JP7768684B2 - Information processing method, hydrogen consumption calculation device, hydrogen consumption calculation program, and non-transitory computer-readable recording medium - Google Patents

Description

The present invention relates to an information processing method, a hydrogen consumption calculation device, a hydrogen consumption calculation program, and a non-transitory computer-readable recording medium.

Diesel fuels used as diesel engine fuels, etc., are produced by hydrotreating straight-run diesel fractions of a specific boiling point range obtained by atmospheric distillation of crude oil, or cracked diesel fractions obtained by cracking heavy oil, or by blending unhydrotreated diesel fractions with hydrotreated diesel fractions. Hydrotreating diesel fractions reduces the sulfur content of the diesel fraction and also improves its properties as a diesel engine fuel, such as color and cetane number.

In the hydrotreating of feedstock containing diesel fractions, operational constraints include reaction temperature and hydrogen consumption. Regarding reaction temperature, hydrotreating equipment has a maximum operating temperature set according to its materials, structure, and the capacity of its surrounding equipment, and is constrained to operate at or below this maximum operating temperature. Regarding hydrogen consumption, depending on the refinery's hydrogen supply environment, a shortage of hydrogen can limit the processing volume of feedstock containing diesel fractions. Therefore, a method for accurately estimating reaction temperature and hydrogen consumption is needed.

Patent Document 1 discloses a method for estimating the reaction temperature required after switching between straight-run diesel fractions with different properties as feedstock during the hydrotreatment of straight-run diesel fractions, based on information about the properties of the straight-run diesel fraction before the switch and the operating conditions, and information about the properties of the straight-run diesel fraction after the switch and the operating conditions other than the reaction temperature.

Japanese Patent Application Publication No. 10-60455

In the hydrotreating method for straight-run diesel fraction described in Patent Document 1, hydrogen consumption is not considered, and a value calculated based on actual results is used as the hydrogen consumption amount. As mentioned above, hydrogen consumption amount can be an operational constraint. Furthermore, since hydrogen consumption amount has a significant impact on hydrotreating costs, a method for accurately estimating hydrogen consumption amount is desired.

The present invention was made in consideration of the above circumstances, and aims to provide an information processing method capable of estimating hydrogen consumption in the hydrotreating reaction of feedstock oil containing a diesel fraction, a hydrogen consumption calculation device capable of estimating the hydrogen consumption, a hydrogen consumption calculation program, and a non-transitory computer-readable recording medium.

In order to solve the above problems, the present invention has the following aspects.
[1] An information processing method for a hydrotreating reaction of a feedstock containing a light oil fraction, comprising: an information acquisition step of acquiring information about the feedstock and information about a product oil for a certain period of time; and a hydrogen amount calculation step of calculating the amount of hydrogen consumed in the hydrotreating reaction for the certain period of time based on the acquired information about the feedstock and information about the product oil.
[2] The information processing method according to [1], wherein the hydrotreating reaction includes a hydrodesulfurization reaction, a hydrocracking reaction, and a hydrogenation reaction, and the hydrogen amount calculation step is a step of calculating the amount of hydrogen consumed in the hydrodesulfurization reaction, the hydrocracking reaction, and the hydrogenation reaction during the certain period.
[3] The information processing method according to [1] or [2], wherein the information about the feedstock oil includes information about the composition of the feedstock oil and the supply amount of the feedstock oil, and the information about the product oil includes information about the composition of the product oil.
[4] The information processing method according to [3], wherein the information on the composition of the feedstock oil includes information on the sulfur concentration in the feedstock oil, information on the naphtha concentration in the feedstock oil, and information on the aromatic compound concentration in the feedstock oil, and the information on the composition of the product oil includes information on the sulfur concentration in the product oil, information on the naphtha concentration in the product oil, and information on the aromatic compound concentration in the product oil.
[5] The information processing method according to [3] or [4], wherein the information about the feedstock oil includes information about the density of the feedstock oil, and the information about the product oil includes information about the density of the product oil.
[6] A hydrogen consumption calculation device including: an acquisition unit that acquires information about a feedstock oil and information about a product oil over a certain period of time regarding a hydrotreating reaction of a feedstock oil containing a light oil fraction; and a calculation unit that calculates the amount of hydrogen consumed in the hydrotreating reaction over the certain period of time based on the information about the feedstock oil and the information about the product oil acquired by the acquisition unit.
[7] The hydrogen consumption calculation device according to [6], wherein the hydrotreating reaction includes a hydrodesulfurization reaction, a hydrocracking reaction, and a hydrogenation reaction, and the calculation unit calculates the amount of hydrogen consumed in the hydrodesulfurization reaction, the hydrocracking reaction, and the hydrogenation reaction during the certain period.
[8] The hydrogen consumption calculation device according to [6] or [7], wherein the information about the feedstock oil includes information about the composition of the feedstock oil and information about the supply amount of the feedstock oil, and the information about the product oil includes information about the composition of the product oil.
[9] The hydrogen consumption calculation device according to [8], wherein the information on the composition of the feedstock oil includes information on the sulfur concentration in the feedstock oil, information on the naphtha concentration in the feedstock oil, and information on the aromatic compound concentration in the feedstock oil, and the information on the composition of the product oil includes information on the sulfur concentration in the product oil, information on the naphtha concentration in the product oil, and information on the aromatic compound concentration in the product oil.
[10] The hydrogen consumption calculation device according to [8] or [9], wherein the information about the feedstock oil includes information about the density of the feedstock oil, and the information about the product oil includes information about the density of the product oil.
[11] A hydrogen consumption calculation program for causing a computer to function as the hydrogen consumption calculation device according to any one of [6] to [10].
[12] A non-transitory computer-readable recording medium storing the program according to [11].

The present invention provides an information processing method capable of estimating hydrogen consumption in a hydrotreating reaction of feedstock oil containing a diesel fraction, a hydrogen consumption calculation device capable of estimating the hydrogen consumption, a hydrogen consumption calculation program, and a non-transitory computer-readable recording medium.

1 is a flowchart of an information processing method according to an embodiment. 1 is a flowchart of an information processing method according to an embodiment. 1 is a configuration block diagram of a hydrogen consumption amount calculation device according to an embodiment. FIG. 1 is a configuration block diagram of a naphtha yield calculation device according to an embodiment.

The following describes in detail the embodiments of the present invention. However, the following description is merely an example of an embodiment of the present invention, and the present invention is not limited to these details and can be modified and implemented within the scope of its essence.

<Information processing method>
The information processing method of this embodiment includes an information acquisition step (S1 in FIG. 1) of acquiring information about the feedstock and information about the product oil over a certain period of time regarding the hydrotreating reaction of the feedstock containing a diesel fraction, and a hydrogen amount calculation step (S2 in FIG. 1) of calculating the amount of hydrogen consumed in the hydrotreating reaction over the certain period of time based on the acquired information about the feedstock and information about the product oil. Each step will be explained below. Note that each step shown below is executed, for example, by the hydrogen consumption calculation device 1 of this embodiment. For example, S1 is executed by the acquisition unit 11, and S2 is executed by the calculation unit 13 in the computer main body 12.

<Information Acquisition Steps>
The information acquisition step of this embodiment is a step of acquiring information about feedstock oil and information about product oil for a certain period of time. The information acquisition step may acquire information about operating conditions for a certain period of time. The certain period is, for example, s days. s may be an integer or a decimal; for example, s = 0.5 means 12 hours. s can be determined appropriately depending on the operating conditions, etc., and may be 0.1 to 1000, or 0.1 to 50. Furthermore, the certain period may be a past period from the time when the information processing method of this embodiment is implemented, a period including the present, or a future period. For example, if the information acquired in the information acquisition step is a measured value, the period will be a past period or a period including the present from the time when the information processing method is implemented. On the other hand, if the information acquired in the information acquisition step is a set value or an estimated value, the period will be a future period.

(Information about feedstock oil)
Examples of the information about the feedstock include information about the composition of the feedstock, information about the density of the feedstock, and information about the feedstock supply amount. Examples of the information about the composition of the feedstock include information about the naphtha concentration in the feedstock, information about the aromatic compound concentration in the feedstock, and information about the sulfur concentration in the feedstock.

Information regarding the sulfur concentration in the feedstock oil can be obtained by methods for measuring sulfur concentration known in the art, such as ultraviolet fluorescence spectroscopy and wavelength dispersive X-ray fluorescence spectroscopy.
Information on the naphtha concentration in the feedstock oil can be obtained by a method for measuring naphtha concentration known in the art, and examples thereof include calculation from the proportion of fractions at 175°C or less by a distillation test such as ASTM D-6730.
Information regarding the concentration of aromatic compounds in the feedstock oil can be obtained by a method for measuring the concentration of aromatic compounds known in the art, such as high performance liquid chromatography (HPLC) or gas chromatography-gravimetric analysis (GC-MS measurement).

Information regarding the density of feedstock oil can be obtained using density measurement methods known in the art. For example, the density of feedstock oil can be obtained by correcting the 15°C density obtained according to JIS K2249 "Crude oil and petroleum products -- Density test methods and density, mass, and volume conversion tables" for temperature.

Information regarding the feedstock supply rate can be obtained using methods for measuring feedstock supply rate known in the art, such as a flow meter. Information regarding the feedstock supply rate can be controlled. In other words, it is preferable that the information regarding the feedstock supply rate is a set value.

(Information about produced oil)
Examples of the information about the product oil include information about the composition of the product oil and information about the density of the product oil. Examples of the information about the composition of the product oil include information about the naphtha concentration in the product oil, information about the aromatic compound concentration in the product oil, and information about the sulfur concentration in the product oil.

Information regarding the sulfur concentration in the produced oil, information regarding the naphtha concentration in the produced oil, and information regarding aromatic compounds in the produced oil can be obtained in the same manner as for the feedstock oil described above. Information regarding the density of the produced oil can be obtained in the same manner as for the feedstock oil described above.

The above explains how to measure information regarding sulfur concentration in feedstock oil and product oil, information regarding naphtha concentration, information regarding aromatic compounds, and information regarding the density of feedstock oil and product oil, but if these values are known or there are assumed values for operation, those values can also be used.

The information regarding feedstock oil and product oil for a certain period of time may be obtained only once during said period of time, or may be obtained multiple times. If the information is obtained multiple times, the average values thereof may be used as the information regarding feedstock oil and product oil for the certain period of time.

(Information about operating conditions)
Examples of information about operating conditions include information about hydrogen partial pressure, information about catalyst loading, and information about the amount of hydrogen supplied. For example, the information about operating conditions is at least one of information about hydrogen partial pressure, information about catalyst loading, and information about the amount of hydrogen supplied. Among these, it is more preferable to include all of information about hydrogen partial pressure, information about catalyst loading, and information about the amount of hydrogen supplied. In addition, the operating conditions also include information about time, such as a certain period of s days after the start of the reaction or an arbitrary number of t days.

Information regarding hydrogen partial pressure, catalyst loading, and hydrogen supply rate can be determined by methods known in the art. Information regarding hydrogen partial pressure, catalyst loading, and hydrogen supply rate can be controlled in the hydrotreating reaction of feedstock containing diesel fractions. Information regarding operating conditions is preferably a set value; that is, the intended operating conditions are used.

Information regarding operating conditions for a certain period of time may be acquired only once during the certain period of time, or may be acquired multiple times. If information regarding operating conditions for the certain period of time is acquired multiple times, the average value of the acquired information may be used as information regarding operating conditions for the certain period of time.

<Hydrogen amount calculation step>
The hydrogen amount calculation step of this embodiment is a step of calculating the amount of hydrogen consumed in the hydrotreating reaction over a certain period of time based on the information about the feedstock oil and the information about the product oil acquired in the information acquisition step. In this embodiment, it is preferable to calculate the amount of hydrogen using a hydrogen consumption calculation function described below.

The inventors of the present application have discovered that by calculating the difference between a specific component contained in the feedstock oil and the same specific component contained in the refined oil, it is possible to focus on the hydrogen consumption resulting from this difference in components and accurately calculate the actual hydrogen consumption.

The hydrogen consumption calculation function in this embodiment is preferably a function that calculates the sum of the amount of hydrogen consumed by the hydrodesulfurization reaction, the amount of hydrogen consumed by the hydrocracking reaction, and the amount of hydrogen consumed by the hydrogenation reaction. An example of such a hydrogen consumption calculation function is the hydrogen consumption function expressed by the following equation 1:

In Equation 1, _HC is the estimated hydrogen consumption amount consumed in a certain period of time, S _F(ave) is the average sulfur concentration in the feed oil for the certain period of time, S _P(ave) is the average sulfur concentration in the product oil for the certain period of time, N A _P(ave) is the average naphtha concentration in the product oil for the certain period of time, N A _F(ave) is the average naphtha concentration in the feed oil for the certain period of time, AR _F(ave) is the average aromatic compound concentration in the feed oil for the certain period of time, AR _P(ave) is the average aromatic compound concentration in the product oil for the certain period of time, L is the feed amount of the feed oil for the certain period of time, and a ₁ , a ₂ , and a ₃ are tuning factors that are constants greater than 0.

