Method for predicting carbon residue value of heavy oil hydrogenation generated oil

Abstract

The invention relates to a method for predicting the carbon residue value of heavy oil hydrogenation generated oil, and the method comprises the following steps: obtaining a heavy oil raw material, and obtaining the characterization data of the characteristic properties of the heavy oil raw material; obtaining hydrogenated generated oil to be detected, wherein the hydrogenated generated oil to be detected is obtained by carrying out hydrogenation carbon residue removal reaction on the heavy oil raw material; substituting the characterization data of the characteristic properties of the heavy oil raw material into the characteristic factor equation of the hydrogenation carbon residue removal reaction, and calculating the characteristic factor of the hydrogenation carbon residue removal reaction; substituting the characteristic factor into the characteristic factor-reaction rate constant relation equation of the hydrogenation carbon residue removal reaction, and calculating the reaction rate constant of the hydrogenation carbon residue removal reaction; and substituting the reaction rate constant into the reaction kinetic equation of the hydrogenation carbon residue removal reaction, and calculating the predicted carbon residue value of the hydrogenation generated oil to be detected. By adopting the method disclosed by the invention, the carbon residue value of the heavy oil hydrogenation generated oil can be accurately predicted.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a method for predicting the carbon residue value of heavy oil hydroprocessing generated oil. BACKGROUND

[0002] At present, the crude oil is becoming heavier and poorer all over the world, while the demand for high-quality light oil is increasing, so heavy oil processing and full utilization have become the main topic of the oil refining industry. Heavy oil hydroprocessing is a widely used deep processing technology for heavy oil. Compared with non-hydroprocessing, the most significant advantage of heavy oil hydroprocessing is high liquid product yield, which can fully utilize valuable petroleum resources, so the application prospect of this process is relatively broad. Heavy oil hydroprocessing is mainly divided into four process types: fixed bed, ebullated bed, moving bed and slurry bed. Among them, the fixed bed heavy oil hydroprocessing technology is mature, easy to operate, the investment of the device is relatively low, and the hydrogen content of the product increases more, so it is the most widely used in industry.

[0003] The reaction kinetics model is used to describe the relationship between the reaction rate and the concentration of reactants, which is a very important part in the process of process research. By establishing the heavy oil reaction kinetics model, a small amount of parameters can be used to predict the properties of the products (heavy oil hydroprocessing generated oil) under different conditions, or the process conditions can be determined according to the requirements of the properties of the raw materials and products. However, due to the complexity of the heavy oil hydroprocessing process, the great difference in the properties of different raw oil (such as atmospheric residue and vacuum residue) and catalysts, it is often difficult to obtain a kinetics model with universal applicability, and the accuracy of product property prediction based on the corresponding kinetics model is not high. SUMMARY

[0004] The purpose of the present disclosure is to provide a method for predicting the carbon residue value of heavy oil hydroprocessing generated oil by reaction kinetics model and improve the prediction accuracy.

[0005] In order to achieve the above-mentioned purpose, the present disclosure provides a method for predicting the carbon residue value of heavy oil hydroprocessing generated oil, which comprises:

[0006] Obtaining a heavy oil raw material, and obtaining characterization data of characteristic properties of the heavy oil raw material, wherein the characteristic properties include at least one of sulfur content, metal component content, hydrocarbon component content, carbon residue value and viscosity;

[0007] Obtaining a heavy oil raw material, and obtaining characterization data of characteristic properties of the heavy oil raw material, wherein the characteristic properties include at least one of sulfur content, metal component content, hydrocarbon component content, carbon residue value and viscosity;

[0008] Substitute the characterization data of the characteristic properties of the heavy oil raw material into the characteristic factor equation of the hydro-decarbon residue reaction to calculate the characteristic factor of the hydro-decarbon residue reaction; wherein the characteristic factor equation is as follows (1):

[0009] HCCR = S a + U b + A c + CCR d + Q e (1)

