Rubber filling oil and preparation method thereof, and device for preparing rubber filling oil

Abstract

The present invention relates to the field of petrochemical technology, and in particular to a rubber filler oil and a preparation method thereof, and a device for preparing the rubber filler oil. The method comprises: (1) subjecting a catalytic cracking oil slurry to a first fractionation to obtain an intermediate fraction with a distillation range of 350-540°C; (2) subjecting the intermediate fraction to a first hydrogenation catalyst in the presence of hydrogen, and subjecting the obtained hydrogenation product I to a second hydrogenation catalyst to a second hydrogenation process to obtain a hydrogenation product II; (3) subjecting the hydrogenation product II to an olefin in the presence of an acidic catalyst to an alkylation process to obtain an alkylated product; (4) subjecting the alkylated product to a second fractionation to obtain a heavy fraction with a distillation range of ≥400°C as the rubber filler oil. The rubber filler oil product provided by the present invention not only meets environmental protection indicators and high viscosity characteristics, but also has the advantages of high yield and high aromatic carbon value.

Description

Technical Field

[0001] The invention relates to the technical field of petrochemical industry, and in particular to a rubber filling oil and a preparation method thereof, and a device for preparing the rubber filling oil. Background Art

[0002] Rubber filler oil (referred to as rubber oil) is a necessary raw material in the rubber production process. Adding a certain amount of rubber oil to the rubber can improve the shaping of the rubber, enhance the elasticity and anti-aging properties of the rubber, and play a very important role in the rubber production and the improvement of the performance of rubber products. Among them, aromatic rubber filler oil has the characteristics of high aromatic carbon content, high density, high viscosity, and good compatibility with polar rubber. However, aromatic rubber filler oil usually contains 10%-25wt% polycyclic aromatic hydrocarbons (Polycyclic Aromatics, abbreviated as PCA, determined by the dimethyl sulfoxide extraction refractive index method using the British Petroleum Institute IP346 standard).

[0003] With increasingly stringent environmental regulations, PCA has become a world-recognized organic pollutant. In 2005, the European Union signed the 2005 / 69 / EC Directive on the Restriction of Polycyclic Aromatic Hydrocarbons, which clearly limits the total content of benzo(a)pyrene and eight carcinogenic polycyclic aromatic compounds in aromatic oils. Aromatic oils that meet the requirements of the directive are called environmentally friendly aromatic rubber filler oils. In addition, my country issued the GB / T 33322-2016 "Rubber Plasticizer Aromatic Mineral Oil" standard for aromatic rubber filler oils in 2016, which requires the content of polycyclic aromatic hydrocarbons to be less than 3wt%.

[0004] In the prior art, environmentally friendly aromatic rubber filler oil is mainly produced using furfural extracted oil as raw material through a solvent extraction method. For example, (1) a single polar solvent is used to produce an aromatic rubber filler oil having an aromatic content greater than 50 wt% and a polycyclic aromatic hydrocarbon (PCA) content less than 3 wt% at a relatively low extraction temperature and a relatively small temperature difference in the extraction tower using furfural extracted oil as raw material; (2) a dual solvent extraction technology is developed for intermediate base extracted oil and cycloalkyl vacuum distillate oil, and the product meets environmental protection requirements, has an aromatic carbon content of more than 22 wt% and a relatively high product viscosity.

[0005] Although environmentally friendly aromatic rubber filler oil can be produced by using furfural extracted oil as raw material through solvent extraction process, low pour point furfural extracted oil is a special petroleum product with limited raw material sources. Catalytic cracking oil slurry is a low-value by-product in refineries and contains a large amount of aromatic components, which can meet the requirements of high aromatic carbon for aromatic rubber filler oil.

[0006] CN101906317A discloses a method of using catalytic cracking oil slurry as raw material, and using saturated hydrocarbon solvents and polar solvents for multiple extractions to obtain a refined oil that is an aromatic rubber oil that meets environmental protection index requirements. However, the yield of the environmentally friendly product obtained by this method is low.