The unit of _HC is not particularly limited as long as it is a unit that represents the amount of hydrogen, and for example, volume, mol, etc. can be used. The units of _SF(ave) and _SP(ave) are not particularly limited as long as they are units that represent concentration, and for example, mass%, volume%, etc. can be used. However, the units of _SF(ave) and _SP(ave) are the same. The units of _NAP(ave) and NAF( _ave) are not particularly limited as long as they are units that represent concentration, and for example, mass%, volume%, etc. can be used. However, the units of _NAP(ave) and _NAF(ave) are the same. The units of AR _F(ave) and _ARP(ave) are not particularly limited as long as they are units that represent concentration, and for example, mass%, volume%, etc. can be used. However, the units of AR _F(ave) and _ARP(ave) are the same. The unit of L is not particularly limited as long as it is a unit that expresses the amount of feedstock oil supplied, and for example, volume, mass, mol, etc. can be used.
In the formula 1, the units of SF _(ave) and _SP(ave) , the units of NAP _(ave) and _NAF(ave) , and the units of AR _F(ave) and _ARP(ave) may be the same or different.
In this embodiment, for example, the unit of _HC can be [ ^Nm3 ], the unit of S _F(ave) and S _P(ave) can be [mass%], the unit of NAP _(ave) and _NAF(ave) can be [volume%], the unit of AR _F(ave) and _ARP(ave) can be [volume%], and the unit of L can be [kL].

In the above formula 1, (S _F(ave) - _{S P(ave)} ) is a term that quantitatively indicates the extent to which the hydrodesulfurization reaction has progressed in a certain period of time, and a ₁ (S _F(ave) - S _P(ave) ) is a term that estimates the amount of hydrogen consumed by the hydrodesulfurization reaction. (NA _P(ave) - NA _F(ave) ) is a term that indicates the extent to which the hydrocracking reaction that produces naphtha has progressed in a certain period of time, and a ₂ (NA _P(ave) - NA _F(ave) ) is a term that estimates the amount of hydrogen consumed by the hydrocracking reaction that produces naphtha. (AR _F(ave) - AR _P(ave) ) is a term that indicates how much the hydrogenation reaction has progressed in a certain period of time, and a ₃ (AR _F(ave) - AR _P(ave) ) is a term that estimates the amount of hydrogen consumed by the hydrogenation reaction.

(Method of setting tuning factors _a1 , _a2 , _a3 )
Tuning factor _a1 is a tuning factor for converting the degree of progress of the hydrodesulfurization reaction that has proceeded over a certain period of time into the amount of hydrogen consumed by the reaction. Tuning factor _a2 is a tuning factor for converting the degree of progress of the hydrocracking reaction that produces naphtha that has proceeded over a certain period of time into the amount of hydrogen consumed by the reaction. Tuning factor _a3 is a tuning factor for converting the degree of progress of the hydrogenation reaction that has proceeded over a certain period of time into the amount of hydrogen consumed by the reaction.

The method for obtaining the tuning factors a ₁ , a ₂ , and a ₃ is not particularly limited, but they can be determined by comparing with the actual measured value of the amount of hydrogen consumed over a certain period of time. An example will be described below.
Using the above method, information on S _F(ave) , S _P(ave) , N A _P(ave) , N A _F(ave) , AR _F(ave) , AR _P(ave) , and L for a certain period is obtained, and the estimated hydrogen consumption amount H _C is calculated using equation 1. In this case, H _C is a function of a ₁ , a ₂ , and a ₃ . It is possible to obtain a ₁ , a ₂ , and a ₃ such that H _RC = H _C, which is the actual measured value of the hydrogen consumption amount for the certain period.

_HRC , which is the actual measured value of hydrogen consumption over a certain period of time, can be obtained by a method for measuring hydrogen consumption known in the art. For an actual machine, the following measurement method can be mentioned as an example. In an actual machine, a constant amount of hydrogen is supplied to the reactor (supplied hydrogen), and unreacted hydrogen (recycled hydrogen) discharged from the reactor outlet is used as part of this supplied hydrogen. On the other hand, the amount of recycled hydrogen is less than the amount of supplied hydrogen. By separately supplying an amount of hydrogen equivalent to this shortage (make-up hydrogen), the amount of supplied hydrogen becomes constant. The amount of this make-up hydrogen is the actual measured value of hydrogen consumption. Make-up hydrogen can be measured using a flow meter.

At bench scale, hydrogen consumption can be calculated, for example, using the following equation 2:

In the above formula 2, H _RC is the actual measured value of the amount of hydrogen consumed over a certain period of time, H _HS is the amount of hydrogen converted from the amount of hydrogen sulfide in the reactor outlet gas over the certain period of time, H _NH is the amount of hydrogen converted from the amount of ammonia in the reactor outlet gas over the certain period of time, H _HC is the amount of hydrogen converted from the amount of hydrocarbons in the reactor outlet gas over the certain period of time, H _P is the amount of hydrogen converted from substances such as hydrocarbons in the produced oil over the certain period of time, H _SOL is the amount of hydrogen dissolved in the produced oil, and _HF is the amount of hydrogen converted from the amount of hydrocarbons such as hydrocarbons in the feed oil.

H _H2S can be calculated by calculating the difference in sulfur concentration over a certain period of time using the above-mentioned (S _F(ave) -S _P(ave) ), converting the obtained difference to H ₂ S, and then calculating the amount of hydrogen converted from the amount of H ₂ S.
H _NH3 can be calculated by calculating the difference between the nitrogen concentration in the feed oil and the nitrogen concentration in the product oil over a certain period of time, converting the obtained difference into _NH3 , and then calculating the amount of hydrogen converted from the amount of _NH3 .
H _HC can be calculated as hydrogen converted from the amount of hydrocarbons having 1 to 6 carbon atoms obtained by analyzing the gas at the outlet of the reactor for a certain period by gas chromatography.
H _P is the amount of hydrogen obtained by CHN macroanalysis of the oil produced over the given period.
H _SOL is the amount of hydrogen calculated from the amount of dissolved hydrogen based on Henry's law.
_HF is the amount of hydrogen obtained by CHN macroanalysis of the feedstock oil for the aforementioned fixed period.
Here, since H 2 _SOL can be set to a constant value regardless of each reaction period, H 2 _SOL may be removed from the above formula 2.

In order to obtain a more accurate estimated hydrogen consumption, it is preferable to compare the actual hydrogen consumption value _HRC with the estimated hydrogen consumption _HC over multiple periods. The actual hydrogen consumption value over a certain period is defined as _HRC (n), and the estimated hydrogen consumption is defined as _HC (n). n represents the number of measured periods and is an integer of 2 or more. It is preferable to obtain _a1 , _a2 , and _a3 such that _HRC (n)/ _HC (n) is 0.9 to 1.1 for all n. n is preferably 10 or more, and more preferably 20 or more. The certain period is not particularly limited, but may be, for example, 10 to 300 days.
The tuning factors a ₁ , a ₂ , and a ₃ may be obtained while carrying out the hydrotreating reaction in an actual reactor, or may be obtained in advance on a bench scale.

The hydrogen consumption function expressed by the following equation 3 may be used as the hydrogen consumption calculation function.

In the above formula 3, H _C , S _F(ave) , S _P(ave) , N A _P(ave) , N A _F(ave) , and L are the same as in the above formula 1, DE _F(ave) is the average density of the feed oil for the certain period, DE _P(ave) is the average density of the product oil for the certain period, and b ₁ , b ₂ , and b ₃ are tuning factors which are constants greater than 0.

The inventors of the present application have found that the degree of progress of the hydrogenation reaction over a certain period of time, (AR _F(ave) - AR _P(ave) ), can be substituted by calculating the difference between the average density in the feedstock oil and the average density in the product oil over the certain period of time.
That is, (DE _F(ave) - DE _P(ave) ) is a term indicating the extent to which the hydrogenation reaction has progressed during the certain period of time, and b ₃ (DE _F(ave) - DE _P(ave) ) is a term for estimating the amount of hydrogen consumed by the hydrogenation reaction. According to Equation 3, it is not necessary to obtain information regarding the concentrations of aromatic compounds in the feedstock oil and information regarding the concentrations of aromatic compounds in the refined oil, and it is possible to more simply obtain the estimated hydrogen consumption amount H _C during the certain period of time.

(Method of setting tuning factors _b1 , _b2 , _b3 )
Tuning factor _b1 is a tuning factor for converting the progress of the hydrodesulfurization reaction that has proceeded over a certain period of time into the amount of hydrogen consumed by the reaction. Tuning factor _b2 is a tuning factor for converting the progress of the hydrocracking reaction that produces naphtha that has proceeded over a certain period of time into the amount of hydrogen consumed by the reaction. Tuning factor _b3 is a tuning factor for converting the progress of the hydrogenation reaction that has proceeded over a certain period of time into the amount of hydrogen consumed by the reaction.

The method for obtaining tuning factors _b1 , _b2 , and _b3 is not particularly limited, but they can be determined by comparing with the actual measured value of hydrogen consumption over a certain period of time, similar to the method for obtaining tuning factors _a1 , _a2 , and _a3 described above. An example is described below.
Using the above method, information on S _F(ave) , S _P(ave) , N A _P(ave) , N A _F(ave) , DE _F(ave) , DE _P(ave) , and L for a certain period is obtained, and the estimated hydrogen consumption amount H _C is calculated using equation 3. In this case, H _C is a function of b ₁ , b ₂ , and b _3. It is possible to obtain b ₁ , b ₂ , and b ₃ such that H _RC = H _C, which is the actual measured value of the hydrogen consumption amount for the certain period.

In order to obtain a more accurate estimated hydrogen consumption amount, it is preferable to compare the actual measured hydrogen consumption amount _HRC with the estimated hydrogen consumption amount _HC over multiple periods. The actual measured hydrogen consumption amount over a certain period is defined as _HRC (n), and the estimated hydrogen consumption amount is defined as _HC (n). n represents the number of measured periods and is an integer of 2 or more. It is preferable to obtain _b1 , _b2 , and _b3 such that _HRC (n)/ _HC (n) is 0.9 to 1.1 for all n. n is preferably 10 or more, and more preferably 20 or more. The certain period is not particularly limited, but may be, for example, 10 to 300 days.
The tuning factors b ₁ , b ₂ , and b ₃ may be obtained while carrying out the hydrotreating reaction in an actual reactor, or may be obtained in advance on a bench scale.

The hydrogen consumption function expressed by the following equation 4 may be used as the hydrogen consumption calculation function.

In the above formula 4, H _C , S _F(ave) , S _P(ave) , N A _P(ave) , N A _F(ave) , DE _F(ave) , L, b ₁ , b ₂ , and b ₃ are the same as in the above formula 3, DE _P(ave) ′ is the estimated average density of the produced oil for the certain period calculated by the following formula 5, and f _H is a tuning factor, which is a constant.

In the above formula 5, DE _F(ave) is the same as in the above formula 3, T is the average reaction temperature (°C) for a certain period of time, and α, β, and σ are catalytic coefficients and constants determined for each catalyst used.

The inventors of the present application have found that, once the catalyst to be used is determined, the estimated average density of the product oil can be obtained from the average reaction temperature over a certain period and the average density of the feedstock oil.
That is, (DE _F(ave) - DE _P(ave) ^' ) is a term indicating the extent to which the hydrogenation reaction has progressed in a certain period of time, and b ₃ (DE _F(ave) - DE _P(ave) ^' )f _H is a term for estimating the amount of hydrogen consumed by the hydrogenation reaction. According to Equation 4, it is not necessary to obtain information on aromatic compounds in the feed oil, information on aromatic compounds in the product oil, and information on the density of the product oil, and the estimated hydrogen consumption amount for the certain period of time can be obtained more simply.

(Method for setting catalyst coefficients α, β, and σ)
The catalyst coefficients α, β, and σ are coefficients determined for each catalyst for calculating the estimated average density of the product oil over a certain period from the average density of the feedstock oil over that period and the average reaction temperature over that period.

The method for obtaining the catalyst coefficients α, β, and σ is not particularly limited, but they can be obtained by comparing with the actual measured value of the average density of the produced oil for a certain period. An example will be described below.
Using the above method, information on DE _F(ave) , DE _P(ave) , and T for a certain period is obtained, and DE _P(ave) ' is calculated using Equation 5. In this case, DE _P(ave) ' is a function of α, β, and σ. It is possible to obtain α, β, and σ such that DE _P = DE _P(ave) '.

In order to obtain a more accurate estimated average density of the produced oil, and therefore an estimated hydrogen consumption amount _HC , it is preferable to compare DE _P(ave) and DE _P(ave) ' over multiple periods. The actual measured value of the average density of the produced oil over a certain period is defined as DE _P(ave) (n), and the estimated average density of the produced oil is defined as DE _P(ave) '(n). n represents the number of measured periods and is an integer of 2 or more. It is preferable to obtain α, β, and σ such that DE _P(ave) (n)/DE _P(ave) '(n) is 0.9 to 1.1 for all n.
The catalyst coefficients α, β, and σ may be obtained while carrying out the hydrotreating reaction in an actual reactor, or may be obtained in advance on a bench scale.

( _fH setting method 1)
f _H is a tuning factor determined for each reactor when calculating the estimated hydrogen consumption amount H _C using the estimated average density of the produced oil for the certain period calculated by Equation 5 above.

