A naphthalenesulfonic acid catalyst composition and its preparation method and application

Abstract

The present invention provides a naphthalenesulfonic acid catalyst composition and a preparation method and application thereof. The naphthalenesulfonic acid catalyst composition comprises a first component: naphthalenesulfonic acid and / or a naphthalenesulfonic acid derivative; and a second component: a naphthalenesulfonic acid salt and / or a naphthalenesulfonic acid derivative salt. The naphthalenesulfonic acid catalyst composition is mixed with crude oil with the participation of clay minerals, can reduce the viscosity of crude oil within 350°C, and generate light components, which is of great significance for the resource utilization of oil reservoirs.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts, and in particular relates to a naphthalenesulfonic acid catalyst composition and a preparation method and application thereof. Background Art

[0002] The world's proven reserves of high-viscosity crude oil are 815 billion tons, accounting for 70% of the remaining reserves of oil, and are a strategic resource of great scale. In-situ reforming, through catalytic reforming in the reservoir, can irreversibly convert heavy oil into light oil and greatly improve the recovery rate, upgrade inferior resources to high-quality resources, and achieve one-time utilization of energy and reduction of consumption and emission in the entire industry chain, which is equivalent to an "underground refinery" and is expected to solve the efficiency and environmental problems of mining, gathering, transportation and refining.

[0003] One of the core reactions of in-situ reforming of high-viscosity crude oil is the catalytic cracking of heavy crude oil components, that is, the process of cracking heavy oil under the action of heat and catalyst and converting it into light, low-viscosity oil and gas. It is an important process in the petroleum refining industry. Among them, the catalyst, as an indispensable key component of catalytic cracking, can effectively reduce the cracking temperature and control the composition of the cracking products. At present, the catalytic cracking process generally requires a reaction above 400-450°C under different catalyst conditions, but this temperature is difficult to reach in the reservoir by conventional means. For example, water vapor can generally heat the reservoir to 350°C at most. Therefore, the development of a catalyst that can crack crude oil within 350°C is a key technical problem in this field.

[0004] CN102134509A discloses a catalytic conversion method for producing propylene and high-octane gasoline from crude oil, wherein pretreated crude oil is used as a raw material and is contacted with a catalyst rich in medium-pore zeolite in a catalytic conversion reactor for reaction, and the method converts inferior crude oil into propylene and high-octane gasoline while significantly reducing the yield of dry gas and coke, thereby achieving efficient utilization of petroleum resources. However, the method needs to be carried out at 450-700°C.

[0005] CN113355126A discloses a method for catalytic cracking of crude oil, in which low-bulk ratio catalytic cracking components are prepared using raw materials such as Y molecular sieve and macroporous alumina. The method can selectively crack heavy components and light components, and is suitable for the catalytic cracking process of crude oil with a wide distillation range and high heavy metal content. The cracked products have low by-product contents such as coke and dry gas, high yield of low-carbon olefins, and low catalyst consumption cost. However, the method requires a temperature above 400°C to achieve a catalytic effect.

[0006] Based on the above research, it can be seen that catalytic cracking reactions can be effectively achieved by using catalysts such as zeolite, molecular sieve or alumina, but the required temperature is above 400°C. However, in underground oil reservoirs, due to the limitations of the maximum temperature and pressure of water vapor heating, it is difficult to meet the lower limit of the process conditions for catalytic cracking. Therefore, it is urgent to develop a catalyst that can achieve catalytic cracking and viscosity reduction of crude oil, especially heavy oil, within 350°C. Summary of the invention

[0007] In view of the shortcomings of the prior art and the actual needs, the purpose of the present invention is to provide a naphthalenesulfonic acid catalyst composition and its preparation method and application. The naphthalenesulfonic acid catalyst composition can reduce the viscosity of heavy crude oil within 350°C and generate light components, which is of great significance for the resource utilization of oil reservoirs.

