Method for catalytically producing special oil product by adopting Beta-type molecular sieve-containing catalyst and shape-selective molecular sieve-containing catalyst

Abstract

The invention relates to the field of special oil product production, and discloses a method for catalytically producing a special oil product by adopting a Beta-type molecular sieve-containing catalyst and a shape-selective molecular sieve-containing catalyst. The method comprises the steps that hydrogen and mixed distillate oil are subjected to a first hydrocracking reaction with a first hydrocracking catalyst, a first product is obtained, the first hydrocracking catalyst comprises a first carrier and a first metal component, the first carrier contains a Beta type molecular sieve, and the first metal component is a VIB group metal component; performing a second hydrocracking reaction on the first product and a second hydrocracking catalyst; wherein the mixed distillate oil comprises a kerosene fraction and a diesel fraction, and based on the total mass of the mixed distillate oil, the mass content of the diesel fraction is 60-90%, and the mass content of the kerosene fraction is 10-40%; the organic nitrogen content of the mixed distillate oil is not higher than 60 mu g / g. By adopting the method disclosed by the invention, the special oil product with low freezing point, high flash point and low viscosity can be obtained.

Description

Technical Field

[0001] The invention relates to the field of special oil product production, and in particular to a method for producing special oil products by catalyzing a Beta-type molecular sieve catalyst and a shape-selective molecular sieve catalyst. Background Art

[0002] The rectifier and inverter technology for converting AC power into DC power transmission requires special and better-performing converter transformer oil, which has lower kinematic viscosity, higher flash point, excellent oxidation and aging stability, high cleaning performance, and gassing properties.

[0003] Among the existing power grids, my country's 800kV, AC 1000kV and above UHV power grids use rectifier inverter technology, which requires transformer oil with better performance, which not only requires moderate kinematic viscosity, but also requires the oil to have the lowest freezing point and the lowest low-temperature fluidity. This dual requirement of high-temperature stability and low-temperature fluidity has led to extensive research in the technical development of special oils.

[0004] CN106753555B discloses a method for preparing low-aromatic transformer oil by medium-pressure hydrogenation of cycloalkyl distillate oil, which comprises: 1) cycloalkyl distillate oil enters the first hydrogenation reactor, passes through the hydrofining reaction zone and the deep dearomatization reaction zone, and realizes the hydrogenation removal of sulfur and nitrogen compounds in the oil product and the hydrogenation saturation of aromatic hydrocarbons; 2) the reaction stream enters the second reactor, passes through the selective ring-opening reaction zone, the isomerization decondensation reaction zone and the supplementary refining reaction zone, respectively, and realizes the selective ring-opening of polycyclic compounds, the isomerization of paraffin (branched chain) and the saturation of cracked olefins; 3) the reaction product is separated by gas-liquid separation and rectification to obtain a low-aromatic transformer oil fraction and a clean light oil fraction. The method is suitable for the quality improvement and value-added processing of transformer oil base oil by cycloalkyl crude oil and coal-based oil fractions, and has the characteristics of simple process flow, small device investment scale, high operation safety, and high transformer oil base oil yield, good product quality, and environmental friendliness.

[0005] The existing technology mainly produces it by hydrofining of cycloalkyl fraction, hydrocracking of high-density secondary processed diesel fraction, hydrocracking of cycloalkyl VGO fraction, etc. This makes its application obviously limited due to the limited source of raw materials. Summary of the invention

[0006] The purpose of the present invention is to overcome the problems existing in the prior art and provide a method for producing special oil products by using a Beta-type molecular sieve catalyst and a shape-selective molecular sieve catalyst. The method of the present invention can produce special oil products with low freezing point, low viscosity and high flash point.

[0007] In order to achieve the above object, the present invention provides a method for producing special oil products, which comprises the following steps:

[0008] (1) subjecting hydrogen and mixed distillate oil to a first hydrocracking reaction with a first hydrocracking catalyst to obtain a first product, wherein the first hydrocracking catalyst comprises a first carrier and a first metal component supported on the first carrier, wherein the first carrier contains a Beta molecular sieve and the first metal component is a Group VIB metal component;

[0009] (2) subjecting the first product obtained in step (1) to a second hydrocracking reaction with a second hydrocracking catalyst, wherein the second hydrocracking catalyst comprises a second carrier and a second metal component supported on the second carrier, wherein the second carrier comprises an MFI molecular sieve, and the second metal component comprises a Group VIB metal component and a Group VIII metal component;

[0010] Wherein, the mixed distillate oil comprises kerosene fraction and diesel fraction, and based on the total mass of the mixed distillate oil, the mass content of the diesel fraction is 60-90%, and the mass content of the kerosene fraction is 10-40%;

[0011] Wherein, the organic nitrogen content of the mixed distillate oil is not higher than 60 μg / g.

[0012] Preferably, the density of the kerosene fraction is 0.82-0.9 g / cm 3 , the distillation range is 165-290℃.

[0013] Preferably, the density of the diesel fraction is 0.85-0.95 g / cm 3 , the distillation range is 170-375℃.