[0010] In formula (1), H CCR represents a characteristic factor, S represents a sulfur content and has a unit of wt%, a is a sulfur content fitting index, U represents a metal component content factor, b is a metal component content factor fitting index, A represents a hydrocarbon component content factor, c is a hydrocarbon component content factor fitting index, CCR represents a carbon residue value and has a unit of wt%, d is a carbon residue value fitting index, Q represents a viscosity factor, and e is a viscosity factor fitting index;

[0011] The characteristic factors are substituted into a characteristic factor-reaction rate constant relationship equation of the hydrodecarbonization reaction to calculate a reaction rate constant of the hydrodecarbonization reaction; wherein the characteristic factor-reaction rate constant relationship equation is a linear regression fitting equation with the characteristic factors as independent variables and the reaction rate constant as a dependent variable;

[0012] The reaction rate constant is substituted into a reaction kinetics equation of the hydrodecarbonization reaction to calculate a predicted value of the carbon residue value of the to-be-tested hydroprocessed oil.

[0013] Optionally, the characteristic properties include a carbon residue value, a nickel content, a vanadium content, a saturates and aromatics content, a gum and asphaltene content, a carbon residue value, and a viscosity;

[0014] In formula (1), U is calculated according to formula (2) below, A is calculated according to formula (3) below, and Q is calculated according to formula (4) below:

[0015]

[0016] In formula (2), m v represents a vanadium content and has a unit of ppm, m Ni represents a nickel content and has a unit of ppm;

[0017]

[0018] In formula (3), m 饱和分芳香分 represents a saturates and aromatics content and has a unit of wt%, and m 胶质沥青质 represents a gum and asphaltene content and has a unit of wt%;

[0019] Q = log μ (4)

[0020] In formula (4), μ represents a viscosity at 100°C and has a unit of mm 2 / s;

[0021] In formula (1), a is 0.085-0.10, b is 0.005-0.016, c is 0.005-0.018, d is -0.013 to -0.005, and e is -1.2 to -0.8.

[0022] Alternatively, the characteristic factor-reaction rate constant relationship equation is as follows formula (5):

[0023] k CCR = pH CCR - q (5)

[0024] In formula (5), k CCR represents the reaction rate constant, p is 0.05-0.1, and q is 0.2-0.4.

[0025] Alternatively, the reaction kinetics equation is as follows formula (6):

[0026]

[0027] In formula (6), C CCR represents the carbon residue value of the hydrogenation product oil to be measured and the unit is wt.%, C CCR0 represents the carbon residue value of the heavy oil feedstock and the unit is wt.%, t represents the residence time of the heavy oil feedstock through the hydrogenation catalyst and the unit is h, and n represents the reaction order of the hydrogenation carbon residue removal reaction.

[0028] Alternatively, in formula (6), n is 1.3-2.2.

[0029] Alternatively, the heavy oil feedstock is atmospheric residue, and the 5 wt.% distillation temperature of the heavy oil feedstock is 350°C or higher; and / or,

[0030] The sulfur content of the heavy oil feedstock is 1.0-7.0 wt.%, and the nitrogen content is 0.01-0.6 wt.%.

[0031] Alternatively, the hydrogenation carbon residue removal reaction is carried out in a fixed bed reactor, and the fixed bed reactor is loaded with a hydrogenation catalyst.

[0032] Alternatively, the hydrogenation desulfurization catalyst comprises an active metal component and a carrier;

[0033] The active metal component is at least one selected from nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum, and cobalt-molybdenum; and the carrier is at least one selected from alumina, silica, and amorphous silica-alumina.

[0034] Alternatively, the hydrogenation catalyst comprises a hydrogenation guard, a hydrogenation demetallization agent, and a hydrogenation desulfurization and carbon residue removal agent loaded in sequence;

[0035] The volume ratio of the hydrogenation protective agent, the hydrogen demetallization agent, and the hydrogen desulfurization and residual carbon removal agent is 1:(5-14):(5-14).