[0008] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a naphthalenesulfonic acid catalyst composition, which comprises a first component: naphthalenesulfonic acid and / or a naphthalenesulfonic acid derivative; and a second component: a naphthalenesulfonic acid salt and / or a naphthalenesulfonic acid derivative salt.

[0010] The present invention adopts a composition of naphthalenesulfonic acid (or a naphthalenesulfonic acid derivative) and a naphthalenesulfonic acid salt (or a naphthalenesulfonic acid derivative salt) as a catalyst, which is applied to the catalytic cracking of crude oil in underground oil reservoirs, can reduce the viscosity of heavy crude oil within 350° C., and generate light components, which is of great significance for the resource utilization of oil reservoirs.

[0011] In the present invention, the mass ratio of the first component to the second component is (1-9):1.

[0012] The (1-9):1 can be 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1 or 9:1, etc.

[0013] Preferably, the naphthalenesulfonic acid catalyst composition comprises naphthalenesulfonic acid, naphthalenesulfonic acid derivatives, naphthalenesulfonic acid salts and naphthalenesulfonic acid derivative salts.

[0014] Preferably, the mass ratio of naphthalenesulfonic acid to the naphthalenesulfonic acid derivative is (3-6):1.

[0015] The (3-6):1 can be 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1 or 6:1, etc.

[0016] Preferably, the mass ratio of the naphthalenesulfonate salt to the naphthalenesulfonic acid derivative salt is (0.6-1.5):1.

[0017] The (0.6-1.5):1 can be 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1 or 1.5:1, etc.

[0018] Other point values ​​within the above numerical range can be selected and will not be described in detail here.

[0019] The naphthalenesulfonic acid involved in the present invention includes α-naphthalenesulfonic acid and / or β-naphthalenesulfonic acid.

[0020] The naphthalenesulfonate involved in the present invention includes a naphthalenesulfonic acid transition metal salt, preferably any one of nickel naphthalenesulfonate, cobalt naphthalenesulfonate or a naphthalenesulfonic acid rare earth compound or a combination of at least two of them. The combination of at least two of them can be a combination of nickel naphthalenesulfonate and cobalt naphthalenesulfonate or a combination of cobalt naphthalenesulfonate and a naphthalenesulfonic acid rare earth compound, and any other combinations can be selected and will not be described one by one here.

[0021] The naphthalenesulfonic acid derivatives involved in the present invention include hydroxy-substituted naphthalenesulfonic acid and / or amino-substituted naphthalenesulfonic acid, preferably hydroxy-substituted naphthalenesulfonic acid.

[0022] The present invention prefers hydroxy-substituted naphthalenesulfonic acid, which not only has the carboxyl group to provide acidity, but also has the hydroxyl group and the carboxyl group in the molecule to jointly form a chelating effect on the metal ions, thereby improving the catalytic efficiency.

[0023] Preferably, the hydroxy-substituted naphthalenesulfonic acid includes any one of 3-hydroxy-2-naphthalenesulfonic acid, 4-hydroxy-1-naphthalenesulfonic acid or 1-hydroxy-5-naphthalenesulfonic acid, or a combination of at least two of them. The combination of at least two can be a combination of 3-hydroxy-2-naphthalenesulfonic acid and 4-hydroxy-1-naphthalenesulfonic acid or a combination of 4-hydroxy-1-naphthalenesulfonic acid and 1-hydroxy-5-naphthalenesulfonic acid, and any other combinations can be selected and will not be described in detail here.

[0024] Preferably, the amino-substituted naphthalenesulfonic acid includes any one of 4-amino-1-naphthalenesulfonic acid, 5-amino-1-naphthalenesulfonic acid or 8-amino-2-naphthalenesulfonic acid, or a combination of at least two thereof. The combination of at least two thereof may be a combination of 4-amino-1-naphthalenesulfonic acid and 5-amino-1-naphthalenesulfonic acid or a combination of 5-amino-1-naphthalenesulfonic acid and 8-amino-2-naphthalenesulfonic acid, and any other combinations may be selected and will not be described in detail herein.