The method for obtaining the tuning factor _fH is not particularly limited, but it can be obtained by comparing with the actual measured value of the amount of hydrogen consumed over a certain period of time. An example will be described below.
Using the above-described method, α, β, and σ are obtained, and information on DE _F(ave) and T for a certain period is obtained, and DE _P(ave) ' is calculated using equation 5. Furthermore, using the above-described method, b ₁ , b ₂ , and b ₃ are obtained, and S _F(ave) , S _P(ave) , _NAP(ave) , _NAF(ave) , and L for a certain period are obtained, and the estimated hydrogen consumption amount H _C is calculated using equation 4. In this case, H _C is a function of f _H. It is possible to obtain f _H such that H _RC = H _C, which is the actual measured value of the hydrogen consumption amount for the certain period. That is, in this embodiment, f _H can be determined directly.

In order to obtain a more accurate estimated hydrogen consumption amount, it is preferable to compare the actual measured hydrogen consumption amount _HRC with the estimated hydrogen consumption amount _HC over multiple periods. The actual measured hydrogen consumption amount over a certain period is defined as _HRC (n), and the estimated hydrogen consumption amount is defined as _HC (n). n represents the number of measured periods and is an integer of 2 or more. It is preferable to obtain _fH such that _HRC (n)/ _HC (n) is 0.9 to 1.1 for all n. n is preferably 10 or more, and more preferably 20 or more. The certain period is not particularly limited, but may be, for example, 10 to 300 days.
The tuning factor _fH must be obtained from the actual device that will be used.

( _fH setting method 2)
As a method for obtaining the tuning factor _fH other than (method 1 for setting _fH ), for example, the following method can be mentioned. In (method 1 for setting _fH ), _b1 , _b2 , and _b3 are obtained in advance, but according to this method, _fH , _b1 , _b2 , and _b3 can be obtained simultaneously.
Using the above-described method, α, β, and σ are obtained, and information on DE _F(ave) and T for a certain period is obtained, and DE _P(ave) ' is calculated using equation 5. Furthermore, S _F(ave) , S _P(ave) , _NAP(ave) , _NAP(ave) , and L for a certain period are obtained, and the estimated hydrogen consumption amount H _C is calculated using equation 4. In this case, H _C is a function of b ₁ , b ₂ , and B ₃ (b ₃ × f _H ). It is possible to obtain b ₁ , b ₂ , and B ₃ such that H _RC = H _C, which is the actual measured value of hydrogen consumption for the certain period. That is, in this embodiment, f _H can be determined indirectly.

In order to obtain a more accurate estimated hydrogen consumption, it is preferable to compare the actual hydrogen consumption value _HRC with the estimated hydrogen consumption _HC over multiple periods. The actual hydrogen consumption value over a certain period is defined as _HRC (n), and the estimated hydrogen consumption is defined as _HC (n). n represents the number of periods measured and is an integer of 2 or greater. It is preferable to obtain _b1 , _b2 , and _B3 such that _HRC (n)/ _HC (n) is 0.9 to 1.1 for all n. n is preferably 10 or greater, and more preferably 20 or greater. The certain period is not particularly limited, but may be, for example, 10 to 300 days.
In this case, the tuning factors b ₁ , b ₂ , and B ₃ must be obtained from the actual device that will actually be used.

The relationship between the estimated hydrogen consumption H _C obtained from the above formulas 1, 3, and 4 and the measured hydrogen consumption H _RC is preferably H _RC /H _C of 0.9 to 1.1. If H _RC /H _C is outside the above range, it is necessary to reset various tuning parameters.

The above explanation has been given on the assumption that SF _(ave) , SP _(ave) , _NAP(ave) , _NAF (ave), AR _F(ave) , _ARP(ave), etc. are measured values. In this case, the certain period is a period including a past period or the present period from the time when the information processing method of this embodiment is carried out. In information processing method A described below, _SF(ave) and _SP(ave) are used as assumed operating values. Furthermore, NAP _(ave) and _NAF(ave) are calculated based on SF _(ave) and SP _(ave ). As AR _F(ave) (DE _F(ave) ) are characteristics derived from the feedstock, they can be used as assumed operating values by selecting the feedstock. Furthermore, when ARP _(ave) (DE _P(ave) , DE _P(ave) ') is calculated from the above formulas 4 and 5, only the reaction temperature is required. In other words, if it is possible to estimate a reaction temperature that can achieve the assumed operating value of _SP(ave) , the information on the feedstock oil and the information on the product oil in the above formula 1 can be estimated rather than obtained by measurement. In this case, the certain period of time can be a future period from the time when the information processing method of this embodiment is carried out. In other words, by obtaining S _F(ave) , SP _{(ave), NAP(ave )} , _NAP(ave) , DE _P(ave) ', and DE _F(ave) using the following information processing method A, it is possible to estimate the hydrogen consumption for a certain period of time in the future.

<<Information Processing Method A>>
The information processing method A of this embodiment includes the following steps for acquiring information about the feedstock, the product oil, and the operating conditions after a predetermined time has elapsed since the start of the hydrotreating reaction of a feedstock containing a diesel fraction (S1A in FIG. 2 ); a degradation calculation step (S2A in FIG. 2 ) for calculating the degradation levels of the desulfurization reaction and the cracking reaction of the catalyst using a degradation function based on the acquired information about the feedstock, the product oil, and the operating conditions; a reaction temperature calculation step (S3A in FIG. 2 ) for calculating the reaction temperature required to satisfy the information about the feedstock, the product oil, and the operating conditions based on the degradation level of the desulfurization reaction of the catalyst; and a naphtha yield calculation step (S4A in FIG. 2 ) for calculating the naphtha yield based on the reaction temperature and the degradation level of the cracking reaction of the catalyst. Each step will be described below. Note that each of the steps shown below is executed, for example, by the naphtha yield calculation device 2 of this embodiment. For example, S1A is executed by the acquisition unit 21, and S2A, S3A, and S4A are executed by the calculation unit 23 in the computer main body 22. Note that the information acquisition step is substantially the same as the information acquisition step described above, and therefore description thereof will be omitted.

<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.

<Deterioration of desulfurization reaction>
The deterioration degree of the desulfurization reaction is expressed by the following formula 6.
Φ=k _t /k ₀ Equation 6
In Equation 6, _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 _kt is the reaction rate constant of the desulfurization reaction of the catalyst after t days of reaction. Note that _k0 and _kt are reaction rate constants of the desulfurization reaction at a temperature T _SOR , which will be described later.

In this embodiment, the degree of degradation of the catalyst's desulfurization reaction can be calculated using the desulfurization reaction degradation function based on the acquired information about the feedstock oil, information about the product oil, and information about the operating conditions.

<Degradation function 1 of desulfurization reaction>
The desulfurization reaction deterioration function is a function for calculating the degree of deterioration of the desulfurization reaction of the catalyst. In this embodiment, the desulfurization reaction deterioration function is preferably a coke deterioration function relating to 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 degree of deterioration relating to coke deterioration of the catalyst. For example, the desulfurization reaction deterioration function 1 expressed by the following formula 7 can be mentioned as an example.

Φ=exp(-Dt) Equation 7
In the above formula 7, 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 (days).

D can be calculated using the following equation (8): Equation (8) below is a formula that can calculate the depletion coefficient of the active species in the desulfurization reaction of the catalyst using specific parameters. It was first discovered by the inventors of this application based on the operating results of an actual plant.

In the above formula 8, α is the catalyst constant of the desulfurization reaction (a constant representing the degradation rate of the desulfurization reaction of the catalyst), S _F is the sulfur concentration (mass%) in the feed oil after t days of reaction, S _P is the sulfur concentration (mass%) in the product oil after t days of reaction, n is the reaction order of the hydrotreating reaction of the feed oil containing the light oil fraction, 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).

As used herein, the term "required temperature" refers to the reaction temperature required to achieve predetermined reaction conditions. That is, the required temperature on day 0 refers to the reaction temperature required to achieve the reaction conditions S _F , S _P , LHSV, G, and P at the start of the reaction.

In this specification, "reference hydrogen partial pressure" refers to the standard pressure under actual reaction conditions. It is calculated as the average reaction pressure used when determining the hydrogen partial pressure coefficient a, which will be described later.

In this specification, the "reference reaction temperature" means the average value of T _SOR obtained over a range of standard operating conditions that may be actually encountered during operation.

In this specification, "reference hydrogen/feed oil ratio" refers to the standard hydrogen/feed oil ratio under actual reaction conditions. It is calculated as the average hydrogen/feed oil ratio used when determining the hydrogen/feed oil ratio coefficient b, which will be described later.

In Equation 8, T _SOR represents the initial activity of the desulfurization reaction of the catalyst, and α represents the degradation rate of the desulfurization reaction of the catalyst. That is, the larger the values of T _SOR and α, the greater the degradation of the desulfurization reaction of the catalyst, and this degradation behavior is reflected in the value of D.

In the above equation 8, the term expressed by (1/S _P ^n-1 -1/S _F ^n-1 )LHSV is a desulfurization reaction rate constant, and is a constant when S _P , S _F , and LHSV are set values and operation is performed under constant conditions. In the above equation 8, the term expressed by (P _B /P) ^a is a term indicating hydrogen partial pressure dependency, and is a constant when P is set value and operation is performed under constant conditions. In the above equation 8, the term expressed by (G _B /G) ^b is a term indicating hydrogen/feed oil ratio dependency, and is a constant when G is set value and operation is performed under constant conditions. In the above equation 8, the term expressed by exp[Ec/R(1/T _B -1/T _SOR )] is a term indicating temperature dependency, and is a constant.

In the above formula 8, 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 above-mentioned information acquisition step. Note that LHSV can be calculated by dividing the feed oil supply rate (volume/h) by the catalyst loading rate (volume). G can be calculated by dividing the hydrogen supply rate (Nm ³ /hour) by the feed oil supply rate (kL/hour).

As described above, S _F , LHSV, P, and G are controllable parameters. Furthermore, S _P is the sulfur concentration of the target product oil. That is, the deterioration coefficient of the active species of the desulfurization reaction of the catalyst under the reaction conditions of S _F , S _P , LHSV, P, and G can be calculated using Equation 8. The method for determining n, which is the reaction order of the hydrotreating reaction of feedstock oil containing a diesel fraction, will be described later.

(How to determine basic degradation parameters)
In the above formula 8, α, P _B , a, G _B , b, Ec, T _B , and T _SOR are constants. 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 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 the parameter in advance on a bench scale based on the operating conditions of the actual machine.
Below, examples of how to determine the basic deterioration parameters P _B , a, G _{B , b, Ec, and T B are shown. These methods (methods for determining P B , a, G B} , b, Ec, and T _{B )} are 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 above-mentioned reaction on the actual plant or a bench-scale reaction under actual plant _{operating conditions} . Two examples of how to determine α and T _SOR are shown, but the present invention is not limited to these. The first example is a method (method 1 for determining α and T SOR) in which the parameters are determined from the deterioration behavior of the catalyst desulfurization reaction (changes in the reaction rate constant of the desulfurization reaction) analyzed from data obtained from the above-mentioned reaction on the actual plant or a bench-scale reaction under actual plant operating conditions. The second example is a method (method 2 for determining α and T _SOR ) in which the parameters are determined from the reaction temperature profile analyzed from data obtained from the above-mentioned reaction on the actual plant or a bench- _scale reaction under actual plant operating conditions.

(How to find P _B , a, G _B , b, Ec, and T _B )
The method for determining the basic deterioration parameters in this embodiment is based on the deterioration behavior of the desulfurization reaction of the catalyst analyzed from data obtained from the 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 9, based on the same concept as equation 6.
Φ'=k _t '/k ₀ ' Equation 9
In Equation 9, k ₀ ′ 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. Note that k ₀ ′ and k _t ′ are reaction rate constants of the desulfurization reaction at a temperature T _SOR ′ described below.

Like Equation 6, Equation 9 is a degradation function based on the reaction rate constant of the desulfurization reaction. The reaction rate constant is expressed by the Arrhenius equation in Equation 10 below.

In Equation 10, k is the reaction rate constant, A is the frequency factor, E is the activation energy (kJ/mol), R is the gas constant: 0.00831 (kJ/(mol·K)), and T is the reaction temperature (K).

The reaction rate constant _k0 ' of the desulfurization reaction at the reaction start temperature T _SOR ' decreases to kt _' after t days of reaction. If the reaction temperature must be set to _Tt ' in order to obtain activity equivalent to the reaction rate constant _k0 ' of the desulfurization reaction after t days of reaction, the following formula 11 can be derived from formulas 9 and 10. Note that since the reaction in this embodiment is a hydrotreating reaction of a feedstock oil containing a light oil fraction, the activation energy E is set to the desulfurization activation energy Ea (kJ/mol).

In this embodiment, P _B , a, G _B , b, Ec, and T _B are calculated based on the above-mentioned formula 11.

(How to calculate Ec and T _B )
The reaction is carried out for a certain period of time under constant conditions of LHSV, hydrogen partial pressure, hydrogen/feed oil ratio, and sulfur concentration in the feed oil so that the sulfur concentration in the product oil reaches a certain value _SPn . Because the catalyst deteriorates due to the reaction, operation is carried out while increasing the reaction temperature in order to maintain the sulfur concentration in the product oil at _SPn . By plotting the reaction time on the horizontal axis and the measured reaction temperature on the vertical axis and drawing a regression line, a straight line expressed as y = a _n x + b _n (0 < a _n ) is obtained. _{a n} and b _n are values reflecting the deterioration behavior of the catalyst. b _n in this straight line is T _SOR ' in the above formula 11. In the above formula 11, by substituting b _n for T _SOR ' and substituting the measured reaction temperature for T _t ', the deterioration degree Φ' of the desulfurization reaction after any t days of reaction can be obtained. Note that the desulfurization activation energy Ea can be a value determined by the method described below. Plotting the logarithm of Φ' on the vertical axis against the reaction time on the horizontal axis and drawing a regression line gives a straight line expressed as y = -a _n ^' x (|-a _n ^' | = a _n ^' ), where _{a n} ^' represents the degradation rate of the catalyst desulfurization reaction.