[0007] CN104593065A discloses a process for producing a rubber oil product that meets environmental protection index requirements and has a high yield by using catalytic cracking oil slurry through hydrogenation treatment, hydrofining and hydromodification. However, the viscosity of the rubber oil product produced by this process is relatively low.

[0008] CN104593067A discloses a method for producing white rubber oil by hydrogenation treatment, hydrogenation modification and hydrogenation supplementary refining of catalytic cracking oil slurry. The rubber oil product meets the environmental protection index of rubber oil, but the aromatic content and viscosity of the product are low.

[0009] Therefore, a new method for preparing rubber filling oil is urgently needed. Summary of the invention

[0010] The purpose of the present invention is to overcome the problem that the existing catalytic cracking oil slurry is difficult to produce environmentally friendly rubber filler oil with high viscosity, high yield and high aromatic carbon value, and to provide a new rubber filler oil and a preparation method thereof, and a device for preparing rubber filler oil. The rubber filler oil prepared by the method has the characteristics of high viscosity, high yield and high aromatic carbon value while meeting the requirements of environmental protection indicators.

[0011] In order to achieve the above object, the present invention provides a method for preparing a rubber filler oil in a first aspect, the method comprising the following steps:

[0012] (1) subjecting the catalytic cracking slurry to a first fractionation to obtain an intermediate fraction having a distillation range of 350-540° C.;

[0013] (2) in the presence of hydrogen, subjecting the middle fraction to a first hydrogenation treatment with a first hydrogenation catalyst, and subjecting the obtained hydrogenated product-I to a second hydrogenation treatment with a second hydrogenation catalyst to obtain a hydrogenated product-II;

[0014] (3) alkylating the hydrogenated product II with an olefin in the presence of an acidic catalyst to obtain an alkylated product;

[0015] (4) subjecting the alkylation product to a second fractionation to obtain a heavy fraction with a distillation range of ≥400° C. as rubber filler oil.

[0016] The second aspect of the present invention provides a rubber filler oil obtained by the method provided in the first aspect.

[0017] The third aspect of the present invention provides a device for preparing rubber filler oil, the device comprising: a distillation tower I, a hydrogenation reactor I, a hydrogenation reactor II, an alkylation reactor, and a distillation tower II connected in sequence;

[0018] The distillation tower I is used to perform a first fractionation on the catalytic cracking slurry to obtain an intermediate fraction with a distillation range of 350-450° C.

[0019] The hydrogenation reactor I is used to carry out a first hydrogenation treatment on the middle distillate and a first hydrogenation catalyst in the presence of hydrogen to obtain a hydrogenated product-I;

[0020] The hydrogenation reactor II is used to carry out a second hydrogenation treatment on the hydrogenated product-I and a second hydrogenation catalyst in the presence of hydrogen to obtain a hydrogenated product-II;

[0021] The alkylation reactor is used to carry out an alkylation reaction between the hydrogenation product-II and olefins in the presence of an acidic catalyst to obtain an alkylated product;

[0022] The distillation tower II is used to perform a second fractionation on the alkylation product to obtain a heavy fraction with a distillation range of ≥400° C. as rubber filler oil.

[0023] Compared with the prior art, the method provided by the present invention has the following advantages:

[0024] (1) The method provided by the present invention uses catalytic cracking oil slurry as raw material, adopts the technical means of first fractionation, two-stage hydrogenation treatment (first hydrogenation treatment, second hydrogenation treatment), alkylation treatment and second fractionation, to obtain an environmentally friendly rubber filler oil with high viscosity, high yield and high aromatic carbon value; in particular, by adjusting the process parameters of the two-stage hydrogenation treatment, the rubber filler oil product meets the environmental protection index requirements and high aromatic hydrocarbons, while more effectively reducing the content of polycyclic aromatic hydrocarbons in the raw material; by adjusting the process parameters of the alkylation treatment, the viscosity of the rubber filler oil product is more effectively increased; at the same time, the method simplifies the process flow and is convenient for industrial production;

[0025] (2) The rubber filler oil product provided by the present invention not only meets environmental protection indicators and high viscosity characteristics, but also has the advantages of high yield and high aromatic carbon value. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The present invention provides a schematic diagram of a device for preparing rubber filling oil.