[0025] Preferably, the naphthalenesulfonic acid derivative salt comprises a hydroxy-substituted naphthalenesulfonic acid transition metal salt and / or an amino-substituted naphthalenesulfonic acid transition metal salt, preferably a hydroxy-substituted naphthalenesulfonic acid transition metal salt.

[0026] The present invention preferably uses a hydroxy-substituted naphthalenesulfonic acid transition metal salt, in which the hydroxyl group and the carboxyl group in the molecule jointly form a chelating effect on the metal ion to improve the catalytic efficiency.

[0027] Preferably, the naphthalenesulfonic acid transition metal salt includes any one of nickel naphthalenesulfonate, cobalt naphthalenesulfonate or a naphthalenesulfonic acid rare earth compound or a combination of at least two of them. The combination of at least two may be a combination of nickel naphthalenesulfonate and cobalt naphthalenesulfonate or a combination of cobalt naphthalenesulfonate and a naphthalenesulfonic acid rare earth compound, and any other combinations may be selected and will not be described in detail here.

[0028] Preferably, the naphthalenesulfonic acid catalyst composition further comprises a solvent.

[0029] Preferably, the solvent comprises any one of diesel, crude oil or decalin.

[0030] In a second aspect, the present invention provides a method for preparing the naphthalenesulfonic acid catalyst composition as described in the first aspect, the preparation method comprising the following steps:

[0031] Naphthalenesulfonic acid and / or naphthalenesulfonic acid derivatives are mixed evenly with an optional solvent to obtain a dispersion, and then naphthalenesulfonate and / or naphthalenesulfonic acid derivative salts are added and mixed evenly to obtain a naphthalenesulfonic acid catalyst composition.

[0032] In a third aspect, the present invention provides a use of the naphthalenesulfonic acid catalyst composition as described in the first aspect in catalytic cracking of crude oil.

[0033] Preferably, the method for using the naphthalenesulfonic acid catalyst composition in the catalytic cracking of crude oil comprises the following steps:

[0034] In the presence of clay minerals, the naphthalenesulfonic acid catalyst composition is mixed with crude oil, heated to 220-350° C., and reacted for 1-200 hours.

[0035] The 220-350°C may be 220°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C or 350°C, etc.

[0036] The 1-200h may be 1h, 5h, 10h, 20h, 40h, 60h, 80h, 100h, 120h, 140h, 150h, 180h or 200h, etc.

[0037] Other point values ​​within the above numerical range can be selected and will not be described in detail here.

[0038] Preferably, the mixing ratio of the mass of the naphthalenesulfonic acid catalyst composition to the volume of the crude oil is 0.01-0.1 g / mL.

[0039] The 0.01-0.1 g / mL may be 0.01 g / mL, 0.02 g / mL, 0.03 g / mL, 0.04 g / mL, 0.05 g / mL, 0.06 g / mL, 0.07 g / mL, 0.08 g / mL, 0.09 g / mL or 0.1 g / mL, etc.

[0040] Other point values ​​within the above numerical range can be selected and will not be described in detail here.

[0041] Preferably, the clay mineral includes any one of illite, kaolinite, chlorite, montmorillonite or vermiculite, or a combination of at least two of them. The combination of at least two of them can be a combination of illite and kaolinite or a combination of kaolinite and chlorite, and any other combinations can be selected and will not be described in detail here.

[0042] Compared with the prior art, the present invention has the following beneficial effects:

[0043] The invention provides a naphthalenesulfonic acid catalyst composition. The naphthalenesulfonic acid catalyst composition, in the presence of clay minerals, can reduce the viscosity of heavy crude oil within 350°C and generate light components, which is of great significance for the resource utilization of oil reservoirs. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 The full hydrocarbon gas chromatogram of the product at 350° C. in Example 1 of the present invention;

[0045] Figure 2 The full hydrocarbon gas chromatogram of the product at 350° C. in Example 4 of the present invention;

[0046] Figure 3 The total hydrocarbon gas chromatogram of the product at 350° C. in Example 9 of the present invention;