The same reaction is carried out for n types of sulfur concentration S _Pn , and n a _n and b _n are determined in the same manner, and n a _n ^' are obtained by the same method as above. n is an integer of 3 or more. The larger the number of n, the more accurate Ec can be obtained. On the other hand, if the number 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 _n ^'s and b _n values thus obtained are respectively substituted into the following formula 12. The following formula 12 is an equation that can calculate the activation energy and reference reaction temperature of coke, and was first discovered by the inventors of the present application based on the operating results of an actual machine, etc.

ln(a _n ^′ )=ln(A)−(Ec/Rb _n ) Equation 12
In Equation 12, A is a frequency factor, Ec is the activation energy of coke deterioration (kJ/mol), and R is the gas constant: 0.00831 (kJ/(mol·K)).

For n combinations of a _n ^' and b _n , ln(a _n ^' ) is plotted 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.

Also, T _B can be obtained by averaging n b _n values.

In determining Ec and _TB , 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 an actual plant.
Such an LHSV is, for example, 0.3 to 2.0 h ⁻¹ , the hydrogen partial pressure is, for example, 3 to 7 MPa, the hydrogen/feed oil 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 n-type sulfur concentrations S _Pn are set to conditions that correspond to the actual operating conditions of the engine. For example, S _Pn is 0.001 mass % or less.
The reaction period is, for example, 30 to 1600 days.

(How to calculate P _B and a)
The reaction is carried out for a certain period of time under conditions of constant LHSV, hydrogen/feed oil ratio, sulfur concentration in the feed oil, and sulfur concentration in the product oil, and hydrogen partial pressure _Pm . Because the catalyst deteriorates due to the reaction, operation is carried out while increasing the reaction temperature in order to maintain a constant sulfur concentration in the product oil. When the reaction time is plotted on the horizontal axis and the measured reaction temperature on the vertical axis and a regression line is drawn, a straight line expressed as y = _amx + _bm (0 < _am ) is obtained. _bm in this line is T _SOR ' in the above-mentioned formula 11. When _bm is substituted for T _SOR ' in the above-mentioned formula 11 and the measured reaction temperature is substituted for _Tt ', the deterioration degree Φ' of the desulfurization reaction after any t days of reaction has elapsed can be obtained. When the reaction time is plotted on the horizontal axis and the logarithm of Φ' on the vertical axis and a regression line is drawn, a straight line expressed as y = -a _m ^' x (|-a _m ^' | = a _m ^' ) is obtained. a _m ^' represents the deterioration rate of the desulfurization reaction of the catalyst.

The same reaction is carried out for m types of hydrogen partial pressure P _m , m a _m and b _m are determined in the same manner, and m a _m ^' are obtained by the same method as above. m is an integer of 3 or more. The larger the number of m, the more accurate a can be obtained. On the other hand, if the number 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 _m 's and P _m obtained in this way are respectively substituted into the following formula 13. The following formula 13 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.

ln( _am ^' )=-aln( _Pm )+B1 Equation 13
In the formula 13, B1 can be 0.

For m combinations of a _m ' and P _m , ln(a _m ^' ) is plotted on the vertical axis and ln(P _m ) on the horizontal axis, a regression line is drawn, and the slope is determined. This slope is the hydrogen partial pressure coefficient a.

In addition, P _B can be obtained by averaging the m types of hydrogen partial pressures P _m .

In determining a and P _B , the LHSV, hydrogen/feed oil ratio, sulfur concentration in the feed oil, and sulfur concentration in the product oil are preferably set to conditions that correspond to the operating conditions of an actual plant.
Such an LHSV is, for example, 0.3 to 2.0 h ⁻¹ , the hydrogen/feed oil 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.
Similarly, it is preferable that the hydrogen partial pressure _Pm of m units is set to a condition that corresponds to the operating conditions of the actual plant. Such _Pm is, for example, 3 to 7 MPa. The reaction period is, for example, 30 to 1600 days.

(How to find _GB and b)
The reaction is carried out for a certain period of time under the conditions of constant LHSV, hydrogen partial pressure, sulfur concentration in the feed oil, and sulfur concentration in the product oil, and a hydrogen/feed oil ratio of G _h . Because the catalyst deteriorates due to the reaction, operation is carried out while increasing the reaction temperature in order to maintain a constant sulfur concentration in the product oil. When the reaction time is plotted on the horizontal axis and the measured reaction temperature on the vertical axis and a regression line is drawn, a straight line expressed as y = a _h x + b _h (0 < a _h ) is obtained. b _h in this line is T _SOR ' in the above-mentioned formula 11. When b _h is substituted for T _SOR ' in the above-mentioned formula 11 and the measured reaction temperature is substituted for T _t ^' , the deterioration degree Φ' of the desulfurization reaction after any t days of reaction has elapsed can be obtained. When the reaction time is plotted on the horizontal axis and the logarithm of Φ' on the vertical axis and a regression line is drawn, a straight line expressed as y = - _{a h} ^' x (|- _{a h} ^' | = a _h ^' ) is obtained. a _h ^' represents the deterioration rate of the desulfurization reaction of the catalyst.

The same reaction is carried out for h types of hydrogen/feed oil ratios _Gh , h a _h and b _h are determined in the same manner, and h a _h ^' are obtained by the same method as above. h is an integer of 3 or more. The larger the number of h, the more accurate b can be obtained. On the other hand, if the number of h is too large, it takes 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 's and G _h 's thus obtained are respectively substituted into the following formula 14. The following formula 14 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.

ln( _ah ')=-bln( _Gh )+B2 Equation 14
In the formula 14, B2 can be 0.

For h combinations of a _h ' and G _h , ln(a _h ') is plotted on the vertical axis and ln(G _h ) on the horizontal axis, a regression line is drawn, and the slope is determined. This slope is the hydrogen/feed oil ratio coefficient b.

Moreover, _GB can be obtained by averaging the above h types of hydrogen/feedstock ratios _Gh .

In determining b and _GB, 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 an actual plant.
Such an 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 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.
Similarly, it is preferable that the hydrogen/feedstock ratio G _h of the h types is set to a condition that corresponds to the actual operating conditions. Such G _h is, for example, 100 to 700 [Nm ³ /kL]. The reaction period is, for example, 30 to 1600 days.

(Method 1 for determining α and T _SOR )
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 actual plant operating conditions. Because the catalyst deteriorates due to the reaction, operation is carried out while increasing the reaction temperature. Examples of the assumed actual plant operating conditions include the operating conditions described in (How to determine Ec and T _B ), (How to determine P _B and a), and (How to determine G _B and b). By plotting the reaction time on the horizontal axis and the measured reaction temperature on the vertical axis and drawing a regression line, a straight line expressed as y = a _α x + b _α is obtained. In this line, a _α is a value correlated with α in Equation 8, and b _α is T _SOR in Equation 8. Substituting b _α for T _SOR ′ and the measured reaction temperature for T _t ′ in Equation 11 gives the degree of deterioration Φ′ of the desulfurization reaction after any t days of reaction have elapsed. Plotting the logarithm of Φ' on the vertical axis against the reaction time on the horizontal axis yields a regression line expressed as y = -a _α ^' x (where |-a _α ^' | = a _α ^' ), where a _α ^' represents the degradation rate of the desulfurization reaction of the catalyst.

D is determined by substituting the operating conditions S _P , S _F , LHSV, P, and G, as well as P _B , a, G _B , b, Ec, T _{B , and} T _SOR (i.e., b _α ) determined by the above method, into Equation 8. Φ is obtained by substituting the determined D into Equation 7. 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 while changing α so that α is 0 < α, multiple straight lines expressed as y = -a _α ^" x (|-a _α ^" | = a _α ^" ) are obtained for each value of α. The α when a _α ^" on each straight line is equal to the above-mentioned a _α ^' can be defined as the α in Equation 8.

(Method 2 for determining α and T _SOR )
A reaction similar to that in (Method 1 for Determining α and T _SOR ) is carried out to obtain a straight line expressed as y = a _α x + b _α , and b _α is defined as T _SOR in the above formula 8. D is determined by substituting the operating conditions S _P , S _F , LHSV, and P, and P _B , a, G _B , b, Ec, T _{B , and} T _SOR (i.e., b _α ) determined by the above method into the above formula 8. Φ is obtained by substituting the determined D into the above formula 7. In this case, Φ is a function of α. Substituting the obtained Φ into Φ' in the above formula 11 and T _SOR (i.e., b _α ) into T _SOR ^' in the above formula 11 and rearranging for T _t ', T _t ' becomes a function of α. The α in the above formula 8 can be defined as the α when the ratio (T _t '/T _obs ) of T _t ' to the measured reaction temperature T _obs is 1. Similarly, it is preferable to calculate N ratios (T _t '/T _obs ) of T _t ' to the reaction temperature T _obs , and define the α when the average of these is closest to 1 as the α in the above formula 8. N is an integer of 10 or more, preferably 10 to 500, and more preferably 50 to 200.

<Degradation function 2 of desulfurization reaction>
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 15, 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 hardly deactivated active species deterioration function relating to the deterioration of hardly deactivated active species in the desulfurization reaction of the catalyst.

Φ=k ₁ ×exp(-D ₁ t)+k ₂ ×exp(-D ₂ t) Equation 15
In Equation 15, _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.

As mentioned above, in the hydrotreating reaction of feedstock containing diesel fractions, catalyst degradation occurs due to coke buildup, and therefore operation must be carried out at elevated reaction temperatures to maintain the sulfur content of the resulting oil below a certain level. In the hydrotreating reaction of feedstock containing diesel fractions, the reaction temperature rises rapidly at the beginning of the reaction. This rapid rise in reaction temperature indicates rapid catalyst degradation at the beginning of the reaction. On the other hand, from the middle of the reaction onwards, the reaction temperature rises gradually. This gradual rise in reaction temperature indicates gradual catalyst degradation at the middle of the reaction onwards.

In other words, the profile of reaction temperature versus reaction time suggests that in the hydrotreating reaction of feedstock containing diesel fractions, rapid catalyst degradation occurs early in the reaction, followed by gradual catalyst degradation from the middle of the reaction onwards.

The inventors of the present application further improved Degradation Function 1 and discovered Degradation Function 2 based on the above-mentioned profile of reaction temperature versus reaction time and the assumption that the catalyst contains active species that are easily deactivated for the desulfurization reaction, which are deactivated early in the reaction, and active species that are difficult to deactivate for the desulfurization reaction, which are deactivated from the middle or later stages of the reaction. As a result, they found that Degradation Function 2 makes it possible to calculate the degree of degradation of the catalyst's desulfurization reaction more accurately than Degradation Function 1. Easily deactivated active species for the desulfurization reaction are active species that lose activity mainly in the early stages of the reaction, and difficult to deactivate active species for the desulfurization reaction are active species that lose activity from the middle or later stages of the reaction.

In the above formula 15, _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 determination will be described later.

_D1 can be calculated using the following formula 16, and _D2 can be calculated using the following formula 17.

In the above formulas 16 and 17, 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 a light oil fraction, 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)), T _B is the reference reaction temperature (K), and T _SOR is the temperature requirement on day 0 (K).
In the above formula 16, _α1 is a 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 17, _α2 is a 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).

In the above-mentioned formulas 16 and 17, 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 above-mentioned information acquisition step, as in the explanation of the above-mentioned formula 8. Note that LHSV can be calculated by dividing the feed oil supply rate (volume/h) by the catalyst loading rate (volume). G can be calculated by dividing the hydrogen supply rate (Nm ³ /hour) by the feed oil supply rate (kL/hour).

As described above, S _F , LHSV, P, and G are controllable parameters. Furthermore, S _P is the sulfur concentration of the target product oil. That is, the deterioration coefficient of the easily deactivated active species in the desulfurization reaction of the catalyst and the deterioration coefficient of the less easily deactivated active species in the desulfurization reaction of the catalyst under the reaction conditions of S _F , S _P , LHSV, and P can be calculated using the above-mentioned Equations 16 and 17. The method for determining n, which is the reaction order of the hydrotreating reaction of feedstock oil containing a diesel fraction, will be described later.

(How to determine basic degradation parameters)
In the above-mentioned formulas 16 and 17, α ₁ , α ₂ , P _B , a, G _B , b, Ec, T _B , and T _SOR are constants, as in the above-mentioned formula 8, 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 performing a reaction in an actual machine, or may be determined in advance on a bench scale based on the actual machine operating conditions. In this embodiment, it is preferable to determine it in advance on a bench scale based on the actual machine operating conditions. In the above-mentioned formulas 16 and 17, P _B , a, G _B , b, Ec, and T _B can be determined by the same method as in the above-mentioned formula 8.
On the other hand, α ₁ , α ₂ and T _SOR can be calculated, for example, by the following two methods. In addition, the active site coefficient k ₁ of the easily deactivated active species in the desulfurization reaction of the catalyst and the active site coefficient k ₂ of the hardly deactivated active species in the desulfurization reaction of the catalyst in the above formula 15 can also be calculated simultaneously as follows.