[0036] Optionally, the conditions of the hydrogen desulfurization and residual carbon removal reaction include a temperature of 320-450℃, a pressure of 10-22MPa, a liquid hourly space velocity of 0.05-1.0h-1, and a hydrogen-oil volume ratio of 250-1500Nm3 / m3. -1 3 3

[0037] By the above technical solution, the present disclosure calculates the characteristic factor and the reaction rate constant of the heavy oil feedstock for the hydrogen desulfurization and residual carbon removal reaction according to the specific characteristic properties of the heavy oil feedstock, and obtains the predicted residual carbon value of the hydrogenated oil by combining the reaction kinetics equation. The method of the present disclosure can realize accurate prediction of the residual carbon value of the heavy oil hydrogenated oil.

[0038] Other features and advantages of the present disclosure will be described in detail in the following specific embodiment part. BRIEF DESCRIPTION OF DRAWINGS

[0039] The accompanying drawings are included to provide a further understanding of the present disclosure and constitute a part of the specification, and are used together with the following specific embodiments to explain the present disclosure but do not constitute a limitation on the present disclosure. In the drawings:

[0040] Figure 1 is a method flowchart for predicting the residual carbon value of heavy oil hydrogenated oil provided by the present disclosure. DETAILED DESCRIPTION

[0041] The specific embodiments of the present disclosure are described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present disclosure, and do not limit the present disclosure.

[0042] The present disclosure provides a method for predicting the residual carbon value of heavy oil hydrogenated oil, referring to Figure 1 The method comprises the following steps S101-S105:

[0043] S101, obtaining a heavy oil feedstock, and obtaining characteristic data of characteristic properties of the heavy oil feedstock, wherein the characteristic properties include at least one of sulfur content, metal component content, hydrocarbon component content, residual carbon value, and viscosity;

[0044] S102, obtaining a to-be-tested hydrogenated oil, which is obtained by hydrogen desulfurization and residual carbon removal reaction of the heavy oil feedstock;

[0045] ​​​S103, substituting the characterization data of the characteristic properties of the heavy oil feedstock into the characteristic factor equation of the hydro-decarbon residue reaction to calculate the characteristic factor of the hydro-decarbon residue reaction; wherein the characteristic factor equation is as follows formula (1):

[0046] H CCR =S a +U b +A c +CCR d +Q e (1)

[0047] In formula (1), H CCR represents the characteristic factor, S represents the sulfur content (wt%), a is the sulfur content fitting index, U represents the metal component content factor, b is the metal component content factor fitting index, A represents the hydrocarbon component content factor, c is the hydrocarbon component content factor fitting index, CCR represents the carbon residue value (wt%), d is the carbon residue value fitting index, Q represents the viscosity factor, and e is the viscosity factor fitting index;

[0048] S104, substituting the characteristic factor into the characteristic factor-reaction rate constant relationship equation of the hydro-decarbon residue reaction to calculate the reaction rate constant of the hydro-decarbon residue reaction; wherein the characteristic factor-reaction rate constant relationship equation is a linear regression fitting equation with the characteristic factor as the independent variable and the reaction rate constant as the dependent variable;

[0049] S105, substituting the reaction rate constant into the reaction kinetics equation of the hydro-decarbon residue reaction to calculate the predicted value of the carbon residue value of the to-be-tested hydrogenerated oil.

[0050] In step S101, the heavy oil feedstock can be atmospheric residue, and specifically, the 5 wt% distillation temperature of the heavy oil feedstock can be 350°C or higher. The method of the present disclosure is suitable for heavy oil feedstocks of various properties, and specifically, the heavy oil feedstock can satisfy at least one of the following characteristics: the viscosity can be 30-1500 mm 2 / s, the sulfur content can be 1.0-7.0 wt%, the nitrogen content can be 0.01-0.6 wt%, the carbon residue value can be 6-20 wt%, the metal component content can be 30-300 ppm, the saturated and aromatic component content can be 50-85 wt%, and the gum and asphaltene component content can be 15-50 wt%.