[0014] Preferably, the second hydrocracking reaction temperature is 60-200°C higher than the first hydrocracking reaction temperature, preferably 80-200°C higher.

[0015] The beneficial effects of the present invention include:

[0016] The present invention adopts a low-nitrogen mixed distillate oil of a specific composition to carry out a simple two-step hydrocracking to obtain a special oil product with a low freezing point, a high flash point and a low viscosity. In the hydrocracking process, a first hydrocracking catalyst comprising a first carrier containing a Beta molecular sieve and a monometallic active component and a second hydrocracking catalyst comprising a second carrier containing an MFI molecular sieve and a bimetallic active component are rationally graded, so that the obtained special oil product has higher comprehensive performance and is suitable for use as transformer oil, and is more suitable for use as ultra-high voltage transformer oil. DETAILED DESCRIPTION

[0017] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0018] In the present invention, the density of the diesel and kerosene fractions is the density at 20°C.

[0019] In the present invention, the dry basis of a substance refers to a solid product obtained by calcining the substance at 600° C. for 3 hours.

[0020] In the present invention, "optional" means not essential, and can be understood as containing or not containing, adding or not adding, adopting or not adopting.

[0021] One aspect of the present invention provides a method for producing a special oil product, the method comprising the following steps:

[0022] (1) subjecting hydrogen and mixed distillate oil to a first hydrocracking reaction with a first hydrocracking catalyst to obtain a first product, wherein the first hydrocracking catalyst comprises a first carrier and a first metal component supported on the first carrier, wherein the first carrier contains a Beta molecular sieve and the first metal component is a Group VIB metal component;

[0023] (2) subjecting the first product obtained in step (1) to a second hydrocracking reaction with a second hydrocracking catalyst to obtain a special oil product, wherein the second hydrocracking catalyst comprises a second carrier and a second metal component supported on the second carrier, wherein the second carrier comprises an MFI molecular sieve, and the second metal component comprises a Group VIB metal component and a Group VIII metal component;

[0024] Wherein, the mixed distillate oil comprises kerosene fraction and diesel fraction, and based on the total mass of the mixed distillate oil, the mass content of the diesel fraction is 60-90%, and the mass content of the kerosene fraction is 10-40%;

[0025] Wherein, the organic nitrogen content of the mixed distillate oil is not higher than 60 μg / g.

[0026] In the present invention, the organic nitrogen content of the mixed distillate oil is not higher than 60 μg / g, preferably not higher than 30 μg / g. Using the mixed distillate oil that meets the above requirements is more conducive to obtaining the target product of the present invention.

[0027] Preferably, based on the total mass of the mixed distillate oil, the mass content of the diesel fraction is 70-90%, and the mass content of the kerosene fraction is 10-30%.

[0028] According to the present invention, preferably, the density of the kerosene fraction is 0.82-0.9 g / cm 3 .

[0029] According to the present invention, preferably, the distillation range of the kerosene fraction is 165-290°C.

[0030] According to the present invention, preferably, the density of the diesel fraction is 0.85-0.95 g / cm 3 .

[0031] According to the present invention, preferably, the distillation range of the diesel fraction is 170-375°C.

[0032] The present invention uses the mixed distillate oil with the above characteristics to more easily obtain the special oil product with low freezing point, high flash point and low viscosity as described in the present invention.

[0033] The present invention has no particular limitation on the source of the mixed distillate oil. As long as the mixed distillate oil meeting the above requirements is within the applicable scope of the present invention, the mixed distillate oil meeting the above requirements can be directly used, or it can be obtained by conventional methods such as hydrofining.

[0034] When conventional methods are used for treatment, the present invention has no particular limitation on the conditions of the conventional methods, as long as a mixed distillate oil meeting the above requirements is obtained.

[0035] According to some embodiments of the present invention, the first hydrocracking catalyst comprises a first carrier and a first metal component supported on the first carrier, wherein the first carrier contains a Beta molecular sieve and the first metal component is a Group VIB metal component. In order to obtain the target product of the present invention, preferably, the first hydrocracking catalyst does not contain a Group VIII metal component. With this preferred embodiment, the first hydrocracking catalyst uses a single metal hydrogenation component and is combined with a carrier containing a Beta molecular sieve, which is beneficial for converting heavy fractions in mixed distillate oil into special oil products.

[0036] According to the present invention, preferably, based on the dry weight of the first hydrocracking catalyst, the content of the first metal component in the first hydrocracking catalyst, calculated as oxide, is 5-30 wt%, preferably 10-25 wt%.

[0037] According to the present invention, preferably, based on the dry weight of the first hydrocracking catalyst, the content of the first carrier in the first hydrocracking catalyst is 70-95 wt%, preferably 75-90 wt%, calculated on a dry basis.

[0038] In the first hydrocracking catalyst, the sum of the contents of the various components is 100%.

[0039] In the present invention, the VIB group metal component can be a conventional choice in the art. Preferably, the VIB group metal component is Mo and / or W, preferably W. This preferred embodiment can promote the conversion of heavy fractions into specialty oils.

[0040] According to the present invention, preferably, the SiO2 / Al2O3 molar ratio of the Beta molecular sieve is 10-300, preferably 20-120.