[0027] Description of Reference Numerals

[0028] 1. Distillation tower I 2. Hydrogenation reactor I 3. Hydrogenation reactor II

[0029] 4. Alkylation reactor 5. Distillation tower II 6. Catalytic cracking slurry

[0030] 7. Light fraction 8. Middle fraction 9. Heavy fraction

[0031] 10. Hydrogenation product-I 11. Hydrogenation product-II 12. Olefins

[0032] 13. Alkylation product 14. Light fraction 15. Heavy fraction

[0033] 16. Hydrogen 17. First hydrogenation catalyst 18. Second hydrogenation catalyst

[0034] 19. Alkylation catalyst DETAILED DESCRIPTION

[0035] 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.

[0036] In the present invention, unless otherwise specified, the "first" and "second" do not indicate a sequence of precedence or a limitation on the materials or steps, but are only used to distinguish the materials or steps. For example, the "first" and "second" in "a first hydrogenation catalyst" and "a second hydrogenation catalyst" are only used to distinguish that they are not the same hydrogenation catalyst; the "first" and "second" in "a first distillation" and "a second distillation" are only used to distinguish that they are not the same distillation.

[0037] A first aspect of the present invention provides a method for preparing a rubber filler oil, the method comprising the following steps:

[0038] (1) subjecting the catalytic cracking slurry to a first fractionation to obtain an intermediate fraction having a distillation range of 350-540° C.;

[0039] (2) in the presence of hydrogen, subjecting the middle fraction to a first hydrogenation treatment with a first hydrogenation catalyst, and subjecting the obtained hydrogenated product-I to a second hydrogenation treatment with a second hydrogenation catalyst to obtain a hydrogenated product-II;

[0040] (3) alkylating the hydrogenated product II with an olefin in the presence of an acidic catalyst to obtain an alkylated product;

[0041] (4) subjecting the alkylation product to a second fractionation to obtain a heavy fraction with a distillation range of ≥400° C. as rubber filler oil.

[0042] The inventors of the present invention have found through research that: using catalytic cracking oil slurry as raw material and adopting two-stage hydrogenation treatment with different processes can effectively reduce the content of polycyclic aromatic hydrocarbons in the raw material, meet the environmental protection index requirements of rubber filler oil products, and at the same time reduce the saturation of aromatic hydrocarbons, which are ideal components of rubber oil, to ensure a higher aromatic carbon value; and then through aromatic alkylation reaction, the viscosity of the product is effectively increased, thereby converting the catalytic cracking oil slurry into a high-viscosity environmentally friendly aromatic rubber filler oil product.

[0043] At the same time, the rubber oil product prepared by the improved method of the present invention not only meets environmental protection indicators and high viscosity characteristics, but also has the advantages of high product yield and high aromatic carbon value.

[0044] In some embodiments of the present invention, preferably, the distillation range of the middle distillate is 350-540°C, for example, 350°C, 400°C, 450°C, 500°C, 520°C, 540°C, and any value in the range of any two values, preferably 400-520°C. When the distillation range of the middle distillate is lower than 350°C, the viscosity of the raw material is too low, and after the first hydrotreatment, the second hydrotreatment and the alkylation treatment, the viscosity requirements of the environmentally friendly rubber filler oil cannot be met; when the distillation range of the middle distillate is higher than 540°C, the content of polycyclic aromatic hydrocarbons is high, and the number of aromatic hydrocarbon rings is relatively large. After hydrotreatment, under the premise of ensuring a high aromatic carbon value, the content of polycyclic aromatic hydrocarbons is difficult to meet the requirements of environmental protection indicators. Therefore, a catalytic cracking oil slurry fraction with a certain viscosity and an appropriate content of polycyclic aromatic hydrocarbons is required.