(Method 1 for determining α ₁ , α _{2 ,} T _SOR , k ₁ , and k ₂ )
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, operation is carried out while increasing the reaction temperature. Reaction time is plotted on the horizontal axis and reaction temperature on the vertical axis. When drawing a regression line between these plots, as described above, two lines are obtained: one line expressed as y = a ₁ x + b ₁ , which correlates with the rapid increase in reaction temperature in the early stage of the reaction (x ₁ to x _n ), and the other line expressed as y = a ₂ x + b ₂ , which correlates with the gradual increase in reaction temperature from the middle stage of the reaction onwards ( _{x n+1} to x _m ). In the above formula, a ₁ > a ₂ > 0, b ₁ < b ₂ , and x ₁ < x _n < x _n+1 < x _m . x _n and x _m represent the reaction time relative to the n(m)th plot from the start of the reaction.

The above-mentioned _a1 is a value correlated with _α1 , _b1 is a value correlated with _k1 + _k2 , and is T _SOR . Furthermore, _a2 is a value correlated with _α2 , and _b2 is a value correlated with _k2 . Next, the intersection point (x _ip , y _ip ) at y = a ₁ x + b ₁ and y = a ₂ x + b ₂ is calculated. This intersection point represents the inflection point of y = a ₁ x + b ₁ and y = a ₂ x + b _2. In other words, up to (x _ip , y _ip ), only active species that are easily deactivated in the desulfurization reaction of the catalyst are considered to exist, and from (x _ip , y _ip ), two active species are considered to exist: an active species that is easily deactivated in the desulfurization reaction of the catalyst and an active species that is difficult to deactivate in the desulfurization reaction of the catalyst.

In the above equation 11, substituting _b1 for T _SOR ' and substituting the reaction temperature for T _t ' will give the degree of deterioration Φ' of the desulfurization reaction after any t days of reaction. Plotting the reaction time on the horizontal axis and the logarithm of Φ' on the vertical axis and drawing a regression line from x ₁ to x _ip will give a line expressed as y = -a ₁ ^' x (|-a ₁ ^' | = a ₁ ^' ). Furthermore, drawing a regression line from x _ip to x _m will give a line expressed as y = -a ₂ ^' x -b ₂ ^' (|-a ₂ ^' | = a ₂ ^' and |-b ₂ ^' | = b ₂ ^' ). _{a 1} ^' is a value correlated with α ₁ , a ₂ ^' is a value correlated with α ₂ , and b ₂ ^' is a value correlated with k ₂ .

_k2 can ^{be found by substituting b2'} _obtained from the regression line described above into the following formula 18. Since _k1 is _k1 + _k2 = 1, k1 can be found from _k1 = 1 - _k2 .
k ₂ =exp(-b ₂ ^' ) Equation 18

D1 and D2 are obtained by substituting the operating conditions S _P , S _F , LHSV, P, and G, as well as P _B , a, G _B , b, _Ec , T _B , and T _SOR (b ₁ ) obtained by the above method, into the above equations 16 and _17. Φ is obtained by substituting the obtained D ₁ , D ₂ , k ₁ , and k ₂ into the above equation 15. In this case, Φ is a function of α ₁ and α ₂ . 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 from x ₁ to x _ip while setting α ₂ =0 and changing α ₁ so that 0 < α ₁ , multiple lines expressed as y = -a _α1 ^'' x (|-a _α1 ^'' | = a _α1 ^'' ) will be obtained for each value of α _1. The α 1 when a _α1 ^'' on each line is equal to the above-mentioned a ₁ ^' can be taken as _{the α 1 in} the above formula 16.
Next, by substituting the obtained _α1 into Φ, which is a function of _α1 and _α2 obtained by the above method, and drawing a regression line from _xip to _xm while changing _α2 so that 0 < _α2 , multiple lines expressed as y = _-aα2 ^" x- _bα2 ^" (| _-aα2 ^" | = _aα2 ^" ) are obtained for each value of _α2 . The α2 when _aα2 on each line is equal to the above-mentioned _a2 ^' can be taken as _{the α2} in the above formula 17.

(Method 2 for determining α ₁ , α _{2 ,} T _SOR , k ₁ , and k ₂ )
A reaction similar to that in (Method 1 for determining _α1 , α2 _, T _SOR , _k1 , and _k2 ) is carried out to obtain T _SOR ( _b1 ). D1 and D2 are obtained by substituting the operating conditions S _P , _SF , LHSV, and P, and P _B , a, Ec, T _B , and T _SOR ( _b1 ) determined by the above method into Equations 16 and 17. Φ is obtained by substituting _the determined _{D1 and D2 into} Equation 15. In this case, Φ is a function of _α1 , _α2 , _k1 , and _k2 . By substituting the obtained Φ for Φ' in the above formula 11 and substituting T _SOR (i.e., b ₁ ) for T _SOR ^' in the above formula 11 and rearranging for T _t ', T _t ' becomes a function of α ₁ , α ₂ , k ₁ , and k _2. If α ₂ is set to 0 and k ₂ = 1 - k ₁ , T _t ' becomes a function of α ₁ and k _1. The combination of α 1 and k ₁ when the ratio of T _t ' to the actually measured reaction temperature T _obs at x ₁ to x _ip (T _t '/T _obs ) is ₁ can be found, and this α ₁ can be used as α ₁ in the above formula 16. Note that k ₁ at this time is a provisional value. Similarly, it is preferable to calculate the ratio of T _t ' to M reaction temperatures T _obs (T _t '/T _obs ), and define α ₁ when the average of these is closest to 1 as α ₁ in the above formula 16. M is an integer of 10 or more, preferably 10 to 500, and more preferably 50 to 200.
Using the obtained _α1 , and setting _k1 = 1 - _k2 , _Tt ' becomes a function of _α2 and _k2 . The combination of _{α2 and k2} when the ratio (Tt'/ _Tobs ) of _Tt ' to the actually measured reaction temperature _Tobs at _xip to _xm is 1 is determined, and these _α2 and _k2 can be used as _α2 and _k2 in the above formula 17. By substituting the obtained _k2 into _k1 = 1 - _k2 , _k1 is determined, and this _k1 can be used as _k1 in the above formula 16. Similarly, it is preferable to calculate the ratios ( _Tt '/ _Tobs ) of _Tt ' to L reaction temperatures _Tobs , and use the _α2 and _k2 when their average is closest to 1 as the _α2 and _k2 in the above formula 17. Furthermore, it is preferable to use the _k1 determined from the obtained _k2 as the _k1 in the above formula 16. L is an integer of 10 or more, preferably 10 to 500, and more preferably 50 to 200.

In this way, in order to find α ₁ , α _{2 ,} T _SOR , k ₁ , and k ₂ , it is necessary to obtain y = a ₁ x + b ₁ and y = a ₂ x + b _2. For example, y = a ₁ x + b ₁ and y = a ₂ x + b ₂ can be found as follows.

Using the method described above, the reaction time is plotted on the horizontal axis and the reaction temperature on the vertical axis. By drawing a regression line from the start of the reaction to the end of the reaction, a straight line expressed as y = a'x + b' is obtained. This line does not take into account the inflection point. Plots are sequentially deleted from the end of the reaction, and the y = a'x + b' is adjusted so that the correlation coefficient approaches 1, resulting in y = _a1'x + _b1 '. Similarly, plots are sequentially deleted from the start of the reaction, and the y = a'x + b' is adjusted so that the correlation coefficient approaches ₁ , resulting in 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 belong to either y=a ₁ x+b ₁ or y=a ₂ x+b ₂ .

The reaction time required to obtain y = a ₁ x + b ₁ and y = a ₂ x + b ₂ 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 more.

<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.

<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 10. Similar to the calculation method for the above-mentioned equation 11, the following equation 19 is derived from the above-mentioned equations 6 and 10.

In Equation 19, Φ is the degree of deterioration of the desulfurization reaction, Ea is the activation energy of desulfurization (kJ/mol), R is the gas constant: 0.00831 (kJ/(mol·K)), _Tt is the required temperature (K) after t days of reaction, and T _SOR is the required temperature (K) on day 0.
By rearranging the above equation 19, the following equation 20 is obtained.

T _t (K) after t days of reaction can be obtained by substituting T _SOR and Φ obtained by the above-mentioned method into the above-mentioned formula 20. The activation energy of the desulfurization reaction in the above-mentioned formula 20 can be calculated as follows.

(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 10. An example will be described below.

First, the reaction order of the desulfurization reaction of feedstock containing a diesel fraction is determined. The reaction temperature, hydrogen partial pressure, hydrogen/feedstock ratio, and sulfur concentration in the feedstock are constant, and the reaction is carried out under LHSV(x) conditions, and the sulfur concentration in the product oil is measured. In the desulfurization reaction rate equation expressed by the following equation 21, the sulfur concentration in the feedstock is substituted for _SF , the sulfur concentration in the resulting product oil for _SP , and LHSV(x) for LHSV. The result of the left-hand side of the equation is plotted on the vertical axis and 1/LHSV on the horizontal axis. In this case, the vertical axis is a function of n.

A similar reaction is carried out for x types of LHSV(x), and x of the above plots are obtained. Based on the obtained plots, a regression line is drawn passing 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 ))), x is 1/LHSV, and c is k. The correlation function is calculated using Excel or similar software, and n is determined for which the correlation coefficient is closest to 1. The obtained n is the reaction order. Note that n can be calculated to one decimal place.

The above x is an integer of 3 or greater. 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 inefficient. In this embodiment, x is preferably 3 to 20, and more preferably 3 to 10.

In determining n, the reaction temperature, hydrogen partial pressure, hydrogen/feedstock ratio, and sulfur concentration in the feedstock are preferably set to conditions that correspond to the operating conditions of an actual plant.
Such a reaction temperature is, for example, 300 to 400°C, the hydrogen partial pressure is, for example, 3 to 7 MPa, the hydrogen/feedstock ratio is, for example, 100 to 700 [Nm ³ /kL], and the sulfur concentration in the feedstock 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 of the engine. Such LHSV(x) is, for example, 0.3 to 2.0 h ⁻¹ .

When the activation energy E in the Arrhenius equation expressed by the above formula 10 is set to the activation energy Ea of desulfurization and the natural logarithm of both sides is taken, the following formula 22 is obtained.

The reaction is carried out under constant conditions of hydrogen partial pressure, hydrogen/feed oil ratio, LHSV, and sulfur concentration in the feed oil at a reaction temperature T(y), and the sulfur concentration in the product oil is measured. The sulfur concentration in the feed oil is substituted for _SF , the sulfur concentration in the resulting product oil for _SP , LHSV for LHSV, and the obtained n in the desulfurization reaction rate equation expressed by Equation 21 above are substituted for LHSV, and the reaction rate constant k is calculated. The obtained reaction rate constant is substituted into Equation 22 above, and the result (lnk) on the left side of the equation obtained is plotted on the vertical axis and 1/T (1/T(y)) on the horizontal axis.

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

The above y is an integer of 3 or greater. The larger the value of y, the more accurate Ea can be obtained. On the other hand, if the value of y is too large, it takes a long time to obtain Ea, which is inefficient. In this embodiment, y is preferably 3 to 20, and more preferably 3 to 10.

The hydrogen partial pressure, hydrogen/feed oil ratio, LHSV, and sulfur concentration in the feed oil used to determine Ea are preferably set to conditions that correspond to the operating conditions of an actual plant.
Such hydrogen partial pressure is, for example, 3 to 7 MPa, the hydrogen/feedstock ratio is 100 to 700 [Nm ³ /kL], the LHSV is 0.3 to 2.0 h ⁻¹ , and the sulfur concentration in the feedstock 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.

By substituting each parameter thus obtained into the above-mentioned formula 20, the reaction temperature _Tt required to achieve the predetermined reaction conditions can be obtained.

The ratio of the reaction temperature _Tt determined by the information processing method of this embodiment to the actually measured reaction temperature _Tobs , _Tt / _Tobs, is preferably 0.97 to 1.03, and more preferably 0.985 to 1.015, in °C. When _Tt / _Tobs is within the above range, it can be determined that the reaction temperature has been estimated with high accuracy.

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

<Naphtha yield calculation function>
The naphtha yield calculation function is expressed by the following equation 23.

In the above-mentioned formula 23, C _t is the naphtha yield (mass %) after t days have passed since the reaction, k _C0(Tt) is the reaction rate constant (h −1 ) of the cracking reaction at the reaction temperature T _t calculated in the above-mentioned reaction temperature calculation step for the catalyst (fresh catalyst) after 0 days have passed since the reaction ( ^i.e. , at the start of the reaction), Φ _C is the degree of deterioration of the cracking reaction, and LHSV is the liquid hourly space velocity (h ⁻¹ ) after t days have passed since the reaction.

In the above-mentioned formula 23, LHSV is a value substituted based on the information on the operating conditions acquired in the information acquisition step described above. Note that LHSV can be calculated by dividing the feed oil supply amount (volume/h) by the catalyst loading amount (volume). How to calculate _{Φ C} and k _C0(Tt) will be described later.