[0041] According to the present invention, preferably, the specific surface area of ​​the Beta molecular sieve is 350-800m 2 / g, preferably 400-600m 2 / g.

[0042] According to the present invention, preferably, the pore volume of the Beta molecular sieve is 0.1-0.6 mL / g, preferably 0.2-0.5 mL / g.

[0043] The use of Beta molecular sieves with the above characteristics is beneficial to the conversion of heavy fractions into special oil products.

[0044] According to the present invention, preferably, in the first hydrocracking catalyst, the first carrier further contains a heat-resistant inorganic oxide.

[0045] The heat-resistant inorganic oxide of the present invention refers to a porous material with a maximum use temperature of not less than 600° C. The heat-resistant inorganic oxide can increase the strength of the hydrocracking catalyst and improve and adjust the physicochemical properties of the hydrocracking catalyst, such as improving the pore structure of the catalyst.

[0046] The present invention has a wide range of heat-resistant inorganic oxides, and various heat-resistant inorganic oxides commonly used in the art can be used. Preferably, the heat-resistant inorganic oxide is selected from at least one of silicon oxide, aluminum oxide, zirconium oxide and titanium oxide, preferably aluminum oxide.

[0047] According to the present invention, preferably, based on the total weight of the first carrier, the content of the Beta molecular sieve is 40-90 wt%, preferably 40-80 wt%; the content of the heat-resistant inorganic oxide is 10-60 wt%, preferably 20-60 wt%.

[0048] The present invention has no particular limitation on the preparation method of the first hydrocracking catalyst. The catalyst can be prepared by conventional methods or purchased commercially. The present invention has no particular limitation on this.

[0049] In the present invention, the second hydrocracking catalyst comprises a second carrier and a second metal component supported on the second carrier, wherein the second carrier contains an MFI type molecular sieve, and the second metal component comprises a VIB group and a VIII group metal component. In this preferred embodiment, the second hydrocracking catalyst uses a bimetallic hydrogenation component and is combined with a carrier containing an MFI type molecular sieve, which is conducive to obtaining the special oil product with low viscosity, low freezing point and high flash point of the present invention.

[0050] According to the present invention, preferably, based on the dry weight of the second hydrocracking catalyst, the content of the second metal component in the second hydrocracking catalyst, calculated as oxide, is 5-30 wt%, preferably 10-30 wt%.

[0051] According to the present invention, preferably, the mass ratio of the VIB group metal component to the VIII group metal component, calculated as oxide, is 1:0.05-0.4, preferably 1:0.1-0.35.

[0052] In the present invention, the Group VIB metal component can be selected from conventional materials in the art. Preferably, the Group VIB metal component is Mo and / or W.

[0053] In the present invention, the Group VIII metal component can be a conventional choice in the art. Preferably, in the second hydrocracking catalyst, the Group VIII metal component is Ni and / or Co.

[0054] According to the present invention, preferably, the second hydrocracking catalyst further contains an auxiliary agent, and the auxiliary agent is selected from at least one of phosphorus, fluorine and boron.

[0055] According to the present invention, preferably, based on the dry mass of the second hydrocracking catalyst, the content of the additive is 1-8% by weight in terms of oxide.

[0056] According to the present invention, preferably, the second hydrocracking catalyst further contains an organic additive.

[0057] According to the present invention, preferably, based on the total weight of the second hydrocracking catalyst, the content of the organic additive is 0.5-15 wt%.

[0058] According to the present invention, preferably, the organic additive is selected from at least one of alcohol compounds, carboxylic acid compounds and organic amine compounds.

[0059] The present invention has a wide range of selection for the type of the carboxylic acid compound, which can be various carboxylic acid compounds commonly used in the art. Preferably, the carboxylic acid compound is selected from at least one of acetic acid, maleic acid, oxalic acid, aminotriacetic acid, aminoacetic acid, citric acid, tartaric acid and malic acid.

[0060] The present invention has a wide range of alcohol compound types, which can be various alcohol compounds commonly used in the art. Preferably, the alcohol compound is selected from at least one of ethylene glycol, glycerol, polyethylene glycol, diethylene glycol and butanediol.

[0061] The present invention has a wide range of selection for the type of the organic amine compound, which can be various organic amine compounds commonly used in the art. Preferably, the organic amine compound is selected from at least one of ethylenediamine, diethylenetriamine, cyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid and ammonium ethylenediaminetetraacetate.

[0062] In the second hydrocracking catalyst, the sum of the contents of the various components is 100%.

[0063] According to the present invention, preferably, the SiO2 / Al2O3 molar ratio of the MFI type molecular sieve is 15-300, preferably 20-80.

[0064] According to the present invention, preferably, the specific surface area of ​​the MFI molecular sieve is 180-650m 2 / g, preferably 300-450m 2 / g.

[0065] According to the present invention, preferably, the pore volume of the MFI molecular sieve is 0.1-0.6 mL / g, preferably 0.2-0.5 mL / g.

[0066] The use of the MFI molecular sieve having the above characteristics is conducive to obtaining the special oil product with low viscosity, low freezing point and high flash point as described in the present invention.