[0045] In some embodiments of the present invention, preferably, the physical property parameters of the middle distillate satisfy: kinematic viscosity at 100°C < 16 mm 2 / s, preferably 10-15mm 2 / s; the aromatic hydrocarbon content is 50-99.9wt%, preferably 70-95wt%; the condensed ring aromatic hydrocarbon content is 20-99.9wt%, preferably 50-90wt%.

[0046] In the present invention, unless otherwise specified, condensed ring aromatic hydrocarbons refer to hydrocarbons containing three or more benzene rings.

[0047] In the present invention, unless otherwise specified, the kinematic viscosity parameters are measured using GB / T 265 (method for determination of kinematic viscosity of petroleum products and method for calculation of dynamic viscosity); the aromatic content parameters are measured using SH / T 0659 (method for determination of hydrocarbons in saturated hydrocarbon fractions in gas oil); and the polycyclic aromatic content parameters are measured using NB / SH / T 0838 (method for determination of polycyclic aromatic hydrocarbons (PCA) content in unused lubricating base oils and asphaltene-free petroleum fractions by dimethyl sulfoxide extraction refractive index method).

[0048] In the present invention, there is a wide range of choices for the source of the catalytic cracking slurry, as long as the physical properties of the catalytic cracking slurry meet the above-mentioned limitations.

[0049] In the present invention, in order to further ensure the long-term safe operation of the process unit, the catalytic cracking oil slurry needs to be desolidified. The solid powder in the catalytic cracking oil slurry will cause erosion and wear hazards to the device pumps and control valves, etc., and the solid content needs to be controlled. Preferably, the method also includes: before performing the first fractionation, the catalytic cracking oil slurry is desolidified.

[0050] In some embodiments of the present invention, preferably, the solid content in the catalytic cracking slurry after the desolidification treatment is ≤0.2wt%, preferably 0.02-0.1wt%, and more preferably 0-0.1wt%. Wherein, the solid content refers to the total amount of catalyst powder and other solid substances insoluble in xylene; the solid content parameter is measured using Q / SH 0742-2018.

[0051] In the present invention, the types of the first hydrogenation catalyst and the second hydrogenation catalyst are not limited. Preferably, the types of the first hydrogenation catalyst and the second hydrogenation catalyst may be the same or different, and are preferably the same.

[0052] In some embodiments of the present invention, preferably, the first hydrogenation catalyst and the second hydrogenation catalyst are each independently a supported catalyst, and each independently comprises a carrier and an active component supported on the carrier.

[0053] In the present invention, the types of the carrier and active component have a wide selection range, and are all carriers and active components of conventional supported catalysts in the art. Preferably, the carriers in the first hydrogenation catalyst and the second hydrogenation catalyst are each independently selected from alumina / silicon oxide, and the active components are each independently selected from nickel and / or cobalt, and molybdenum and / or tungsten.

[0054] In some embodiments of the present invention, preferably, in the first hydrogenation catalyst, the nickel and / or cobalt content is 0.1-10wt%, preferably 0.5-8wt%, more preferably 1-5wt%; the molybdenum and / or tungsten content is 5-35wt%, preferably 10-30wt%.

[0055] In some embodiments of the present invention, preferably, the nickel and / or cobalt content of the second hydrogenation catalyst is 0.1-10wt%, preferably 0.5-8wt%, more preferably 1-5wt%; the molybdenum and / or tungsten content is 5-35wt%, preferably 10-30wt%.

[0056] In the present invention, the sources of the first hydrogenation catalyst and the second hydrogenation catalyst have a wide selection range and can be prepared or purchased, for example, purchased from Changling Catalyst of Sinopec Catalyst Branch, a commercial product with the brand name RL-2 catalyst.