[0051] In a preferred embodiment, the sulfur content of the heavy oil feedstock is 1.5-6.0 wt%, and further preferably 3.0-5.0 wt%; the nitrogen content is 0.02-0.5 wt%, and further preferably 0.1-0.4 wt%. The method of the present disclosure is particularly suitable for heavy oil feedstocks having the above-mentioned ranges of sulfur content and nitrogen content, and the accuracy of the prediction of the carbon residue value of the hydro-up product obtained after the heavy oil feedstock is subjected to the hydro-decarbon residue reaction is high.

[0052] The characteristic properties are parameters used to establish the characteristic factor equation of the hydro-decarbon residue reaction. The inventors of the present disclosure found in research that the sulfur content, metal component content, hydrocarbon component content, carbon residue value and viscosity of the heavy oil feedstock have specific effects on the hydro-decarbon residue reaction and the properties of the hydro-up product obtained, and the establishment of the characteristic factor equation using the above-mentioned characteristic properties is conducive to achieving accurate prediction of the carbon residue value of the hydro-up product. Further, the metal components in the heavy oil feedstock can include nickel, vanadium, iron, calcium, etc.; the hydrocarbon components in the heavy oil feedstock may, for example, include saturates and aromatics, resins and asphaltenes, etc. The above-mentioned characteristic properties can be easily obtained in oil refineries and laboratories, making the method of the present disclosure easy to implement.

[0053] In a preferred embodiment, the characteristic properties include sulfur content, nickel content, vanadium content, saturates and aromatics content, resins and asphaltenes content, carbon residue value and viscosity. The sulfur content can be obtained by testing according to GB / T 17040-2008, the nickel content and vanadium content can be obtained by testing according to SH / T 0715, the saturates, aromatics, resins and asphaltenes content can be obtained by testing according to SH / T 0509, the carbon residue value can be obtained by testing according to GB / T 17144-1997, and the viscosity can be obtained by testing according to GB / T 11137-1989(2004).

[0054] In step S102, the hydro-decarbon residue reaction can be carried out in a fixed bed reactor filled with a hydro-up catalyst. The hydro-up catalyst can be conventional in the art, and specifically, the hydro-up catalyst can include an active metal component and a carrier; wherein the active metal component can be at least one selected from nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum and cobalt-molybdenum; and the carrier can be at least one selected from alumina, silica and amorphous silica-alumina.

[0055] Further, the hydrogenation catalyst can include a hydrogenation protective agent, a hydrogenation demetallization agent and a hydrogenation desulfurization and de-carbon residue agent which are sequentially filled in the fixed bed reactor. The hydrogenation protective agent is used to remove most of iron, calcium and sodium in the residual oil, and better accommodate dirt. The hydrogenation demetallization agent is used to remove metal impurities in the heavy oil raw material, mainly nickel and vanadium. The hydrogenation desulfurization and de-carbon residue agent is used to remove sulfides, nitrides and carbon residues in the heavy oil raw material. The volume ratio of the hydrogenation protective agent, the hydrogenation demetallization agent and the hydrogenation desulfurization and de-carbon residue agent can be adjusted within a certain range. Specifically, the volume ratio of the hydrogenation protective agent, the hydrogenation demetallization agent and the hydrogenation desulfurization and de-carbon residue agent can be 1:(5-14):(5-14), preferably 1:(7-12):(7-12).

[0056] The conditions of the hydrogenation de-carbon residue reaction can include a temperature of 320-450°C, a pressure of 10-22 MPa, a liquid hourly space velocity of 0.05-1.0 h-1, and a hydrogen-oil volume ratio of 250-1500 Nm3 / m3. -1 3 3

[0057] In step S103, the characteristic factor equation of the hydrogenation de-carbon residue reaction can be obtained by a multivariate power function fitting method using the characterization data of the existing heavy oil hydrogenation de-carbon residue reaction process, and can be obtained by using common fitting software such as 1stOpt.