[0047] Figure 4 The full hydrocarbon gas chromatogram of the product at 350° C. in Comparative Example 1 of the present invention;

[0048] Figure 5 It is the total hydrocarbon gas chromatogram of the product at 350°C in Comparative Example 2 of the present invention. DETAILED DESCRIPTION

[0049] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0050] The purchase sources of the corresponding materials and raw materials in the following preparation examples, embodiments, comparative examples and test examples are as follows:

[0051] Among them, the naphthalenesulfonic acid rare earth compound was made in the laboratory; decahydronaphthalene and quartz sand were purchased from Sinopharm Reagent Group; heavy oil was taken from Liaohe Oilfield in Liaoning Province, with a viscosity of 4386mPa·s (at 50°C); natural clay was taken from Liaohe Oilfield; oil-bearing sandstone was taken from the Jurassic heavy oil reservoir in the northwest margin of the Junggar Basin, with an original crude oil viscosity of 22370mPa·s (at 50°C), which is super heavy oil, and the original oil saturation is 68%. The remaining materials and raw materials can be obtained from other commercial channels unless otherwise specified.

[0052] Preparation Example 1

[0053] This preparation example provides a naphthalenesulfonic acid catalyst composition, the raw materials include: β-naphthalenesulfonic acid, β-naphthalenesulfonic acid cobalt, 4-hydroxy-1-naphthalenesulfonic acid, 6-hydroxy-2-naphthalenesulfonic acid nickel and decalin. The preparation method is as follows:

[0054] (1) Add 4 g of β-naphthalenesulfonic acid and 1.2 g of 4-hydroxy-1-naphthalenesulfonic acid to 100 g of decalin and stir for 20 min until completely dissolved to form a dispersion;

[0055] (2) 1.5 g of cobalt β-naphthalenesulfonate and 1 g of nickel 6-hydroxy-2-naphthalenesulfonate were added to the above dispersion and stirred for 20 min until they were completely dissolved to form a naphthalenesulfonic acid catalyst composition.

[0056] Preparation Example 2

[0057] This preparation example provides a naphthalenesulfonic acid catalyst composition, the raw materials include: α-naphthalenesulfonic acid, naphthalenesulfonic acid rare earth compound (a mixture of α-naphthalenesulfonic acid and rare earth elements), 3-hydroxy-2-naphthalenesulfonic acid, 6-hydroxy-2-naphthalenesulfonic acid nickel and diesel (commercially available No. 0 diesel). The preparation method is as follows:

[0058] (1) Add 5 g of α-naphthalenesulfonic acid and 1 g of 3-hydroxy-2-naphthalenesulfonic acid to 100 g of diesel and stir for 30 min until they are completely dissolved to form a dispersion;

[0059] (2) Add 1 g of naphthalenesulfonic acid rare earth compound and 1 g of 6-hydroxy-2-naphthalenesulfonic acid nickel to the above dispersion and stir for 30 min until the mixture is completely dissolved to form a naphthalenesulfonic acid catalyst composition.

[0060] Preparation Example 3

[0061] This preparation example provides a naphthalenesulfonic acid catalyst composition, the raw materials include: α-naphthalenesulfonic acid, β-naphthalenesulfonic acid cobalt, 5-amino-1-naphthalenesulfonic acid, 6-hydroxy-2-naphthalenesulfonic acid nickel and diesel (commercially available No. 0 diesel). The preparation method is as follows:

[0062] (1) Add 6 g of α-naphthalenesulfonic acid and 1 g of 5-amino-1-naphthalenesulfonic acid to 100 g of diesel and stir for 40 min until completely dissolved to form a dispersion;

[0063] (2) 1.2 g of cobalt β-naphthalenesulfonate and 1.2 g of nickel 6-hydroxy-2-naphthalenesulfonate were added to the above dispersion and stirred for 40 min until they were completely dissolved to form a naphthalenesulfonic acid catalyst composition.