[0067] In the present invention, the type of the MFI type molecular sieve can be selected in a wide range. Preferably, the MFI type molecular sieve is a ZSM-5 molecular sieve.

[0068] The present invention has no particular limitation on the source of the MFI molecular sieve, which can be purchased from commercial sources or prepared by conventional methods.

[0069] According to the present invention, preferably, in the second hydrocracking catalyst, the second carrier further contains a heat-resistant inorganic oxide. The heat-resistant inorganic oxide of the present invention can improve the strength of the hydrocracking catalyst and improve and adjust the physicochemical properties of the hydrocracking catalyst, such as improving the pore structure of the catalyst.

[0070] The type of the heat-resistant inorganic oxide in the second carrier of the present invention can be the same as the type of the heat-resistant inorganic oxide in the first carrier, and will not be described in detail here.

[0071] According to the present invention, preferably, based on the total weight of the second carrier, the content of the MFI molecular sieve is 40-90 wt%, preferably 40-80 wt%; the content of the heat-resistant inorganic oxide is 10-60 wt%, preferably 20-60 wt%.

[0072] The present invention has no particular limitation on the preparation method of the above-mentioned second hydrocracking catalyst, as long as the second hydrocracking catalyst of the above-mentioned composition can be prepared. In order to further improve the catalytic performance of the second hydrocracking catalyst, the present invention also provides a preparation method of the above-mentioned second hydrocracking catalyst.

[0073] Preferably, the preparation method of the second hydrocracking catalyst comprises the following steps:

[0074] (a) mixing an MFI molecular sieve and an optional heat-resistant inorganic oxide precursor to prepare a second carrier;

[0075] (b) introducing the second metal component, optional promoter and optional organic additive onto the second support by impregnation.

[0076] In the present invention, the method for preparing the second carrier in step (a) is well known to those skilled in the art, and the present invention has no particular limitation on this. For example, the method in step (a) may include: mixing and molding the MFI molecular sieve with an optional heat-resistant inorganic oxide precursor, and then drying and calcining to obtain the second carrier. The heat-resistant inorganic oxide precursor may be a conventional choice in the art. The molding in step (a) may be carried out by any conventional method in the art, for example, the molding may be carried out by tablet molding, ball rolling molding or extrusion molding. The drying and calcining conditions in step (a) may be carried out by conventional methods in the art, and the present invention has no particular limitation on this.

[0077] The present invention also has no particular limitation on the shape of the second carrier, which may be spherical, bar-shaped (including solid or hollow bars), block-shaped, etc. The bar-shaped may be a clover-shaped, four-leaf clover-shaped, or other multi-leaf clover-shaped or deformed forms thereof.

[0078] According to the present invention, preferably, step (b) comprises: introducing the second metal component, optional auxiliary agent and optional organic additive onto the second carrier by impregnation.

[0079] Preferably, in step (b), the step of introducing the second metal component onto the second carrier by impregnation comprises: contacting the second carrier with an impregnation solution containing a second metal precursor, an optional auxiliary agent precursor and an optional organic additive, followed by drying and optionally calcining.

[0080] In the present invention, when introducing the auxiliary agent, the second metal component and the auxiliary agent can be introduced together or separately, and the present invention has no requirement for this. The present invention adopts the method of introducing together as an example.

[0081] The present invention does not have any particular limitation on the contact temperature of step (b), which can be any temperature that the impregnation liquid can reach. There is no particular limitation on the contact time, as long as the required amount of metal precursor can be loaded on the carrier. In general, the higher the contact temperature and the greater the concentration of the impregnation liquid, the shorter the time required to reach the same impregnation amount (i.e., the weight difference between the carrier after impregnation and before impregnation); and vice versa. Once the required impregnation amount and conditions are determined, it is easy to select a suitable contact time. The specific operation of the impregnation method is well known to those skilled in the art, and the impregnation method can be a saturated impregnation method or a supersaturated impregnation method. There is no particular limitation on the environment of the impregnation method. According to conventional methods in the art, it can be carried out under sealed conditions or in an open environment. The lost solvent can be replenished during the contact process, or it can not be replenished. Various gases, such as air, nitrogen, water vapor, etc., can be introduced during the contact process, or no new components can be introduced.

[0082] The present invention has no particular limitation on the type and amount of the solvent in the impregnation solution, and the impregnation solution can be prepared according to conventional methods in the art.

[0083] Preferably, the second metal precursor is a soluble compound of the second metal, preferably selected from at least one of an oxide of the second metal, an inorganic salt of the second metal, and an organic substance of the second metal. For example, the inorganic salt of the second metal may be selected from at least one of a nitrate of the second metal, a carbonate of the second metal, a basic carbonate of the second metal, a hypophosphite of the second metal, a phosphate of the second metal, a sulfate of the second metal, and a chloride of the second metal. The organic substituent in the organic substance of the second metal may be selected from at least one of a hydroxyl group, a carboxyl group, an amine group, a ketone group, an ether group, and an alkyl group.