[0057] In the present invention, since the hydrogenation saturation reaction rate of polycyclic aromatic hydrocarbons is much higher than the saturation rate of monocyclic and dicyclic aromatic hydrocarbons, the first hydrogenation treatment aims to convert most of the polycyclic aromatic hydrocarbons in the middle fraction into low-ring aromatic hydrocarbons; the second hydrogenation treatment aims to further convert part of the unconverted polycyclic aromatic hydrocarbons into monocyclic and dicyclic aromatic hydrocarbons, while reducing the hydrogenation saturation ring-opening cracking of monocyclic and dicyclic aromatic hydrocarbons, and increasing the content of the ideal component of environmentally friendly rubber filler oil in the hydrogenated oil slurry.

[0058] In some embodiments of the present invention, preferably, the conditions of the first hydrotreatment include: temperature of 290-380°C, preferably 320-360°C; pressure of 8-16MPa, preferably 10-14MPa; volume space velocity of 0.3-2h -1 , preferably 0.5-1h -1 The volume ratio of hydrogen to oil is 500-1500:1, preferably 800-1200:1. The volume ratio of hydrogen to oil refers to the volume ratio of hydrogen to the middle distillate.

[0059] In the present invention, unless otherwise specified, the pressure refers to the gauge pressure.

[0060] In some embodiments of the present invention, preferably, the conditions of the second hydrotreatment include: temperature of 260-350°C, preferably 290-320°C; pressure of 5-12MPa, preferably 6-10MPa; volume space velocity of 0.3-2h -1 , preferably 0.5-1h -1 The volume ratio of hydrogen to oil is 500-1500:1, preferably 800-1200:1. The volume ratio of hydrogen to oil refers to the volume ratio of hydrogen to hydrogenation product-I.

[0061] In the present invention, the middle fraction is subjected to the first hydrogenation treatment and the second hydrogenation treatment in sequence, so that most of the polycyclic aromatic hydrocarbons in the middle fraction are hydrogenated and saturated, that is, the refractive index is significantly reduced. When the refractive index at 20°C is not greater than 1.52, the content of polycyclic aromatic hydrocarbons in the hydrogenated product-II is less than 3wt%; at the same time, in order to avoid further hydrogenation saturation of monocyclic and bicyclic aromatic hydrocarbons, the refractive index of the hydrogenated product-II cannot be too low, that is, the refractive index at 20°C is not less than 1.49.

[0062] According to the present invention, preferably, the refractive index of the hydrogenated product-II at 20°C is 1.49-1.52, for example, 1.49, 1.5, 1.505, 1.51, 515, 1.52, and any value in the range of any two values, preferably 1.5-1.515; the kinematic viscosity at 100°C is 6-10 mm 2 / s, preferably 7-9mm 2 The preferred conditions are adopted to make the content of polycyclic aromatic hydrocarbons in the rubber extension oil less than 3wt%.

[0063] In the present invention, unless otherwise specified, the refractive index parameters are measured using SH / T 0724 (Method for Determination of Refractive Index and Refractive Dispersion of Liquid Hydrocarbons).

[0064] In some embodiments of the present invention, preferably, in step (3), the weight ratio of the hydrogenated product-II to the olefin is 1:0.3-5, for example, 1:0.3, 1:0.5, 1:1, 1:1.5, 1:2, 1:3, 1:4, 1:5, and any value in the range of any two values, preferably 1:0.5-2. The preferred conditions can ensure that the hydrogenated product undergoes alkylation reaction with sufficient olefins, so that the rubber filler oil has the characteristics of high viscosity.

[0065] In some embodiments of the present invention, preferably, the weight ratio of the acid catalyst to the olefin is 0.01-0.5:1, for example, 0.01:1, 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.5:1, and any value in the range consisting of any two values, preferably 0.05-0.3:1.

[0066] In some embodiments of the present invention, preferably, the alkylation reaction conditions include: temperature of 20-150° C., preferably 60-120° C.; time of 5-300 min, preferably 10-60 min. With the preferred conditions, the rubber filler oil has the characteristic of high viscosity.

[0067] In the present invention, the type of the acidic catalyst has a wide selection range. Preferably, the acidic catalyst is selected from at least one of metal halides, hydrogen fluoride, boron trifluoride, concentrated sulfuric acid and ionic liquids containing halide anions, preferably metal halides; further preferably, the metal halide is selected from at least one of aluminum trichloride, ferric trichloride and zinc chloride, preferably aluminum trichloride.