[0058] In the embodiment in which the characteristic properties include sulfur content, nickel content, vanadium content, saturates and aromatic content, gum and asphaltene content, carbon residue value and viscosity, in formula (1), U is calculated according to formula (2) below, A is calculated according to formula (3) below, and Q is calculated according to formula (4) below:

[0059]

[0060] In formula (2), m represents vanadium content (ppm), m represents nickel content (ppm). v Ni

[0061]

[0062] In formula (3), m represents saturates and aromatic content (wt%), and m represents gum and asphaltene content (wt%). 饱和分芳香分 胶质沥青质

[0063] Q=logμ (4)

[0064] In formula (4), μ represents viscosity (100°C, mm / s). 2 ​​​​​​​​

[0065] Further, in formula (1), a can be 0.085-0.10, for example 0.087-0.091 or 0.090-0.095; b can be 0.005-0.016, for example 0.006-0.009 or 0.010-0.015; c can be 0.005-0.018, for example 0.007-0.010 or 0.011-0.015; d can be -0.013 to -0.005, for example -0.015 to -0.010 or -0.009 to -0.006; e can be -1.2 to -0.8, for example -1.18 to -0.98 or -0.95 to -0.87; when each fitting index is within the above range, the prediction accuracy of the measured hydrogenation generated oil residual carbon value is improved. For example, a can be 0.09, b can be 0.01, c can be 0.01, d can be -0.01, and e can be -0.923; or a can be 0.093, b can be 0.008, c can be 0.013, d can be -0.007, and e can be -1.083.

[0066] In step S104, the characteristic factor-reaction rate constant relationship equation of the hydrodecarbonization reaction can be obtained by linear regression fitting method using the existing characterization data of the heavy oil hydrodecarbonization reaction process.

[0067] In one embodiment, the characteristic factor-reaction rate constant relationship equation is as follows:

[0068] k CCR = pH CCR - q (5)

[0069] In formula (5), k CCR represents the reaction rate constant, and p and q are fitting coefficients and are both constants.

[0070] Further, p can be 0.05-0.1 and q can be 0.2-0.4; when the fitting coefficients are within the above range, the prediction accuracy of the measured hydrogenation generated oil residual carbon value is improved. For example, p can be 0.078 and q can be 0.320.

[0071] In step S105, the reaction kinetics equation of the hydrodecarbonization reaction refers to the relationship equation between the reaction rate constant and the residual carbon value of the hydrogenation generated oil to be measured.

[0072] In one embodiment, the reaction kinetics equation is as follows:

[0073]

[0074] In formula (6), C CCRrepresenting the carbon residue number (wt%) of the heavy oil feedstock, t represents the residence time (h) of the heavy oil feedstock through the hydrogenation catalyst, and n represents the reaction order of the hydro-decarbon residue reaction. CCR0 representing the carbon residue number (wt%) of the heavy oil feedstock, t represents the residence time (h) of the heavy oil feedstock through the hydrogenation catalyst, and n represents the reaction order of the hydro-decarbon residue reaction.

[0075] Further, n can be 1.3-2.2, for example, 1.5-1.8 or 1.9-2.1. For example, n can be 1.7; or n can be 2.

[0076] The present disclosure innovatively establishes the relationship between the characteristic factor H CCR and the reaction rate constant k CCR , so that the carbon residue number of the hydrogenation product oil under different process conditions can be predicted according to the specific characteristic properties of the heavy oil feedstock, with high prediction accuracy. The characteristic properties involved are all conventional parameters that are easy to obtain, making the process of implementing the present disclosure more convenient, without the need for additional complex tests or professional equipment, reducing the operation difficulty and cost. In addition, the reaction kinetics model and the method for predicting the carbon residue number of the hydrogenation product oil established by the present disclosure can also be used to determine appropriate process conditions according to the requirements of the properties of the heavy oil feedstock and the product (i.e. the prediction results), which has practical guiding significance for the optimization of the formulation scheme in industrial applications and the development of future higher performance heavy oil hydrogenation catalysts.

[0077] The following examples will further illustrate the present disclosure, but do not limit the present disclosure.