As described above, in the above formula 1 _{, NAP(ave)} is the average naphtha concentration in the product oil over the certain period, and _NAF(ave) is the average naphtha concentration in the feed oil over the certain period. Here, the naphtha concentration in the product oil after any t days of reaction during the certain period is _NAP , and the naphtha concentration in the feed oil is _NAF . If naphtha is not contained in the light oil fraction ( _NAF = 0), then ( _NAP - _NAF ) becomes _NAP . Furthermore, if naphtha is considered to be produced by the cracking reaction of the light oil fraction, _NAP is expressed as the amount of naphtha obtained, _Ct (mass%). That is, according to this embodiment, ( _NAP - _NAF ) = _Ct .

The degradation degree of the decomposition reaction in the above formula 23 is expressed by the following formula 24.
Φ _C =k _Ct(T0) /k _C0(T0) Formula 24
In the above equation 24, k _C0(T0) is the reaction rate constant of the decomposition reaction of the catalyst (fresh catalyst) after 0 days of reaction (i.e., at the start of the reaction), and k _Ct(T0) is the reaction rate constant of the decomposition reaction of the catalyst after t days of reaction. Note that k _Ct(T0) and k _C0(T0) are the reaction rate constants of the decomposition reaction at the above-mentioned temperature T _SOR .

Equation 23 is derived based on the assumption that the cracking reaction of diesel is a first-order reaction and that naphtha is produced by the cracking reaction. The method for deriving equation 23 is explained below.

The decomposition reaction rate equation is expressed by the following equation 25.
k _Ct(Tt) = ln(C _F /C _P )×LHSV Equation 25
In the above equation 25, k _Ct(Tt) is the reaction rate constant (h ⁻¹ ) of the catalytic cracking reaction at the reaction temperature T _t calculated in the above-mentioned reaction temperature calculation step after t days have passed since the reaction, C _F is the diesel oil concentration (mass %) in the feedstock oil after t days have passed since the reaction, C _P is the diesel oil concentration (mass %) in the product oil after t days have passed since the reaction, and LHSV is the liquid hourly space velocity (h ⁻¹ ) after t days have passed since the reaction.

Since C _F /C _P is dimensionless, if C _F is set to 1, the conversion rate C _t (%) of the cracking reaction after any t days of reaction is C _t = (1 - C _P ) × 100. Therefore, C _P can be expressed as 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 (%) also becomes the amount of naphtha obtained (mass %). Substituting these values into the above formula 25, the following formula 26 is obtained.

When the above-mentioned formula 26 is summarized for _Ct , the following formula 27 is obtained.

From the above formula 24, the deterioration degree of the decomposition reaction can also be expressed by the following formula 28.

Φ _C =k _Ct(Tt) /k _C0(Tt) Formula 28
In the above formula 28, k _C0(Tt) is the reaction rate constant of the decomposition reaction of the catalyst (fresh catalyst) after 0 days of reaction (i.e., at the start of the reaction), and k _Ct(Tt) is the reaction rate constant of the decomposition reaction of the catalyst after t days of reaction. Note that k _Ct(Tt) and k _C0(Tt) are the reaction rate constants of the decomposition reaction at the reaction temperature _Tt after t days of reaction calculated in the reaction temperature calculation step described above.

From the above-mentioned equation 28, k _Ct(Tt) =Φ _C ×k _C0(Tt) , and by substituting this value into the above-mentioned equation 27, the above-mentioned equation 23 is derived.

Next, how to obtain Φ _C and k _C0(Tt) will be described.

(How to calculate _kC0(Tt) )
_kC0(Tt) is a parameter (constant) determined depending on the catalyst used, and may be determined while performing the reaction in an actual reaction system, or may be determined in advance on a bench scale based on the operating conditions of the actual reaction system. In this embodiment, it is preferable to determine it in advance on a bench scale based on the operating conditions of the actual reaction system.
_kC0(Tt) can be calculated by the following formula 29. The following formula 29 is based on the Arrhenius equation expressed by the above formula 10.

In the above formula 29, k _C0(T0) is the reaction rate constant (h ⁻¹ ) of the decomposition reaction of the catalyst (fresh catalyst) at the reaction temperature T _SOR after 0 days of reaction (i.e., at the start of the reaction), k _C0(Tt) is the reaction rate constant (h ⁻¹ ) of the decomposition reaction at the reaction temperature T _t after any t days of reaction calculated in the above-mentioned reaction temperature calculation step, E _D is the activation energy of the decomposition (kJ/mol), and R is the gas constant: 0.00831 (kJ/(mol·K)).

Since k _C0(T0) is the reaction rate constant of the decomposition reaction of the fresh catalyst at the reaction temperature T _SOR , it can be calculated using the following equation 30 based on the above equation 26.

In the above formula 30, C _t0 is the naphtha yield (mass %) when a desulfurization reaction of a feedstock containing a light oil fraction is carried out using a fresh catalyst at a reaction temperature T _SOR , and LHSV is the liquid hourly space velocity (h ⁻¹ ).

That is, k _C0(T0) can be calculated from the above-mentioned formula 30 by performing a hydrotreating reaction on a bench scale using a fresh catalyst, setting the reaction temperature to the above-mentioned T _SOR , and performing the hydrotreating reaction at LSHV, which is the operating condition of the actual plant, and measuring the amount of naphtha obtained at that time.

When determining _kC0(T0) on the bench scale, 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 an actual plant.
Such hydrogen partial pressure is, for example, 3 to 7 MPa, the hydrogen/feedstock ratio is 100 to 700 [Nm ³ /kL], the LHSV is 0.3 to 2.0 h ⁻¹ , and the sulfur concentration in the feedstock is 0.5 to 2.0 mass %.

_kC0(T0) may be determined while carrying out the reaction in an actual reactor as follows. It can be determined by substituting the amount of naphtha obtained and LHSV at the reaction temperature T _int immediately after the start of the reaction in the actual reactor (after t _int days of reaction) into the above-mentioned formula 30. T _int is preferably 20 days or less, more preferably 10 days or less. When t _int is equal to or less than the above-mentioned upper limit, a value very close to the reaction rate constant of the decomposition of a fresh catalyst can be obtained. Note that T _int is a value determined in the above-mentioned reaction temperature calculation step from the degree of deterioration of the desulfurization reaction.

The activation energy _ED of decomposition can be calculated as follows:

When the activation energy E in the Arrhenius equation expressed by the above formula 10 is set as the activation energy _ED of decomposition and the natural logarithm of both sides is taken, the following formula 31 is obtained.

The activation energy of cracking may be determined while the reaction is carried out in an actual plant, or may be determined in advance on a bench scale based on the operating conditions of the actual plant. The hydrogen partial pressure, hydrogen/feed oil ratio, LHSV, and sulfur concentration in the feed oil are constant, and the reaction is carried out at a reaction temperature T(y'), and the naphtha yield in the product oil is measured. The naphtha yield and LHSV obtained are substituted into Equation 26 to determine the reaction rate constant k. The obtained reaction rate constant is substituted into Equation 31, and the result (lnk) of the left-hand side obtained is plotted on the vertical axis and 1/T (1/T(y')) on the horizontal axis.

A similar reaction is carried out for y' types of reaction temperatures T(y'), and y' plots of the above are obtained. A regression line is drawn from the obtained plots, and its slope is determined. Since this slope is _ED /R, the activation energy of decomposition _ED can be determined by subtracting R from the slope.

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

In determining _ED , 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 an actual plant.
Such hydrogen partial pressure is, for example, 3 to 7 MPa, the hydrogen/feedstock ratio is 100 to 700 [Nm ³ /kL], the LHSV is 0.3 to 2.0 h ⁻¹ , and the sulfur concentration in the feedstock 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.

By substituting the thus obtained k _C0(T0) , the decomposition activation energy E _D , T _SOR , and the reaction temperature T _t calculated in the reaction temperature calculation step described above into the above equation 29, k _C0(Tt) is calculated.

<Deterioration of decomposition reaction>
When the desulfurization reaction activity of a catalyst decreases, the cracking reaction activity also decreases. Therefore, it is believed that there is a correlation between the degree of degradation of the desulfurization reaction and the degree of degradation of the cracking reaction. The inventors of the present application focused on this correlation and discovered for the first time that the degree of degradation of the cracking reaction Φ _C can be calculated based on the above-mentioned degree of degradation of the desulfurization reaction Φ. Below, we will explain how to calculate the degree of degradation of the cracking reaction Φ _C based on the desulfurization reaction deterioration function 1 and the desulfurization reaction deterioration function 2.

(Method 1 for determining the degradation level of decomposition reaction)
Method 1 for determining Φ _C is a method for determining Φ _C based on the degradation function 1 of the desulfurization reaction. Φ _C can be determined by the following equation 32.

Φ _C = βΦ Equation 32
In the above formula 32, Φ _C is the degradation degree of the decomposition reaction, Φ is the degradation degree of the desulfurization reaction (degradation function 1 of the desulfurization reaction), and β is the degradation coefficient of the decomposition reaction (constant).

Since Φ can be calculated by the above-mentioned method, once β is determined, Φ _C can be calculated from Φ. In addition, in the above formula 32, Φ _C at the time when the reaction has elapsed 0 is βΦ=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 those of the assumed actual plant operating conditions. Because the catalyst deteriorates due to the reaction, operation is carried out while increasing the reaction temperature. The reaction temperature at this time may be the reaction temperature _Tt calculated in the reaction temperature calculation step described above. Examples of assumed actual plant operating conditions include the conditions used to calculate the activation energy of cracking described above. ΦC is calculated by measuring the naphtha yield Ct _' after t' days have passed since any reaction, and substituting the obtained _{Ct' , kC0(Tt)} ( _kC0(Tt') ) calculated by the above method, and LHSV into Equation 23. _ΦC is also calculated after t' days have passed since any reaction using the above method. _ΦC and Φ are calculated in the same manner for multiple reactions after t' have passed. The combinations of _ΦC and Φ obtained during the same reaction are plotted with Φ on the x-axis and _ΦC on the y-axis. 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 for determining β is preferably 10 to 100, more preferably 10 to 50. Furthermore, the time t' for determining β is preferably 3 days or more after the reaction has started.

(Method 2 for determining the degradation level of decomposition reaction)
Method 2 of determining Φ _C is a method of determining Φ _C based on the degradation function 2 of the desulfurization reaction. Φ _C can be determined by the following equation 33.

Φ _C = β ₁ Φ ₁ + β ₂ Φ ₂ Equation 33
In the above formula 33, Φ _C is the degradation degree of the decomposition reaction, Φ ₁ is k ₁ × exp(−D ₁ t) in the above formula 15, Φ ₂ is k ₂ × exp(−D ₂ t) in the above formula 15, β ₁ is the decomposition degradation coefficient (constant) of the easily deactivated active species of the catalyst, and β ₂ is the decomposition degradation coefficient (constant) of the hardly deactivated active species of the catalyst.

Since Φ ₁ and Φ ₂ can be determined by the above-mentioned method, once β ₁ and β ₂ are determined, Φ _C can be determined from Φ ₁ and Φ _2. In addition, in the above formula 33, Φ _C at the time when the reaction has elapsed for 0 days is β ₁ Φ ₁ + β ₂ Φ ₂ = 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 those of the assumed actual plant operating conditions. Because the catalyst deteriorates due to the reaction, operation is carried out while increasing the reaction temperature. The reaction temperature at this time may be the reaction temperature _Tt calculated in the reaction temperature calculation step described above. The naphtha yield Ct _' is measured after t' days of any reaction have elapsed, and _ΦC is calculated by substituting the obtained Ct _' , _kC0(Tt) ( _kC0(Tt') ) calculated by the above method, and LHSV into Equation 23. Also, _Φ1 and _Φ2 after t' days of any reaction are calculated using the above method. The obtained _ΦC , _Φ1 , and _Φ2 are substituted into Equation 33. Similarly, _ΦCn , _Φ1n , and _Φ2n are obtained after t' days of n-number of reactions have elapsed. If Equation 33 is satisfied for each combination, a simultaneous two-variable linear equation of Φ _Cn = β ₁ 'Φ _1n + β ₂ 'Φ _2n is obtained. In this equation, β ₁ ' and β ₂ ' with minimum error can be determined by two-variable linear regression with Φ _Cn as the dependent variable _{and Φ 1n} and Φ _2n as independent variables. The obtained β ₁ ' can be used as β ₁ in Equation 33, and the obtained β ₂ ' can be used as β ₂ in Equation 33. The number of combinations of Φ _C , Φ ₁ , and Φ ₂ in determining β ₁ and β ₂ is preferably 10 to 100, and more preferably 10 to 50. Furthermore, the aforementioned t' in determining β ₁ and β ₂ is preferably after 3 days of reaction have elapsed.

Using β or _β1 and _β2 obtained by the above method, _ΦC can be calculated from the above formula 32 or formula 33.

By substituting k _C0(Tt) obtained by the above-mentioned method, Φ _C obtained by the above-mentioned formula 32 or the above-mentioned formula 33, and LHSV into the above-mentioned formula 23, the yield of naphtha after t days of reaction can be calculated.

The ratio of the naphtha yield _Ct calculated by the information processing method of this embodiment to the actually measured naphtha yield C _obs , C _t /C _obs , is preferably 0.80 to 1.20, and more preferably 0.85 to 1.15, in mass %. When C _t /C _obs is within the above range, it can be determined that the naphtha yield has been estimated with high accuracy.