[0064] Preparation Example 4

[0065] This preparation example provides a naphthalenesulfonic acid catalyst composition, which differs from Preparation Example 1 only in that the raw material does not include α-naphthalenesulfonic acid, and its reduced mass is supplemented by 3-hydroxy-2-naphthalenesulfonic acid, and the other parameters are consistent with Preparation Example 1. The preparation method refers to Preparation Example 1.

[0066] Preparation Example 5

[0067] This preparation example provides a naphthalenesulfonic acid catalyst composition, which differs from Preparation Example 1 only in that the raw material does not include 3-hydroxy-2-naphthalenesulfonic acid, and the reduced mass is supplemented by α-naphthalenesulfonic acid, and the other parameters are consistent with Preparation Example 1. The preparation method refers to Preparation Example 1.

[0068] Preparation Example 6

[0069] This preparation example provides a naphthalenesulfonic acid catalyst composition, which differs from Preparation Example 1 only in that the raw material does not include a naphthalenesulfonic acid rare earth compound, and the reduced mass is supplemented by 6-hydroxy-2-naphthalenesulfonic acid nickel, and the other parameters are consistent with Preparation Example 1. The preparation method is referred to Preparation Example 1.

[0070] Preparation Example 7

[0071] This preparation example provides a naphthalenesulfonic acid catalyst composition, which differs from Preparation Example 1 only in that the raw material does not include nickel 6-hydroxy-2-naphthalenesulfonate, and the reduced mass is supplemented by a naphthalenesulfonic acid rare earth compound, and the other parameters are consistent with Preparation Example 1. The preparation method is referred to Preparation Example 1.

[0072] Preparation Example 8

[0073] This preparation example provides a naphthalenesulfonic acid catalyst composition, which differs from Preparation Example 1 only in that an equal amount of 6-hydroxy-2-naphthalenesulfonic acid nickel is replaced by 6-hydroxy-2-naphthalenesulfonic acid sodium, and the other parameters are consistent with Preparation Example 1. The preparation method is referred to Preparation Example 1.

[0074] Comparative Preparation Example 1

[0075] This comparative preparation example provides a catalyst, which is different from Preparation Example 1 only in that the raw materials do not include α-naphthalenesulfonic acid and 3-hydroxy-2-naphthalenesulfonic acid, and the reduced mass is supplemented by naphthalenesulfonic acid rare earth compound and 6-hydroxy-2-naphthalenesulfonic acid nickel, the mass ratio of the naphthalenesulfonic acid rare earth compound and 6-hydroxy-2-naphthalenesulfonic acid nickel remains unchanged, and the other parameters are consistent with Preparation Example 1. The preparation method refers to Preparation Example 1.

[0076] Comparative Preparation Example 2

[0077] This comparative preparation example provides a catalyst, which is different from Preparation Example 1 only in that the raw materials do not include naphthalenesulfonic acid rare earth compound and 6-hydroxy-2-naphthalenesulfonic acid nickel, and the reduced mass is supplemented by α-naphthalenesulfonic acid and 3-hydroxy-2-naphthalenesulfonic acid, the mass ratio of α-naphthalenesulfonic acid and 3-hydroxy-2-naphthalenesulfonic acid remains unchanged, and the other parameters are consistent with Preparation Example 1. The preparation method refers to Preparation Example 1.

[0078] Example 1

[0079] This embodiment provides a method for using a naphthalenesulfonic acid catalyst composition, the steps are as follows:

[0080] (1) Add 25 mL of heavy oil, 10 g of quartz sand and 1 g of natural clay to a 100 mL PARR reactor, heat to 90 °C, stir evenly, and cool to 25 °C;

[0081] (2) At 25°C and 1 atm, inject 1 g of the naphthalenesulfonic acid catalyst composition obtained in Preparation Example 1 into the reaction kettle, heat to 90°C, stir evenly, and cool to 25°C;

[0082] (3) The reactor was then heated stepwise to 200°C, 220°C, 240°C, 280°C, 300°C and 350°C at a heating rate of 2°C / min. The reaction was carried out at each temperature for 1 h. After each reaction, the reactor was cooled to 25°C and 1 mL of sample was taken for testing.

