiment can obtain a plot of estimated naphtha yield over time.The relationship between the plot and the upper limit of the naphtha withdrawal capacity of the atmospheric distillation gas oil hydrotreating treatment device can be considered for the following applications.

[0159] As a method of utilization, it is possible to estimate the reaction conditions (reaction temperature, processing volume (LHSV)) to make the naphtha yield below the upper limit of the naphtha extraction capacity, and to plan the production of secondary processing equipment using cracked naphtha by estimating and knowing the future naphtha production volume in advance. In other words, when a predetermined naphtha yield is set for a predetermined operating time, the above formula 18 can be expressed as follows: K CO(Tt) , Φ C , LHSV. k is a function of CO(Tt) , Φ C The reaction conditions in this combination will result in a naphtha yield that is below the upper limit of the naphtha extraction capacity, and will be the estimated reaction conditions that will allow us to know in advance the future naphtha production amount. [Example]

[0160] 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.

[0161] [Example 1] A bench-scale hydrotreating reaction was carried out by contacting a feedstock containing 99% by volume of atmospheric distillation gas oil with hydrotreating catalyst A. 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 10 was used. The parameters in the formulas 10 to 12 were calculated by the above-mentioned method, and the results were k1 = 0.45, k2 = 0.55, α1 = 0.01, α2 = 0.002, P B =3.234(MPa), a=2, G B =400(Nm 3 / kL), b=1.3, E C = 83.1 (kJ / mol), T B =625(K), T SOR =630(K), n=1.2. The reaction was carried out in an actual reactor using the same feedstock and hydrotreating catalyst as in the bench-scale hydrotreating reaction. F =1.57(mass%), P=4.9(MPa), G=250(Nm 3 / kL), LHSV=2.0(h-1 ), S P = 0.0008 (mass%). In addition, the activation energy of desulfurization and decomposition were calculated in advance using the method described above, and Ea = 120 (kJ / mol), E D =120 (kJ / mol).

[0162] From the measured value of naphtha yield at 1 day of reaction time, k C0(T0) The result was 0.14[h -1 The measured value of the reaction temperature, T0, at this time was 631 (K). In the initial stage of the reaction, Φ1(k1 × exp(-D1t)) and Φ2(k2 × exp(-D2t)) calculated by the above formula 10, the measured value of the amount of naphtha obtained, and the above k C0(T0) , and Φ calculated from Equation 18 by LHSV C When β1 and β2 were calculated from the above formula 28, β1=0.45 and β2=1.35. Using the above parameters, the required temperature T t From the above formula 18, (3) naphtha yield C t The results are shown in Table 1.

[0163] [Example 2] A bench-scale hydrotreating reaction was carried out by contacting a feedstock containing 99% by volume of atmospheric distillation gas oil with hydrotreating catalyst B. Based on the obtained results, the degradation function was calculated. In this example, degradation function 2 expressed by the above-mentioned formula 10 was used. The basic degradation parameters in the formulas 10 to 12 were calculated by the above-mentioned method, and the results were k1 = 0.45, k2 = 0.55, α1 = 0.01, α2 = 0.002, P B =3.234(MPa), a=2, G B =400(Nm 3 / kL), b=1.3, E C = 83.1 (kJ / mol), T B =625(K), T SOR =629(K), n=1.2. The reaction was carried out in an actual reactor using the same feedstock and hydrotreating catalyst as in the bench-scale hydrotreating reaction. F =1.57(mass%), P=4.9(MPa), G=250(Nm 3 / kL), LHSV=2.0(h -1 ), S P = 0.0008 (mass%). In addition, the activation energy of desulfurization and decomposition were calculated in advance using the method described above, and Ea = 120 (kJ / mol), E D =120 (kJ / mol).

[0164] From the measured value of naphtha yield at 1 day of reaction time, k C0(T0) The result was 0.069[h -1 The measured value of the reaction temperature, T0, at this time was 629 (K). After that, in the initial stage of the reaction, Φ1(k1 × exp(-D1t)) and Φ2(k2 × exp(-D2t)) calculated by the above formula 10, the measured value of the naphtha yield, C0(T0) , and Φ calculated from Equation 18 by LHSV C When β1 and β2 were calculated from the above formula 28, β1=0.45 and β2=1.35. Using the above parameters, the required temperature T t From the above formula 18, (3) naphtha yield C t The results are shown in Table 2.