[0084] The auxiliary agent precursor of the present invention can be any conventional choice in the art, as long as it contains auxiliary agent elements, for example, soluble salts of auxiliary agents, inorganic acids of auxiliary agents, etc.

[0085] The present invention has no particular limitation on the order of adding the above substances in step (b), and they can be added together or separately. The present invention adopts the method of adding together as an example.

[0086] The drying and calcining in step (b) are conventional steps for preparing catalysts and are not particularly limited. For example, the drying conditions in step (b) may be: a temperature of 80-350° C., preferably 100-300° C.; a time of 0.5-24 hours, preferably 1-12 hours. The calcining conditions in step (b) may be: a temperature of 350-600° C., preferably 400-550° C.; a time of 0.2-12 hours, preferably 1-10 hours.

[0087] According to the present invention, preferably, the second hydrocracking reaction temperature is 60-200° C. higher than the first hydrocracking reaction temperature, preferably 80-200° C. higher. By adopting this preferred embodiment, the special oil product with low viscosity, low freezing point and high flash point of the present invention is obtained.

[0088] According to the present invention, preferably, the conditions of the first hydrocracking reaction include: reaction pressure of 10-17 MPa; reaction temperature of 240-380°C; hydrogen-oil volume ratio of 700-1300:1; liquid hourly space velocity of 0.5-3h -1 .

[0089] According to the present invention, preferably, the conditions of the second hydrocracking reaction include: reaction pressure of 10-17 MPa; reaction temperature of 330-430°C; hydrogen-oil volume ratio of 700-1300:1; liquid hourly space velocity of 0.5-4h -1 .

[0090] In the present invention, the first hydrocracking catalyst and the second hydrocracking catalyst may be loaded in different reaction zones of the same reactor, or may be loaded in different reactors. The selection may be made according to actual conditions, and the present invention has no particular limitation on this.

[0091] The hydrocracking reaction of the present invention can be carried out in any reactor that is sufficient to allow the hydrocarbon feedstock to contact and react with the catalyst under hydrogenation reaction conditions, for example, it can be a fixed bed reactor, a moving bed reactor, an ebullating bed reactor or a slurry bed reactor, and the present invention has no particular limitation on this.

[0092] According to the present invention, preferably, the second hydrocracking reaction product obtained in step (2) is fractionated to obtain a special oil product.

[0093] According to the present invention, preferably, the initial boiling point of the special oil product is 220-240° C. The use of this preferred embodiment is conducive to improving the flash point of the special oil product.

[0094] Preferably, the first hydrocracking catalyst and the second hydrocracking catalyst are presulfided before use.

[0095] The present invention has no particular limitation on the specific conditions of the pre-sulfurization, and the pre-sulfurization can be carried out according to the commonly used methods in the art.

[0096] The pre-sulfurization of the present invention can be carried out outside the vessel, or in-situ sulfidation can be carried out inside the vessel to convert it into a sulfide type.

[0097] According to the present invention, preferably, the freezing point of the special oil is not higher than -60°C; the flash point is not lower than 135°C; the density is not greater than 895kg / m 3 ; 40℃ kinematic viscosity value is not more than 11mm 2 / s.

[0098] Compared with existing special oil products, the special oil products of the present invention have higher high-temperature stability and better low-temperature fluidity, higher comprehensive performance, better adaptability, and are conducive to expanding the scope of application.

[0099] The special oil product of the present invention can be applied to a variety of application occasions, is more suitable for use as transformer oil, and is particularly preferably suitable for use as ultra-high voltage transformer oil.

[0100] The present invention will be described in detail below through examples.

[0101] In the following examples, the density, 40°C kinematic viscosity value, and flash point of the special oil products of the present invention are measured with reference to the GB2536-90 standard, and the freezing point of the special oil products of the present invention is measured with reference to the GB6537-2018 standard;

[0102] The pore volume and specific surface area of ​​the molecular sieve were determined by the static low-temperature adsorption capacity method (using the national standard GB / T5816-1995 method) using an ASAP 2400 automatic adsorption instrument from Micromertics Instruments, Inc., USA. The specific method is as follows: vacuum degassing for 4 hours at 250°C and 1.33 Pa, using nitrogen as the adsorbent, contacting with the adsorbent at -196°C, and static adsorption equilibrium was achieved; the amount of nitrogen adsorbed by the adsorbent was calculated from the difference between the nitrogen intake and the amount remaining in the gas phase after adsorption, and then the pore size distribution was calculated using the BJH formula, and the specific surface area and pore volume were calculated using the BET formula;

[0103] The crystal structure of the molecular sieve was determined using a D5005 X-ray diffractometer from Siemens, Germany, using the industry standard SH / T0339-92 method. Experimental conditions: Cu target, Ka radiation, solid detector, tube voltage 40kV, tube current 40mA, step scan, step width 0.02°, prefabrication time 2s, scanning range 5°~70°. The diffraction angle position refers to the 2θ angle value of the highest value of the diffraction peak;

[0104] The silicon content and aluminum content of the molecular sieve were determined by using a 3271E X-ray fluorescence spectrometer produced by Rigaku Corporation of Japan. The determination method is as follows: the powder sample was pressed into tablets, a rhodium target was used, a laser voltage of 50 kV, a laser current of 50 mA, a scintillation counter and a proportional counter were used to detect the intensity of the spectral lines of each element, and the external standard method was used to perform quantitative and semi-quantitative analysis of the element content.