[0083] Example 2

[0084] This embodiment provides a method for using a naphthalenesulfonic acid catalyst composition, the steps are as follows:

[0085] (1) Add 20 mL of heavy oil, 8 g of quartz sand and 0.8 g of natural clay into a 100 mL PARR high temperature and high pressure reactor, heat to 88 ° C, stir evenly, and cool to 25 ° C;

[0086] (2) At 25°C and 1 atmosphere, 0.8 g of the naphthalenesulfonic acid catalyst composition obtained in Preparation Example 2 was injected into the reaction kettle, the temperature was raised to 88°C, the mixture was stirred evenly, and the mixture was cooled to 25°C;

[0087] (3) The reactor was then heated stepwise to 200°C, 220°C, 240°C, 280°C, 300°C and 350°C at a heating rate of 2°C / min. The reaction was carried out at each temperature for 2 h. After each reaction, the reactor was cooled to 25°C and 1 mL of sample was taken for testing.

[0088] Example 3

[0089] This embodiment provides a method for using a naphthalenesulfonic acid catalyst composition, the steps are as follows:

[0090] (1) A core of 15 cm in length and 10 cm in diameter was drilled from an oil-bearing sandstone having a clay mineral content of 2.7%, and the core was placed in an annular stainless steel pressure-resistant holder. 5 g of the naphthalenesulfonic acid catalyst composition obtained in Preparation Example 3 was injected into the core at 25° C. and 1 atmosphere;

[0091] (2) The holder was then heated to 200°C, 220°C, 240°C, 280°C, 300°C and 350°C in sequence at a heating rate of 2°C / min. The reaction was carried out for 1.5 h at each temperature. After each reaction, the mixture was cooled to 25°C and 1 mL of sample was taken for detection.

[0092] Example 4

[0093] This embodiment provides a method for using a naphthalenesulfonic acid catalyst composition, the steps are as follows:

[0094] (1) A core of 18 cm in length and 12 cm in diameter was drilled from an oil-bearing sandstone having a clay mineral content of 5%, and the core was placed in an annular stainless steel pressure-resistant holder. 5 g of the naphthalenesulfonate catalyst composition obtained in Preparation Example 3 was injected into the core at 25° C. and 1 atmosphere;

[0095] (2) The holder was then heated to 200°C, 220°C, 240°C, 280°C, 300°C and 350°C in sequence at a heating rate of 2°C / min. The reaction was carried out at each temperature for 1 h. After each reaction, the mixture was cooled to 25°C and 1 mL of sample was taken for detection.

[0096] Embodiment 5-9

[0097] Examples 5-9 provide methods for using five naphthalenesulfonic acid catalyst compositions, which differ from Example 1 only in that the naphthalenesulfonic acid catalyst compositions obtained in Preparation Example 1 are replaced by the naphthalenesulfonic acid catalyst compositions obtained in Preparation Examples 4-8 in equal amounts, and the remaining parameters are consistent with Example 1. The experimental method is referenced to Example 1.

[0098] Comparative Example 1-2

[0099] This comparative example provides a method for using a naphthalenesulfonic acid catalyst. Compared with Example 1, the naphthalenesulfonic acid catalyst composition obtained in Preparation Example 1 is replaced by an equal amount of the catalyst obtained in Comparative Preparation Example 1-2, and the other parameters are consistent with Example 1. The experimental method is similar to Example 1.

[0100] Comparative Example 3

[0101] This comparative example provides a method for using a naphthalenesulfonic acid catalyst composition, which differs from Example 1 only in that natural clay is not added in step (1), and the other parameters are consistent with Example 1. The experimental method is similar to Example 1.

[0102] Test Example 1

[0103] In this test example, the products obtained at different temperatures from Examples 1-9 and Comparative Examples 1-3 were used as samples, 0.8 mL was taken, and the viscosity was measured by a rotational viscometer. The measurement method was carried out according to the [Petroleum and Natural Gas Industry Standard] SY T 0520-2008 Crude Oil Viscosity Determination Rotational Viscometer Balance Method.