[0078] In the examples, the sulfur content of the heavy oil feedstock was tested by the method of GB / T 17040-2008, the nickel content was tested by the method of SH / T 0715, the vanadium content was tested by the method of SH / T 0715, the saturated fraction and aromatic fraction contents were tested by the method of SH / T 0509, the gum and asphaltene contents were tested by the method of SH / T 0509, the carbon residue number was tested by the method of GB / T 17144-1997, and the viscosity was tested by the method of GB / T 11137-1989(2004). The catalysts used in the examples were all purchased from Sinopec Catalyst Co., Ltd. Changling Branch.

[0079] Example 1

[0080] The heavy oil feedstock 1 used in this example was atmospheric residue, and the 5 wt% distillation temperature thereof was 382.6℃. The characteristic property characterization data such as the sulfur content thereof are shown in Table 1.

[0081] The heavy oil feed 1 was sent to a fixed bed reactor to perform a hydroresid reaction, and a hydrogenerated oil to be measured was obtained. The fixed bed reactor was filled with a hydroprotection agent RG-30B, a hydrodemetallization agent RDM-32, and a hydrodesulfurization and hydroresid removal agent RMS-30 in the order of 1:9.9:9.9 by volume ratio. The hydroresid reaction conditions were 380°C of temperature, 15.0 MPa of pressure, 0.2 h -1 -1 of liquid hourly space velocity, and 700 Nm 3 / m 3 of hydrogen to oil ratio.

[0082] The sulfur content, nickel content, vanadium content, saturates and aromatics content, gum and asphaltene content, carbon residue value, and viscosity of the heavy oil feed 1 were substituted into a characteristic factor equation of the following formula (1) to calculate a characteristic factor H CCR :

[0083] H CCR = S a + U b + A c + CCR d + Q e (1)

[0084] In formula (1), H CCR represents a characteristic factor, S represents a sulfur content (wt%), a is 0.09, U represents a metal component content factor and is calculated according to the following formula (2), b is 0.01, A represents a hydrocarbon component content factor and is calculated according to the following formula (3), c is 0.01, CCR represents a carbon residue value (wt%), d is -0.01, Q represents a viscosity factor and is calculated according to the following formula (4), and e is -0.923;

[0085]

[0086] In formula (2), m v represents a vanadium content (ppm), and m Ni represents a nickel content (ppm);

[0087]

[0088] In formula (3), m 饱和分芳香分 represents a saturates and aromatics content (wt%), and m 胶质沥青质 represents a gum and asphaltene content (wt%);

[0089] Q = log μ (4)

[0090] In formula (4), μ represents a viscosity (100°C, mm 2 / s).

[0091] The calculated characteristic factor H CCRSubstituting the characteristic factor-reaction rate constant relationship into the following equation (5), the reaction rate constant k is calculated. CCR :

[0092] k CCR =pH CCR -q (5)

[0093] In equation (5), k CCR The values ​​represent the reaction rate constants, with p = 0.078 and q = 0.320.

[0094] The calculated reaction rate constant k CCR Substituting into the reaction kinetic equation (6) below, the predicted carbon residue value of the hydrogenated oil to be tested is calculated:

[0095]

[0096] In equation (6), C CCR The carbon residue (wt%) of the tested hydrotreated oil is represented by C. CCR0 The carbon residue value (wt%) represents the heavy oil feedstock, t is the residence time (h) of the heavy oil feedstock after passing through the hydrogenation catalyst, and n is 1.7.

[0097] The carbon residue value of the hydrogenated oil to be tested was measured, and the measured values ​​and predicted values ​​are listed in Table 2. The deviation between the measured values ​​and the predicted values ​​is calculated according to the following formula (7).

[0098] Deviation = |Predicted value - Measured value| / Predicted value × 100% (7)

[0099] Example 2

[0100] The carbon residue value of the hydrotreated product oil obtained by hydrotreating heavy oil feedstock 2 with carbon removal was predicted according to the method in Example 1. Heavy oil feedstock 2 is atmospheric residue oil with a 5% wt distillation temperature of 380.0℃. Its sulfur content and other characteristic properties are shown in Table 1. The measured and predicted carbon residue values ​​of the obtained hydrotreated product oil are listed in Table 2.