[0105] The content of each component of the catalyst is calculated by the feed amount.

[0106] Example 1

[0107] Pseudo-boehmite (produced by Sinopec Catalyst Changling Branch, trade name PB90, 68 wt% on dry basis) and Beta molecular sieve (85 wt% on dry basis, specific surface area 438 m 2 / g, silicon aluminum molar ratio of 25, pore volume of 0.37mL / g) were mixed, extruded into a trilobal strip with an circumscribed circle diameter of 1.6 mm, dried at 120°C for 3h, and calcined at 600°C for 3h to obtain the first carrier. The first carrier was impregnated with 152mL of an aqueous solution containing 55g of ammonium metatungstate at room temperature, then dried at 120°C for 3h, and calcined at 480°C for 4h to obtain the first hydrocracking catalyst C-Beta-1. Its composition is shown in Table 1.

[0108] Pseudo-boehmite (produced by Sinopec Catalyst Changling Branch, trade name PB90, 71 wt% on dry basis) and ZSM-5 molecular sieve (95 wt% on dry basis, specific surface area of ​​332 m 2 / g, silicon aluminum molar ratio of 30, pore volume of 0.32mL / g) were mixed, extruded into trilobal strips with an circumscribed circle diameter of 1.6 mm, dried at 120°C for 3h, and calcined at 600°C for 3h to obtain the second carrier. After cooling to room temperature, 75mL of an aqueous solution containing molybdenum oxide, nickel carbonate with a weight content of 51% nickel oxide, phosphoric acid with a weight content of 61% phosphorus oxide, and citric acid was heated until completely dissolved, and the second carrier prepared by the above method was impregnated, and dried at 120°C for 3h to obtain catalyst C-MFI-1. Its composition is shown in Table 1.

[0109] The hydrocracking activity test was conducted on a fixed bed hydrocracking unit using the mixed distillate oil-1 (kerosene fraction is 20wt%, diesel fraction is 80wt%) described in Table 2. In the direction of the flow, the hydrocracking section used C-Beta-1 and C-MFI-1, which were placed in two reactors in sequence to conduct two hydrocracking reactions. The above catalyst was subjected to programmed temperature sulfurization before use: using straight run kerosene containing 2% dimethyl disulfide by mass as the sulfurized oil, the temperature was increased from 110°C to 230°C at a rate of 20°C / h, and maintained for 6h; then the temperature was increased to 360°C at a rate of 20°C / h, and maintained for 6h.

[0110] The volume ratio of C-Beta-1 and C-MFI-1 catalysts was 1.5, the reaction pressure was 10.5 MPa, the hydrogen-to-oil volume ratio was 750, and the liquid hourly space velocity was 1.5 h -1 The temperature of the first hydrocracking reaction is 280°C, the temperature of the second hydrocracking reaction is 380°C, the second hydrocracking reaction product is fractionated, and the components with a cutting temperature above 220°C are special oil products. The special oil products in the generated oil are analyzed, and the results are shown in Table 3.

[0111] Example 2

[0112] Pseudo-boehmite (68 wt% on dry basis) and Beta molecular sieve (85 wt% on dry basis, specific surface area of ​​558 m 2 / g, silicon aluminum molar ratio of 90, pore volume of 0.43mL / g) were mixed, extruded into a trilobal strip with an circumscribed circle diameter of 1.6 mm, dried at 120°C for 3h, and calcined at 600°C for 3h to obtain the first carrier. 200g of the first carrier was impregnated with 152mL of aqueous solution containing ammonium metatungstate, dried at 120°C for 3h, and calcined at 480°C for 4h to obtain the first hydrocracking catalyst C-Beta-2. Its composition is shown in Table 1.

[0113] Pseudo-boehmite (71 wt%) and ZSM-5 molecular sieve (95 wt% on dry basis, specific surface area of ​​401 m 2 / g, silicon aluminum molar ratio of 70, pore volume of 0.38mL / g) were mixed, extruded into a trilobal strip with an circumscribed circle diameter of 1.6 mm, dried at 120°C for 3h, and calcined at 600°C for 3h to obtain a second carrier. At room temperature, 75mL of an aqueous solution containing molybdenum oxide, nickel carbonate with a nickel oxide weight content of 51%, phosphoric acid with a phosphorus oxide weight content of 61%, and citric acid was completely dissolved, and the second carrier prepared by the above method was impregnated, and dried at 120°C for 3h to obtain a second hydrocracking catalyst C-MFI-2. Its composition is shown in Table 1.

[0114] The hydrocracking activity test was conducted on a fixed bed reactor using the mixed distillate oil-1 described in Table 2. In the direction of the flow, the hydrocracking section used C-Beta-2 and C-MFI-2, which were placed in two reactors in sequence to conduct two hydrocracking reactions. The above catalyst was subjected to programmed temperature sulfurization before use: using straight-run kerosene containing 2% dimethyl disulfide by mass as the sulfurized oil, the temperature was increased from 110°C to 230°C at a rate of 20°C / h and maintained for 6h; then the temperature was increased to 360°C at a rate of 20°C / h and maintained for 6h.