[0165] [Table 1]

[0166] [Table 2]

[0167] As shown in Tables 1 and 2, the naphtha yield C obtained by the present invention t It was found that the yield of naphtha was almost the same as the measured value. [Explanation of symbols]

[0168] 1. Naphtha yield calculation device 11...Acquisition part 12...Calculator body 13... Arithmetic section 14. Output section

Claims

1. With respect to the hydrotreating reaction of a feedstock oil containing atmospheric distillation gas 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 naphtha yield calculation step of calculating a naphtha yield based on the reaction temperature and a deterioration degree of the decomposition reaction of the catalyst, The information processing method, wherein the degradation function is a function expressed by the following equation 2: Φ=exp(-Dt) Formula 2 In the above formula 2, Φ is the degree of deterioration of the catalyst, D is the deterioration coefficient of the active species 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 a catalyst constant (a constant representing the catalyst deterioration rate), 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 atmospheric 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.

2. An information acquisition step for acquiring information about the feedstock oil, information about the product oil, and information about operating conditions after a predetermined time has elapsed since the start of the reaction, in relation to a hydrotreating reaction of a feedstock oil including atmospheric distillation gas oil; 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 naphtha yield calculation step of calculating a naphtha yield based on the reaction temperature and a deterioration degree of the decomposition reaction of the catalyst, The information processing method, wherein the degradation function is a function expressed by the following equation 10: Φ=k 1 ×exp(-D 1 t)+k 2 ×exp(-D 2 t) Equation 10 In the above formula (10), 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 (11), 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 (12), 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 2] [Equation 3] In the above formulas 11 and 12, 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 atmospheric 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 11, α 1 is the catalytic constant of the easily deactivated active sites in the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction of the catalyst), and in equation 12, α 2 is the catalytic constant of the hardly deactivated active sites in 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.

3. A naphtha yield calculation device comprising: an acquisition unit that acquires information about the feedstock oil, information about the product oil, and information about operating conditions when a predetermined time has elapsed since the start of a hydrotreating reaction of a feedstock oil containing atmospheric distillation gas 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 oil, the information about the product oil, and the information about the operating conditions acquired by the acquisition unit, calculates a reaction temperature required to satisfy the information about the feedstock oil, the 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 naphtha yield based on the calculated reaction temperature and the deterioration level of the cracking reaction of the catalyst, The naphtha yield calculation device, wherein the deterioration function is a function expressed by the following equation 2. Φ=exp(-Dt) Formula 2 In the above formula 2, Φ is the degree of deterioration of the catalyst, D is the deterioration coefficient of the active species of the catalyst and is calculated using the following formula 3, and t is the number of days elapsed since the reaction began. [Equation 4] In the above formula 3, α is a catalyst constant (a constant representing the catalyst deterioration rate), 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 atmospheric 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.

4. A naphtha 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 atmospheric distillation light oil; and a calculation unit that calculates a degradation level of the desulfurization reaction and a degradation level 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 a reaction temperature required to satisfy the operating conditions based on the calculated degradation level of the desulfurization reaction of the catalyst, and calculates the naphtha yield based on the calculated reaction temperature and the degradation level of the cracking reaction of the catalyst, The naphtha yield calculation device, wherein the deterioration function is a function expressed by the following equation 10. Φ=k 1 ×exp(-D 1 t)+k 2 ×exp(-D 2 t) Equation 10 In the above formula (10), 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 (11), 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 (12), 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 11 and 12, 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 atmospheric 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 11, α 1 is the catalytic constant of the easily deactivated active sites in the desulfurization reaction (a constant representing the deterioration rate of the desulfurization reaction of the catalyst), and in equation 12, α 2 is the catalytic constant of the hardly deactivated active sites in 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.

5. A naphtha yield calculation program for causing a computer to function as the naphtha yield calculation device according to claim 3 or 4.

6. A non-transitory computer-readable recording medium storing the program according to claim 5.

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