[0101] Example 3

[0102] The carbon residue value of the hydrotreated product oil obtained by hydrotreating heavy oil feedstock 3 according to the method in Example 1 was predicted. Heavy oil feedstock 3 is atmospheric residue oil with a 5% wt distillation temperature of 378.4℃. Its characteristic properties, such as sulfur content, are shown in Table 1. The measured and predicted carbon residue values ​​of the obtained hydrotreated product oil are listed in Table 2.

[0103] Example 4

[0104] The carbon residue value of the hydrotreated product oil obtained from the hydrodecarbonization reaction of heavy oil feedstock 1 was predicted according to the method in Example 1. The difference was that the conditions for the hydrodecarbonization reaction were: temperature 390°C, pressure 16.0 MPa, and liquid hourly space velocity 0.25 h⁻¹. -1 Hydrogen-to-oil ratio 800 Nm 3 / m 3 The measured and predicted carbon residue values ​​of the hydrogenated oil are listed in Table 2.

[0105] Example 5

[0106] The carbon residue value of the hydrotreated product oil obtained by hydrotreating heavy oil feedstock 4 according to the method in Example 1 was predicted. Heavy oil feedstock 4 is atmospheric residue oil with a 5% wt distillation temperature of 380.2℃. Its sulfur content and other characteristic properties are shown in Table 1. The measured and predicted carbon residue values ​​of the obtained hydrotreated product oil are listed in Table 2.

[0107] Example 6

[0108] The carbon residue value of the hydrotreated product oil obtained by hydrotreating heavy oil feedstock 5 with carbon removal was predicted according to the method in Example 1. Heavy oil feedstock 5 is atmospheric residue oil with a 5% by weight distillation temperature of 395.6℃. Its sulfur content and other characteristic properties are shown in Table 1. The measured and predicted carbon residue values ​​of the obtained hydrotreated product oil are listed in Table 2.

[0109] Table 1

[0110]

[0111] Table 2

[0112]

[0113]

[0114] As shown in Table 2, the predicted carbon residue values ​​of the hydrotreated oil obtained using the method disclosed in this paper are close to the measured values, indicating high prediction accuracy. In particular, when the heavy oil feedstock has specific sulfur and nitrogen content ranges, it is beneficial to further improve the prediction accuracy.

[0115] The preferred embodiments of this disclosure have been described in detail above with reference to the accompanying drawings. However, this disclosure is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this disclosure, various simple modifications can be made to the technical solutions of this disclosure, and these simple modifications all fall within the protection scope of this disclosure.

[0116] It should be further noted that various specific technical features described in the above specific embodiments can be combined in any suitable manner, and the disclosure will not be repeated here for various possible combinations.

[0117] Furthermore, various different embodiments of the disclosure can also be combined with each other, as long as it does not violate the idea of the disclosure, it should also be considered as disclosed by the disclosure.

Claims

1. A method of predicting the carbon residue number of a heavy oil hydroprocessing oil, characterized by, The method comprises: obtaining a heavy oil raw material, and obtaining characterization data of characteristic properties of the heavy oil raw material, wherein the characteristic properties include sulfur content, metal component content, hydrocarbon component content, carbon residue value, and viscosity; obtaining a to-be-tested hydrogenated oil, which is obtained after a hydro-decarbon residue reaction of the heavy oil raw material; substituting the characterization data of the characteristic properties of the heavy oil raw material into a characteristic factor equation of the hydro-decarbon residue reaction to calculate a characteristic factor of the hydro-decarbon residue reaction; wherein the characteristic factor equation is as follows (1): H CCR = S a + U b + A c + CCR d + Q e (1) In formula (1), H CCR represents a characteristic factor, S represents the sulfur content and has the unit wt%, a is a fitting index for the sulfur content, U represents a metal component content factor, b is a fitting index for the metal component content factor, A represents a hydrocarbon component content factor, c is a fitting index for the hydrocarbon component content factor, CCR represents the carbon residue value and has the unit wt%, d is a fitting index for the carbon residue value, Q represents a viscosity factor, and e is a fitting index for the viscosity factor; substituting the characteristic factor into a characteristic factor-reaction rate constant relationship equation of the hydro-decarbon residue reaction to calculate a reaction rate constant of the hydro-decarbon residue reaction; wherein the characteristic factor-reaction rate constant relationship equation is a linear regression fitting equation with the characteristic factor as the independent variable and the reaction rate constant as the dependent variable; substituting the reaction rate constant into a reaction kinetics equation of the hydro-decarbon residue reaction to calculate a predicted value of the carbon residue value of the to-be-tested hydrogenated oil.