[0115] The volume ratio of C-Beta-2 and C-MFI-2 catalysts was 1.5, the reaction pressure was 15 MPa, the hydrogen-to-oil volume ratio was 1200, and the liquid hourly space velocity was 0.8 h -1The temperature of the first hydrocracking reaction is 240°C, the temperature of the second hydrocracking reaction is 330°C, the second hydrocracking reaction product is fractionated, and the components with a cutting temperature above 240°C are special oil products. The special oil products in the generated oil are analyzed, and the results are shown in Table 3.

[0116] Table 1

[0117]

[0118]

[0119] Example 3

[0120] The method of Example 1 was followed, except that the mixed oil fraction-2 described in Table 2 was used. The special oil products in the generated oil were analyzed, and the results are shown in Table 3.

[0121] Comparative Example 1

[0122] 103 g of pseudo-boehmite (produced by Sinopec Catalyst Changling Branch, trade name PB90, 71 wt% on dry basis) and 422 g of ZSM-5 molecular sieve (produced by Sinopec Catalyst Jianchang Branch, specific surface area 325 m 2 / g, skeleton silicon-aluminum ratio of 70, pore volume of 0.31mL / g, dry basis 95wt%), extruded into trilobal strips with an circumscribed circle diameter of 1.6mm, dried at 120℃ for 3h, calcined at 600℃ for 3h to obtain a carrier, cooled to room temperature, 150g of the carrier was impregnated with 75ml NiW standard solution (38.4g nickel nitrate and 44g ammonium metatungstate, and appropriate amount of water were mixed and stirred evenly, heated to 80℃, completely dissolved, and water was added to adjust to 75ml to obtain the standard solution), dried at 120℃ for 3h to obtain catalyst R-1.

[0123] The hydrocracking activity test was carried out on a fixed-bed hydrocracking unit using the mixed distillate oil-1 feedstock described in Table 2. The refining section used industrial catalyst RN-411 (produced by Sinopec Catalyst Changling Branch), the cracking section used catalyst R-1, the refining catalyst and cracking catalyst loading volume ratio was 1.5, the reaction pressure was 10.5 MPa, the hydrogen-to-oil volume ratio was 750, and the refined liquid hourly space velocity was 1.5 h -1 The refining temperature is 330℃, the cracking temperature is 280℃, and the special oil products in the generated oil are analyzed. The results are shown in Table 3.

[0124] Comparative Example 2

[0125] The method of Example 1 was followed, except that C-Beta-1 and C-MFI-1 were swapped, i.e., C-MFI-1 was used in the first hydrocracking reaction, and C-Beta-1 was used in the second hydrocracking reaction. The special oil products in the generated oil were analyzed, and the results are shown in Table 3.

[0126] Table 2

[0127]

[0128] Table 3

[0129]

[0130] From the results in Table 3, it can be seen that the special oil product obtained by the method of the present invention has low viscosity, low freezing point and high flash point, and has higher comprehensive performance. The special oil product of the present invention is suitable for use as transformer oil, and is more suitable for use as ultra-high voltage transformer oil.

[0131] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for producing special oil products, characterized in that: The method comprises the following steps: (1) subjecting hydrogen and mixed distillate oil to a first hydrocracking reaction with a first hydrocracking catalyst to obtain a first product, wherein the first hydrocracking catalyst comprises a first carrier and a first metal component supported on the first carrier, wherein the first carrier contains a Beta molecular sieve and the first metal component is a Group VIB metal component; (2) subjecting the first product obtained in step (1) to a second hydrocracking reaction with a second hydrocracking catalyst, wherein the second hydrocracking catalyst comprises a second carrier and a second metal component supported on the second carrier, wherein the second carrier comprises an MFI molecular sieve, and the second metal component comprises a Group VIB metal component and a Group VIII metal component; Wherein, the mixed distillate oil comprises kerosene fraction and diesel fraction, and based on the total mass of the mixed distillate oil, the mass content of the diesel fraction is 60-90%, and the mass content of the kerosene fraction is 10-40%; Wherein, the organic nitrogen content of the mixed distillate oil is not higher than 60 μg / g.

2. The method according to claim 1, wherein: Based on the total mass of the mixed distillate oil, the mass content of the diesel fraction is 70-90%, and the mass content of the kerosene fraction is 10-30%; Preferably, the density of the kerosene fraction is 0.82-0.9 g / cm 3 , distillation range is 165-290℃; and / or, the density of the diesel fraction is 0.85-0.95 g / cm 3 , the distillation range is 170-375℃.

3. The method according to claim 1, wherein: Based on the dry weight of the first hydrocracking catalyst, the first metal component content in the first hydrocracking catalyst is 5-30 wt%, preferably 10-25 wt%, calculated as oxide; and / or Based on the dry weight of the first hydrocracking catalyst, the content of the first carrier in the first hydrocracking catalyst is 70-95% by weight, preferably 75-90% by weight, calculated on a dry basis; Preferably, the Group VIB metal component is Mo and / or W.