From the above, S _F and S _P are set as set values, and the reaction temperature T _t required to achieve these set values is estimated. Furthermore, the naphtha yield (C _t) is calculated based on the reaction temperature and the degree of deterioration of the cracking reaction of the catalyst. During the certain period, S _F and S _P can be set as constant values, and these values can be set as S _F(ave) and S _P(ave) . Furthermore, during the certain period, C _t (NA _P - _NAF ) can be calculated one or more times, and the average can be set as (NA _P(ave) - _NAF(ave) ). Furthermore, during the certain period, DE _F can be set as a constant value, and this value can be set as DE _F(ave) . Furthermore, during the certain period, T _t can be obtained one or more times, and an estimated density DE _P ' of the product oil after any t days of reaction have passed can be obtained from Equation 5, and the average can be set as DE _P(ave) '.
The method may further include an information output step (S5A in FIG. 2) of outputting the information calculated by information processing method A of this embodiment. Furthermore, the information may be output (transmitted) to the information acquisition step of the information processing method of the present invention. For example, S5A is executed by the output unit 24. S _F , S _P , _NAP , _NAP , DE _F , and DE _P ' obtained by the information processing method of this embodiment are information obtained after t days have elapsed since any reaction, and it is sufficient that the time t days have elapsed is included in the certain period.

The ratio of hydrogen consumption H _C calculated by the data processing method of this embodiment to the actually measured hydrogen consumption H _RC , H _{C /H RC, is preferably 0.85 to 1.15, and more preferably 0.9 to 1.1, in terms of Nm 3. When H C /} ^H _{RC is} within this range, it can be determined that the hydrogen consumption has been estimated with high accuracy.

<Information output step>
The method may further include an information output step (S3 in FIG. 1) of outputting information indicating the amount of hydrogen consumed in the hydrotreating reaction calculated in this manner. For example, S3 is executed by the output unit 14.

<Hydrotreatment reaction of feedstock containing diesel fraction>
The hydrotreating reaction of feedstock containing diesel fractions will be outlined below.
In this specification, the term "diesel fraction" refers to a boiling point range of 150 to 380°C, and includes, for example, catalytically cracked diesel fuel, thermally cracked diesel fuel, hydrotreated diesel fuel, desulfurized diesel fuel, and mixtures thereof, which are obtained by subjecting straight-run diesel fuel and heavy oil obtained by atmospheric distillation of crude oil to catalytic cracking, thermal cracking, hydrotreating, and desulfurization, respectively, followed by fractional distillation. The content of the diesel fraction in the feedstock oil may be, for example, 50% by volume or more, or 80% by volume or more.
Incidentally, fractions other than the light oil fraction contained in the feedstock include naphtha and the like.

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.
In this specification, the term "aromatic compound" refers to a cyclic unsaturated organic compound, and among these, a compound having 1 to 3 or more rings.

The hydrotreating reaction of a feedstock containing a gas oil fraction can be carried out by contacting the feedstock containing a gas oil fraction with a hydrotreating catalyst.
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 among aluminas, γ-alumina being particularly preferred. These inorganic oxides may be used alone or in combination of two or more.

The metal contained in the support as an active component is at least one metal selected from Group 6 and Groups 8-10 of the Periodic Table, preferably molybdenum, tungsten, cobalt, and nickel. These metals are effective in 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 10-25 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 low, preventing hydrotreating activity (hereinafter simply referred to as hydrotreating activity), including desulfurization activity. Conversely, if the supported metal content is greater than 25 mass%, metal aggregation occurs, reducing the number of active sites and, as a result, reducing hydrotreating activity. Furthermore, if necessary, phosphorus, boron, zinc, zirconia, etc. can be contained in addition to the active metals consisting of Groups 6 and 8 of the Periodic Table. When applying the method of the present invention, there are no restrictions on the form of the catalyst bed, and it can be applied to catalyst bed reactors such as fixed beds, moving beds, and fluidized beds.

The conditions for the hydrotreating reaction of feedstock containing a diesel fraction are generally a reaction temperature of 300 to 400°C, preferably 330 to 380°C, a hydrogen partial pressure of 3 to 7 MPa, preferably 4 to 6 MPa, a liquid hourly space velocity in the reactor of 0.3 to 2 hr ^-1 , preferably 0.5 to 1.5 hr ^-1 , and a hydrogen/feedstock ratio of 100 to 700 [Nm ³ /kL], preferably 200 to 500 [Nm ³ /kL].

<Hydrogen consumption calculation device>
The hydrogen consumption calculation device of this embodiment includes an acquisition unit that acquires information about a feedstock containing a light oil fraction and information about a product oil over a certain period of time regarding a hydrotreatment reaction of the feedstock containing a light oil fraction, and a calculation unit that calculates the amount of hydrogen consumed in the hydrotreatment reaction over the certain period of time based on the information about the feedstock and the information about the product oil acquired by the acquisition unit. The hydrogen consumption calculation device of this embodiment may also have an output unit that outputs information about the calculated amount of hydrogen consumed in the hydrotreatment reaction over the certain period of time.

The naphtha yield calculation device of this embodiment includes an acquisition unit that acquires information about the feedstock, information about the product oil, and information about operating conditions a predetermined time after the start of the hydrotreating reaction of a feedstock containing a light oil fraction; and a calculation unit that calculates the degree of degradation of the desulfurization reaction and the degree of degradation of the cracking reaction of the catalyst using a degradation function based on the information about the feedstock, information about the product oil, and information about the operating conditions acquired by the acquisition unit; calculates the reaction temperature required to satisfy the information about the feedstock, information about the product oil, and the operating conditions based on the calculated degree of degradation of the desulfurization reaction of the catalyst; and calculates the naphtha yield based on the calculated reaction temperature and the degree of degradation of the cracking reaction of the catalyst. The naphtha yield calculation device of this embodiment may also have an output unit that outputs information about the calculated naphtha yield.

The hydrogen consumption calculation device 1 and naphtha yield calculation device 2 of this embodiment are configured using information processing devices such as personal computers, server devices, and dedicated devices. The hydrogen consumption calculation device 1 and naphtha yield calculation device 2 may be configured using one or more information processing devices. Furthermore, the hydrogen consumption calculation device 1 and naphtha yield calculation device 2 may be configured using an integrated information processing device. For example, the hydrogen consumption calculation device 1 and naphtha yield calculation device 2 may be configured as a cluster machine, a cloud, or in any other manner. The hydrogen consumption calculation device 1 (naphtha yield calculation device 2) includes, for example, an acquisition unit 11 (acquisition unit 21) and a computer main body 12 (computer main body 22) that processes information from the acquisition unit, as shown in FIG. 3 (FIG. 4). The hydrogen consumption calculation device 1 (naphtha yield calculation device 2) may also include an output unit 14 (output unit 24) that outputs information processed in the computer main body 12 (computer main body 22) to the outside. These components are implemented by a hardware processor, such as a central processing unit (CPU), executing a program (software). Some or all of these components may be implemented by hardware (including circuitry), such as a large-scale integrated circuit (LSI), an application-specific integrated circuit (ASIC), a field-programmable gate array (FPGA), or a graphics processing unit (GPU), or by a combination of software and hardware. The program may be stored in advance on a storage device (a storage device with a non-transitory storage medium) such as a hard disk drive (HDD) or flash memory, or on a removable storage medium (a non-transitory storage medium) such as a DVD or CD-ROM, and installed on the storage device by inserting the storage medium into a drive. The storage device may be, for example, an HDD, flash memory, electrically erasable programmable read-only memory (EEPROM), read-only memory (ROM), or random access memory (RAM).

The acquisition unit 11 (acquisition unit 21) receives predetermined information input by the reaction operator and transmits the information acquired through this input to the computer main body 12. The acquisition unit 11 may also acquire information calculated by the naphtha yield calculation device. The information acquired by the acquisition unit 11 in this embodiment is information about the feedstock oil and the product oil over a certain period of time, regarding the hydrotreating reaction of feedstock oil containing a light oil fraction. The information about the feedstock oil and the product oil over a certain period of time is 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 about the feedstock oil and the product oil over a certain period of time, and the acquisition method is not particularly limited. The information acquired by the acquisition unit 21 in this embodiment is information about the feedstock oil, the product oil, and the operating conditions after a certain time has elapsed since the start of the reaction, regarding the hydrotreating reaction of feedstock oil containing a light oil fraction. The information about the feedstock oil, the product oil, and the operating conditions after a certain time has elapsed since the start of the reaction are as described above. For example, the acquisition unit 21 executes the information acquisition step of the above-described information processing method A. The acquisition unit 21 only needs to acquire information about the feedstock oil, information about the product oil, and information about the operating conditions a predetermined time after the start of the reaction, and there are no particular limitations on the acquisition method.

In this embodiment, the acquisition unit 11 (acquisition unit 21) is configured with a single keyboard. The specific configuration of the acquisition unit 11 (acquisition unit 21) is not limited, and although it is a keyboard in this embodiment, it may also be a touch panel, etc. Note that acquisition units that acquire various types of information may be configured separately, and each may be independently connected to the computer main body 12 (computer main body 22). Furthermore, the acquisition unit 11 (acquisition unit 21) may be configured to directly acquire each piece of information via wired or wireless connections from a computer, etc. used for controlling the reactor, etc. The acquisition unit 11 may also be configured to directly acquire each piece of information via wired or wireless connections from the computer main body 22.

The computer main body 12 (computer main body 22) is, for example, a so-called computer capable of processing various types of information. The computer main body 12 (computer main body 22) is equipped with an arithmetic unit 13 (arithmetic unit 23). For example, a predetermined program is installed in this computer main body 12 (computer main body 22), and the arithmetic unit 13 (arithmetic unit 23) is functionally configured by executing this program. Specifically, this arithmetic unit 13 calculates the amount of hydrogen consumed in the hydrotreating reaction over a certain period of time based on information about the feedstock oil and information about the product oil acquired by the acquisition unit 11. As described above, the amount of hydrogen can be determined, for example, from the hydrogen consumption function described above. Furthermore, the calculation unit 23 calculates the degree of catalyst deterioration 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 21 at the time a predetermined time has elapsed since the start of the reaction. The calculation unit 23 calculates the reaction temperature required to satisfy the information on the feed oil, the information on the product oil, and the operating conditions based on the degree of catalyst deterioration, and calculates the naphtha yield based on the reaction temperature and the degree of catalyst deterioration. The deterioration function is as described above. As described above, the reaction temperature can be determined, for example, from a deterioration rate equation. The naphtha yield can be determined, for example, from a naphtha yield function. The calculation unit 13 (calculation unit 23) may include, for example, a processor such as a CPU (Central Processing Unit) or an MPU (Micro Processing Unit) and a non-volatile or volatile semiconductor memory (for example, RAM (Random Access Memory), ROM (Read Only Memory), flash memory, EPROM (Erasable Programmable Read Only Memory), or EEPROM (Electrically Erasable Programmable Read Only Memory)). For example, the calculation unit 13 (calculation unit 23) may be a microcontroller such as an MCU.

The calculation unit 13 may output information indicating the amount of hydrogen consumed in the hydrotreating reaction determined as described above to the output unit 14. The calculation unit 23 may output information indicating the amount of naphtha obtained as described above to the output unit 24.

The output unit 14 (output unit 24) receives the calculation results (such as the amount of hydrogen consumed in the hydrotreating reaction and the amount of naphtha obtained) output by the computer main body 12 (computer main body 22) (more specifically, the calculation unit 13 (calculation unit 23)), and outputs the received calculation results to the outside. In this embodiment, the output unit 14 (output unit 24) is configured as a display unit such as a CRT display, LCD display, or 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 diesel). The output unit 14 (output unit 24) may also be a combination of these. For example, the output unit 14 (output unit 24) executes the information output step described above.

In addition, this embodiment provides a hydrogen consumption calculation program or a naphtha yield calculation program for causing a computer to function as a hydrogen consumption calculation device or 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 tape (such as digital data storage (DSS)), magnetic disks (such as hard disk drives (HDDs) and flexible disks (FDs)), optical disks (such as compact disks (CDs), digital versatile disks (DVDs), and Blu-ray disks (BDs)), magneto-optical disks (MOs), and flash memory (such as solid-state drives (SSDs), memory cards, and USB memory).

<Method of using the information processing method and naphtha yield calculation device>
According to the information processing method and naphtha yield calculation device of this embodiment, it is possible to estimate the amount of hydrogen consumed in the hydrotreating reaction of feedstock oil containing a light oil fraction.

The present invention will be explained in more detail below using examples, but the present invention is not limited to the following examples.

[Analysis of the composition of feedstock oil and product oil]
The sulfur concentrations in the feedstock and the product oil were obtained by wavelength dispersive X-ray fluorescence spectroscopy.
The naphtha concentrations in the feed oil and the product oil were calculated from the proportion of fractions below 175°C by distillation tests.
The concentrations of aromatic compounds in the feedstock and the product were obtained by high performance liquid chromatography (HPLC).

[Actual hydrogen consumption values]
As described above, the amount of make-up hydrogen was measured with a flow meter, and the measured value was taken as the actual hydrogen consumption amount.