2. The method of claim 1, wherein, The characteristic properties include sulfur content, nickel content, vanadium content, saturated component and aromatic component content, gum and asphaltene content, carbon residue value, and viscosity; In formula (1), U is calculated according to formula (2) below, A is calculated according to formula (3) below, and Q is calculated according to formula (4) below: In formula (2), m v represents the vanadium content and has the unit ppm, m Ni represents the nickel content and has the unit ppm; In formula (3), m 饱和分芳香分 represents the saturates and aromatics content and is in wt.% 胶质沥青质 represents the gum and asphaltenes content and is in wt.% Q = log μ (4) In formula (4), μ represents viscosity at 100°C and the unit is mm 2 / s; In formula (1), a is 0.085-0.10, b is 0.005-0.016, c is 0.005-0.018, d is -0.013 to -0.005, and e is -1.2 to -0.

8.

3. The method of claim 2, wherein, The characteristic factor-reaction rate constant relationship equation is as follows (5): k CCR = pH CCR - q (5) In formula (5), k CCR represents a reaction rate constant, p is 0.05 to 0.1, and q is 0.2 to 0.

4.

4. The method of claim 3, wherein, The reaction kinetics equation is as follows (6): In formula (6), C CCR represents the carbon residue value of the heavy oil feedstock and has a unit of wt%, t represents the residence time of the heavy oil feedstock in the hydrogenation catalyst and has a unit of h, and n represents the reaction order of the hydrogenation de-carbon residue reaction. CCR0 represents the carbon residue value of the heavy oil feedstock and has a unit of wt%, t represents the residence time of the heavy oil feedstock in the hydrogenation catalyst and has a unit of h, and n represents the reaction order of the hydrogenation de-carbon residue reaction.

5. The method of claim 4, wherein, In formula (6), n is 1.3-2.

2.

6. The method of claim 1, wherein, The heavy oil raw material is atmospheric residue, and the 5% by weight distillation temperature of the heavy oil raw material is 350°C or higher; and / or, The sulfur content of the heavy oil raw material is 1.0-7.0% by weight, and the nitrogen content is 0.01-0.6% by weight.

7. The method of claim 1, wherein, The hydro-decarbon residue reaction is carried out in a fixed bed reactor filled with a hydrogenation catalyst.

8. The method of claim 7, wherein, The hydrogenation catalyst comprises an active metal component and a carrier; The active metal component is at least one selected from nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum, and cobalt-molybdenum; and the carrier is at least one selected from alumina, silica, and amorphous silica-alumina.

9. The method of claim 7, wherein, The hydrogenation catalyst comprises a hydrogenation guard, a hydro-demetalization agent, and a hydro-desulfurization and decarbonization agent, which are sequentially filled; The volume ratio of the hydrogenation guard, the hydro-demetalization agent, and the hydro-desulfurization and decarbonization agent is 1:(5-14):(5-14).

10. The method of claim 1 or 7, wherein, The conditions of the hydro-decarbon residue reaction include: temperature 320-450℃, pressure 10-22MPa, liquid hourly space velocity 0.05-1.0h -1 , hydrogen-oil volume ratio 250-1500Nm 3 / m 3 .

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