4. The method according to any one of claims 1 to 3, wherein: The SiO2 / Al2O3 molar ratio of the Beta molecular sieve is 10-300, preferably 20-120; the specific surface area of ​​the Beta molecular sieve is 350-800m 2 / g, preferably 400-600m 2 / g; the pore volume of the Beta molecular sieve is 0.1-0.6mL / g, preferably 0.2-0.5mL / g; Preferably, in the first hydrocracking catalyst, the first carrier further comprises a heat-resistant inorganic oxide; Preferably, based on the total weight of the first carrier, the content of the Beta molecular sieve is 40-90% by weight, preferably 40-80% by weight; the content of the heat-resistant inorganic oxide is 10-60% by weight, preferably 20-60% by weight; Preferably, the heat-resistant inorganic oxide is selected from at least one of silicon oxide, aluminum oxide, zirconium oxide and titanium oxide.

5. The method according to any one of claims 1 to 4, wherein: Based on the dry weight of the second hydrocracking catalyst, the content of the second metal component in the second hydrocracking catalyst, calculated as oxide, is 5-30 wt%, preferably 10-30 wt%; Preferably, the mass ratio of the Group VIB metal component to the Group VIII metal component, calculated as oxide, is 1:0.05-0.4, preferably 1:0.1-0.35; Preferably, in the second hydrocracking catalyst, the Group VIB metal component is Mo and / or W; Preferably, in the second hydrocracking catalyst, the Group VIII metal component is Ni and / or Co.

6. The method according to any one of claims 1 to 5, wherein: The second hydrocracking catalyst further contains an auxiliary agent, wherein the auxiliary agent is selected from at least one of phosphorus, fluorine and boron; Preferably, based on the dry mass of the second hydrocracking catalyst, the content of the additive is 1-8 wt % in terms of oxide; Preferably, the second hydrocracking catalyst further contains an organic additive; Preferably, the content of the organic additive is 0.5-15 wt % based on the total weight of the second hydrocracking catalyst; Preferably, the organic additive is selected from at least one of an alcohol compound, a carboxylic acid compound and an organic amine compound; Preferably, the carboxylic acid compound is selected from at least one of acetic acid, maleic acid, oxalic acid, aminotriacetic acid, aminoacetic acid, citric acid, tartaric acid and malic acid; Preferably, the alcohol compound is selected from at least one of ethylene glycol, glycerol, polyethylene glycol, diethylene glycol and butanediol; Preferably, the organic amine compound is selected from at least one of ethylenediamine, diethylenetriamine, cyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid and ammonium ethylenediaminetetraacetate.

7. The method according to any one of claims 1 to 6, wherein: The SiO2 / Al2O3 molar ratio of the MFI molecular sieve is 15-300, preferably 20-80; the specific surface area of ​​the MFI molecular sieve is 180-650m 2 / g, preferably 300-450m 2 / g; the pore volume of the MFI molecular sieve is 0.1-0.6mL / g, preferably 0.2-0.5mL / g; Preferably, the MFI type molecular sieve is a ZSM-5 molecular sieve; Preferably, in the second hydrocracking catalyst, the second carrier further comprises a heat-resistant inorganic oxide; Preferably, based on the total weight of the second carrier, the content of the MFI molecular sieve is 40-90% by weight, preferably 40-80% by weight; the content of the heat-resistant inorganic oxide is 10-60% by weight, preferably 20-60% by weight; Preferably, the heat-resistant inorganic oxide is selected from at least one of silicon oxide, aluminum oxide, zirconium oxide and titanium oxide.

8. The method according to claim 7, wherein: The preparation method of the second hydrocracking catalyst comprises the following steps: (a) mixing an MFI molecular sieve and an optional heat-resistant inorganic oxide precursor to prepare a second carrier; (b) introducing the second metal component, optional promoter and optional organic additive onto the second support by impregnation.

9. The method according to any one of claims 1 to 8, wherein: The second hydrocracking reaction temperature is 60-200°C higher than the first hydrocracking reaction temperature, preferably 80-200°C higher; Preferably, the conditions of the first hydrocracking reaction include: reaction pressure of 10-17 MPa; reaction temperature of 240-380°C; hydrogen-oil volume ratio of 700-1300:1; liquid hourly space velocity of 0.5-3h -1 ; Preferably, the conditions of the second hydrocracking reaction include: reaction pressure of 10-17 MPa; reaction temperature of 330-430°C; hydrogen-oil volume ratio of 700-1300:1; liquid hourly space velocity of 0.5-4h -1 .

10. The method according to any one of claims 1 to 9, wherein: fractionating the second hydrocracking reaction product obtained in step (2) to obtain a special oil product; Preferably, the initial distillation point of the specialty oil product is 220-240°C.

11. The method according to any one of claims 1 to 10, wherein: The freezing point of the special oil is not higher than -60℃; the flash point is not lower than 135℃; the density is not more than 895kg / m 3 ; 40℃ kinematic viscosity value is not more than 11mm 2 / s.

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