[0104] The viscosity reduction rate calculation formula is:

[0105] Viscosity reduction rate = (1-oil viscosity after viscosity reduction / oil viscosity before viscosity reduction) × 100%.

[0106] The statistical results are shown in Table 1 below:

[0107] Table 1

[0108]

[0109] As shown in the above table, compared with comparative examples 1-2, the viscosity reduction of heavy crude oil in Example 1 is higher, indicating that naphthalenesulfonic acid (or naphthalenesulfonic acid derivatives) and naphthalenesulfonate (or naphthalenesulfonic acid derivative salt) are used in combination, and the viscosity reduction of its heavy crude oil can be synergistically improved. Compared with comparative example 3, the viscosity reduction of heavy crude oil in Example 1 is higher, indicating that when using naphthalenesulfonic acid catalyst composition to carry out catalytic cracking of crude oil, clay is an indispensable key component. Compared with Examples 5-8, the viscosity reduction of heavy crude oil in Example 1 is higher, indicating that when lacking any one component in naphthalenesulfonic acid, naphthalenesulfonic acid derivatives, naphthalenesulfonic acid derivative salts or naphthalenesulfonic acid salts, the catalytic effect of catalyst composition can be affected. Compared with Example 9, the viscosity reduction of heavy crude oil in Example 1 is higher, indicating that naphthalenesulfonic acid transition metal salts have better catalytic effect than naphthalenesulfonic acid non-transition metal salts.

[0110] Test Example 2

[0111] In this test example, the products at 350°C in Example 1, Example 4, Example 9, Comparative Example 1 and Comparative Example 2 were used as samples, 0.2 mL of the samples were taken, and the light and heavy components were detected by total hydrocarbon gas chromatography. The determination method was tested according to the petroleum standard-SYT5779-1995 crude oil total hydrocarbon gas chromatography analysis method.

[0112] The results are as follows Figure 1-5 As shown, Figure 1 is the full hydrocarbon gas chromatogram of the product at 350°C in Example 1, Figure 2 is the full hydrocarbon gas chromatogram of the product at 350°C in Example 4, Figure 3 is the full hydrocarbon gas chromatogram of the product at 350°C in Example 9, Figure 4 This is the full hydrocarbon gas chromatogram of the product at 350°C in Comparative Example 1, Figure 5 This is the full hydrocarbon gas chromatogram of the product at 350°C in Comparative Example 2. Among them, the peak before 30 minutes in the full hydrocarbon gas chromatogram is the light component, and the peak after 30 minutes is the heavy component. Figure 1-2 and Figure 3-5 The comparison shows that Figure 1-2 There are many peaks before 30 minutes, and the peaks are relatively high. Figure 3-5 In the experiment, almost no peak appeared before 30 minutes. The results show that the naphthalenesulfonic acid catalyst composition provided by the present invention can reduce the viscosity of heavy crude oil within 350°C and generate light components. Among them, when the first component and the second component in the naphthalenesulfonic acid catalyst composition are missing or when the naphthalenesulfonic acid transition metal salt in the naphthalenesulfonic acid catalyst composition is replaced by a naphthalenesulfonic acid non-transition metal salt, the catalytic effect of the naphthalenesulfonic acid catalyst composition will be significantly affected.

[0113] In summary, the present invention provides a naphthalenesulfonic acid catalyst composition, which, with the participation of clay minerals, can reduce the viscosity of heavy crude oil within 350°C and generate light components, which is of great significance for the resource utilization of oil reservoirs.