[Feedstock oil supply amount]
The feed oil supply rate was controlled by a feed oil delivery pump.
[Example 1]
A hydrotreating reaction was carried out by contacting a feedstock containing a diesel fraction with a hydrotreating catalyst. The compositions of the feedstock and the product oil were analyzed over time. The results are shown in Table 1. Table 1 also shows the value (( _HRC )/L) obtained by dividing the actual hydrogen consumption value ( _HRC ) for the corresponding period by the feedstock feed rate (L). The actual hydrogen consumption value and the feedstock feed rate were measured using the method described above. Data No. 1 represents data for a one-day (24-hour) period on the fourth day of operation, Data No. 2 represents data for a one-day (24-hour) period on the eighth day of operation, and so on. Measurement was carried out once per day, and the value was taken as the average for that day.
Using all the results of Data 1 to 10, multivariate analysis (with the intercept set to 0) was performed with the hydrogen consumption amount on the Y axis and _a1 (S _F -S _P ) + _a2 (NA _P -NA _F ) + _a3 (AR _F -AR _P ) on the X axis to determine _a1 , _a2 , and _a3 in Equation 1. The results were _a1 = 32.14, _a2 = 0.36, and _a3 = 2.96.

Using the obtained _a1 , _a2 , _a3 , (S _F -S _P ), (NA _P -NA _F ), and (AR _F -AR _P ), the value ((H C )/L ₎ obtained by dividing the amount of hydrogen consumed (H _C ) by the amount of feed oil supplied (L) was calculated using the results of Data 1 to 20 according to Equation 1. The results are shown in Table 2. As in Table 1, Data No. 1 represents data for a one-day (24-hour) period on the fourth day of operation, Data 2 represents data for a one-day (24-hour) period on the eighth day of operation, and so on.

As shown in Table 2, it was found that the hydrogen consumption calculated using the present invention was almost equivalent to the actual measured hydrogen consumption.

DESCRIPTION OF SYMBOLS 1... Hydrogen consumption amount calculation device 11... Acquisition unit 12... Computer main body 13... Calculation unit 14... Output unit 2... Naphtha yield calculation device 21... Acquisition unit 22... Computer main body 23... Calculation unit 24... Output unit

Claims (8)

an information acquisition step of acquiring information about the feedstock and information about the product oil for a certain period of time regarding the hydrotreating reaction of the feedstock containing the light oil fraction;
and a hydrogen amount calculation step of calculating the amount of hydrogen consumed in the hydrotreating reaction during the certain period based on the acquired information on the feedstock oil and information on the product oil,
the information about the feedstock oil includes information about the density of the feedstock oil , information about the composition of the feedstock oil, and information about the feedstock oil supply amount , and the information about the product oil includes information about the density of the product oil and information about the composition of the product oil ;
the hydrotreating reaction includes a hydrodesulfurization reaction, a hydrocracking reaction, and a hydrogenation reaction, and the hydrogen amount calculating step is a step of calculating the amounts of hydrogen consumed in the hydrodesulfurization reaction, the hydrocracking reaction, and the hydrogenation reaction during the certain period of time;
The amount of hydrogen consumed in the hydrogenation reaction is calculated based on information about the density of the feedstock oil and information about the density of the product oil ;
The information on the composition of the feedstock oil includes information on the sulfur concentration in the feedstock oil and information on the naphtha concentration in the feedstock oil, and the information on the composition of the product oil includes information on the sulfur concentration in the product oil and information on the naphtha concentration in the product oil,
The information processing method , wherein the hydrogen amount calculation step is a step of calculating the hydrogen amount using a hydrogen consumption amount calculation function expressed by the following equation 3:
In Equation 3, HC _is the estimated hydrogen consumption amount consumed in a certain period of time, S _F(ave) is the average sulfur concentration in the feed oil for the certain period of time, S _P(ave) is the average sulfur concentration in the product oil for the certain period of time, N A _P(ave) is the average naphtha concentration in the product oil for the certain period of time, N A _F(ave) is the average naphtha concentration in the feed oil for the certain period of time, DE _F(ave) is the average density of the feed oil for the certain period of time, DE _P(ave) is the average density of the product oil for the certain period of time, L is the feed amount of the feed oil for the certain period of time, and b ₁ , b ₂ , and b ₃ are tuning factors that are constants greater than 0. an information acquisition step of acquiring information about the feedstock and information about the product oil for a certain period of time regarding the hydrotreating reaction of the feedstock containing the light oil fraction;
and a hydrogen amount calculation step of calculating the amount of hydrogen consumed in the hydrotreating reaction during the certain period based on the acquired information on the feedstock oil and information on the product oil,
the information about the feedstock oil includes information about the density of the feedstock oil, information about the composition of the feedstock oil, and information about the feedstock oil supply amount, and the information about the product oil includes information about the density of the product oil and information about the composition of the product oil;
the hydrotreating reaction includes a hydrodesulfurization reaction, a hydrocracking reaction, and a hydrogenation reaction, and the hydrogen amount calculating step is a step of calculating the amounts of hydrogen consumed in the hydrodesulfurization reaction, the hydrocracking reaction, and the hydrogenation reaction during the certain period of time;
The amount of hydrogen consumed in the hydrogenation reaction is calculated based on information about the density of the feedstock oil and information about the density of the product oil;
The information on the composition of the feedstock oil includes information on the sulfur concentration in the feedstock oil and information on the naphtha concentration in the feedstock oil, and the information on the composition of the product oil includes information on the sulfur concentration in the product oil and information on the naphtha concentration in the product oil,
An information processing method, wherein the information regarding the density of the produced oil is information obtained from information regarding the density of the feedstock oil, and the hydrogen amount calculation step is a step of calculating the hydrogen amount using a hydrogen consumption amount calculation function expressed by the following equation 4.
In the above formula 4, _HC is the estimated hydrogen consumption amount consumed in a certain period of time, S _F(ave) is the average sulfur concentration in the feed oil for the certain period of time, S _P(ave) is the average sulfur concentration in the product oil for the certain period of time, NAP _(ave) is the average naphtha concentration in the product oil for the certain period of time, _NAF(ave) is the average naphtha concentration in the feed oil for the certain period of time, DE _F(ave) is the average density of the feed oil for the certain period of time, DE _P(ave) ' is the estimated average density of the product oil for the certain period of time calculated by the following formula 5, _fH is a tuning factor and is a constant, L is the supply amount of the feed oil for the certain period of time, and _b1 , _b2 , and _b3 are tuning factors and are constants greater than 0.
In the above formula 5, DE _F(ave) is the average density of the feedstock oil for the certain period, T is the average reaction temperature (°C) for the certain period, and α, β, and σ are catalytic coefficients determined for each catalyst used and are constants. an information acquisition step of acquiring information about the feedstock and information about the product oil for a certain period of time regarding the hydrotreating reaction of the feedstock containing the light oil fraction;
and a hydrogen amount calculation step of calculating the amount of hydrogen consumed in the hydrotreating reaction during the certain period based on the acquired information on the feedstock oil and information on the product oil,
The information processing method, wherein the hydrogen amount calculation step is a step of calculating the hydrogen amount using a hydrogen consumption amount calculation function expressed by the following equation 1:
In Equation 1, _HC is the estimated hydrogen consumption amount consumed in a certain period of time, S _F(ave) is the average sulfur concentration in the feed oil for the certain period of time, S _P(ave) is the average sulfur concentration in the product oil for the certain period of time, N A _P(ave) is the average naphtha concentration in the product oil for the certain period of time, N A _F(ave) is the average naphtha concentration in the feed oil for the certain period of time, AR _F(ave) is the average aromatic compound concentration in the feed oil for the certain period of time, AR _P(ave) is the average aromatic compound concentration in the product oil for the certain period of time, L is the feed amount of the feed oil for the certain period of time, and a ₁ , a ₂ , and a ₃ are tuning factors that are constants greater than 0. A hydrogen consumption calculation device comprising: an acquisition unit that acquires information about a feedstock oil and information about a product oil for a certain period of time in relation to a hydrotreating reaction of a feedstock oil containing a light oil fraction; and a calculation unit that calculates an amount of hydrogen consumed in the hydrotreating reaction for the certain period of time based on the information about the feedstock oil and the information about the product oil acquired by the acquisition unit,
the information about the feedstock oil includes information about the density of the feedstock oil , information about the composition of the feedstock oil, and information about the feedstock oil supply amount , and the information about the product oil includes information about the density of the product oil and information about the composition of the product oil ;
the hydrotreating reaction includes a hydrodesulfurization reaction, a hydrocracking reaction, and a hydrogenation reaction, and the calculation of the amount of hydrogen is performed by calculating the amounts of hydrogen consumed in the hydrodesulfurization reaction, the hydrocracking reaction, and the hydrogenation reaction during the certain period of time;
The amount of hydrogen consumed in the hydrogenation reaction is calculated based on information about the density of the feedstock oil and information about the density of the product oil ;
The information on the composition of the feedstock oil includes information on the sulfur concentration in the feedstock oil and information on the naphtha concentration in the feedstock oil, and the information on the composition of the product oil includes information on the sulfur concentration in the product oil and information on the naphtha concentration in the product oil,
The hydrogen consumption calculation device calculates the amount of hydrogen using a hydrogen consumption calculation function expressed by the following equation 3 .
In Equation 3, HC _is the estimated hydrogen consumption amount consumed in a certain period of time, S _F(ave) is the average sulfur concentration in the feed oil for the certain period of time, S _P(ave) is the average sulfur concentration in the product oil for the certain period of time, N A _P(ave) is the average naphtha concentration in the product oil for the certain period of time, N A _F(ave) is the average naphtha concentration in the feed oil for the certain period of time, DE _F(ave) is the average density of the feed oil for the certain period of time, DE _P(ave) is the average density of the product oil for the certain period of time, L is the feed amount of the feed oil for the certain period of time, and b ₁ , b ₂ , and b ₃ are tuning factors that are constants greater than 0. A hydrogen consumption calculation device comprising: an acquisition unit that acquires information about a feedstock oil and information about a product oil for a certain period of time in relation to a hydrotreating reaction of a feedstock oil containing a light oil fraction; and a calculation unit that calculates an amount of hydrogen consumed in the hydrotreating reaction for the certain period of time based on the information about the feedstock oil and the information about the product oil acquired by the acquisition unit,
the information about the feedstock oil includes information about the density of the feedstock oil, information about the composition of the feedstock oil, and information about the feedstock oil supply amount, and the information about the product oil includes information about the density of the product oil and information about the composition of the product oil;
the hydrotreating reaction includes a hydrodesulfurization reaction, a hydrocracking reaction, and a hydrogenation reaction, and the calculation of the amount of hydrogen is performed by calculating the amounts of hydrogen consumed in the hydrodesulfurization reaction, the hydrocracking reaction, and the hydrogenation reaction during the certain period of time;
The amount of hydrogen consumed in the hydrogenation reaction is calculated based on information about the density of the feedstock oil and information about the density of the product oil;
The information on the composition of the feedstock oil includes information on the sulfur concentration in the feedstock oil and information on the naphtha concentration in the feedstock oil, and the information on the composition of the product oil includes information on the sulfur concentration in the product oil and information on the naphtha concentration in the product oil,
A hydrogen consumption calculation device, wherein the information about the density of the product oil is information obtained from information about the density of the feedstock oil, and the calculation of the amount of hydrogen is performed using a hydrogen consumption calculation function expressed by the following equation 4.
In the above formula 4, _HC is the estimated hydrogen consumption amount consumed in a certain period of time, S _F(ave) is the average sulfur concentration in the feed oil for the certain period of time, S _P(ave) is the average sulfur concentration in the product oil for the certain period of time, NAP _(ave) is the average naphtha concentration in the product oil for the certain period of time, _NAF(ave) is the average naphtha concentration in the feed oil for the certain period of time, DE _F(ave) is the average density of the feed oil for the certain period of time, DE _P(ave) ' is the estimated average density of the product oil for the certain period of time calculated by the following formula 5, _fH is a tuning factor and is a constant, L is the supply amount of the feed oil for the certain period of time, and _b1 , _b2 , and _b3 are tuning factors and are constants greater than 0.
In the above formula 5, DE _F(ave) is the average density of the feedstock oil for the certain period, T is the average reaction temperature (°C) for the certain period, and α, β, and σ are catalytic coefficients determined for each catalyst used and are constants. A hydrogen consumption calculation device comprising: an acquisition unit that acquires information about a feedstock oil and information about a product oil over a certain period of time in relation to a hydrotreating reaction of a feedstock oil containing a light oil fraction; and a calculation unit that calculates an amount of hydrogen consumed in the hydrotreating reaction over the certain period of time based on the information about the feedstock oil and the information about the product oil acquired by the acquisition unit, wherein the calculation of the amount of hydrogen is performed using a hydrogen consumption calculation function expressed by the following equation 1.
In Equation 1, _HC is the estimated hydrogen consumption amount consumed in a certain period of time, S _F(ave) is the average sulfur concentration in the feed oil for the certain period of time, S _P(ave) is the average sulfur concentration in the product oil for the certain period of time, N A _P(ave) is the average naphtha concentration in the product oil for the certain period of time, N A _F(ave) is the average naphtha concentration in the feed oil for the certain period of time, AR _F(ave) is the average aromatic compound concentration in the feed oil for the certain period of time, AR _P(ave) is the average aromatic compound concentration in the product oil for the certain period of time, L is the feed amount of the feed oil for the certain period of time, and a ₁ , a ₂ , and a ₃ are tuning factors that are constants greater than 0. A hydrogen consumption calculation program for causing a computer to function as the hydrogen consumption calculation device according to any one of claims 4 to 6 . A non-transitory computer-readable recording medium storing the program according to claim 7 .