[0114] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A naphthalenesulfonic acid catalyst composition for catalytic cracking of crude oil, characterized in that: The naphthalenesulfonic acid catalyst composition comprises a first component: naphthalenesulfonic acid and naphthalenesulfonic acid derivatives; and a second component: naphthalenesulfonic acid salts and naphthalenesulfonic acid derivative salts; The naphthalenesulfonic acid derivatives include hydroxy-substituted naphthalenesulfonic acid and / or amino-substituted naphthalenesulfonic acid, the naphthalenesulfonic acid salts include naphthalenesulfonic acid transition metal salts, and the naphthalenesulfonic acid derivative salts include hydroxy-substituted naphthalenesulfonic acid transition metal salts and / or amino-substituted naphthalenesulfonic acid transition metal salts; The naphthalenesulfonic acid catalyst composition further includes a solvent; The solvent includes any one of diesel, crude oil or decalin.

2. The naphthalenesulfonic acid catalyst composition according to claim 1, characterized in that: The mass ratio of the first component to the second component is (1-9):

1.

3. The naphthalenesulfonic acid catalyst composition according to claim 1, characterized in that: The mass ratio of the naphthalenesulfonic acid to the naphthalenesulfonic acid derivative is (3-6):

1.

4. The naphthalenesulfonic acid catalyst composition according to claim 1, characterized in that: The mass ratio of the naphthalenesulfonate salt to the naphthalenesulfonic acid derivative salt is (0.6-1.5):

1.

5. The naphthalenesulfonic acid catalyst composition according to claim 1, characterized in that: The naphthalenesulfonic acid includes α-naphthalenesulfonic acid and / or β-naphthalenesulfonic acid.

6. The naphthalenesulfonic acid catalyst composition according to claim 1, characterized in that: The naphthalenesulfonic acid derivative is a naphthalenesulfonic acid substituted with a hydroxyl group.

7. The naphthalenesulfonic acid catalyst composition according to claim 1, characterized in that: The hydroxy-substituted naphthalenesulfonic acid includes any one of 3-hydroxy-2-naphthalenesulfonic acid, 4-hydroxy-1-naphthalenesulfonic acid or 1-hydroxy-5-naphthalenesulfonic acid or a combination of at least two thereof.

8. The naphthalenesulfonic acid catalyst composition according to claim 1, characterized in that: The amino-substituted naphthalenesulfonic acid includes any one of 4-amino-1-naphthalenesulfonic acid, 5-amino-1-naphthalenesulfonic acid or 8-amino-2-naphthalenesulfonic acid or a combination of at least two thereof.

9. The naphthalenesulfonic acid catalyst composition according to claim 1, characterized in that: The naphthalenesulfonic acid derivative salt is a naphthalenesulfonic acid transition metal salt substituted with a hydroxyl group.

10. The naphthalenesulfonic acid catalyst composition according to claim 1, characterized in that: The naphthalenesulfonic acid transition metal salt includes any one of naphthalenesulfonate nickel, naphthalenesulfonate cobalt or naphthalenesulfonate rare earth compounds or a combination of at least two thereof.

11. A method for preparing a naphthalenesulfonic acid catalyst composition according to any one of claims 1 to 10, characterized in that: The preparation method comprises the following steps: Naphthalenesulfonic acid and naphthalenesulfonic acid derivatives are mixed evenly with a solvent to obtain a dispersion, and then naphthalenesulfonate and naphthalenesulfonic acid derivative salts are added and mixed evenly to obtain a naphthalenesulfonic acid catalyst composition.

12. Use of the naphthalenesulfonic acid catalyst composition according to any one of claims 1 to 10 in catalytic cracking of crude oil.

13. The use according to claim 12, characterized in that: The method for using the naphthalenesulfonic acid catalyst composition in catalytic cracking of crude oil comprises the following steps: In the presence of clay minerals, the naphthalenesulfonic acid catalyst composition is mixed with crude oil, heated to 220-350° C., and reacted for 1-200 h.

14. The use according to claim 13, characterized in that: The mixing ratio of the mass of the naphthalenesulfonic acid catalyst composition to the volume of the crude oil is 0.01-0.1 g / mL.

15. The use according to claim 13, characterized in that: The clay mineral includes any one of illite, kaolinite, chlorite, montmorillonite or vermiculite, or a combination of at least two of them.

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