[0068] In some embodiments of the present invention, preferably, the olefin is a C5-C 18 The linear α-olefins and / or internal olefins preferably have C6-C 10of linear alpha-olefins and / or internal olefins.

[0069] In some embodiments of the present invention, preferably, the distillation range of the rubber filler oil is ≥ 450° C., preferably 450-540° C. The use of the preferred conditions is more conducive to improving the viscosity parameters of the rubber filler oil.

[0070] In some embodiments of the present invention, preferably, the kinematic viscosity of the rubber filler oil at 100°C is ≥ 20 mm 2 / s, preferably 20-26mm 2 / s, the content of condensed aromatic hydrocarbons is less than 3wt%, preferably 2-2.9wt%.

[0071] In the present invention, unless otherwise specified, the rubber filler oil meeting the product index means that the aromatic carbon value parameter, pour point parameter and flash point parameter of the rubber filler oil all meet GB / T 33322-2016, that is, the aromatic carbon value of the rubber filler oil product is ≥18, the pour point is ≥20°C, and the flash point is ≥220°C.

[0072] In the present invention, unless otherwise specified, the aromatic carbon value parameter is measured using SH / T 0725 (calculation method for carbon type composition of petroleum-based insulating oil); the pour point parameter is measured using GB / T 3535-2008 (pour point determination method for petroleum products); and the flash point parameter is measured using CB / T 6540 (color determination method for petroleum products).

[0073] According to a particularly preferred embodiment of the present invention, the method comprises the following steps:

[0074] (1) subjecting the catalytic cracking slurry to a first fractionation to obtain an intermediate fraction having a distillation range of 400-520° C.;

[0075] (2) in the presence of hydrogen, subjecting the middle fraction to a first hydrogenation treatment with a first hydrogenation catalyst, and subjecting the obtained hydrogenated product-I to a second hydrogenation treatment with a second hydrogenation catalyst to obtain a hydrogenated product-II;

[0076] (3) alkylating the hydrogenated product II with an olefin in the presence of an acidic catalyst to obtain an alkylated product;

[0077] (4) subjecting the alkylation product to a second fractionation to obtain a heavy fraction with a distillation range of 450-540° C. as rubber extender oil;

[0078] The conditions of the first hydrotreatment include: temperature of 320-360°C; pressure of 10-14 MPa; volumetric space velocity of 0.5-1 h -1; Hydrogen oil volume ratio is 800-1200:1; The second hydrotreatment conditions include: temperature 290-320 ° C; pressure 6-10MPa; volume space velocity 0.5-1h -1 ; The volume ratio of hydrogen to oil is 800-1200:1;

[0079] The refractive index of the hydrogenated product II at 20°C is 1.5-1.515; the kinematic viscosity at 100°C is 7-9 mm 2 / s.

[0080] The second aspect of the present invention provides a rubber filler oil obtained by the method provided in the first aspect.

[0081] The rubber filling oil product prepared by the method provided by the present invention not only meets environmental protection indicators and high viscosity characteristics, but also has the advantage of high yield.

[0082] The third aspect of the present invention provides a device for preparing rubber filler oil, the device comprising: a distillation tower I, a hydrogenation reactor I, a hydrogenation reactor II, an alkylation reactor, and a distillation tower II connected in sequence;

[0083] The distillation tower I is used to perform a first fractionation on the catalytic cracking slurry to obtain an intermediate fraction with a distillation range of 350-450° C.

[0084] The hydrogenation reactor I is used to carry out a first hydrogenation treatment on the middle distillate and a first hydrogenation catalyst in the presence of hydrogen to obtain a hydrogenated product-I;

[0085] The hydrogenation reactor II is used to carry out a second hydrogenation treatment on the hydrogenated product-I and a second hydrogenation catalyst in the presence of hydrogen to obtain a hydrogenated product-II;

[0086] The alkylation reactor is used to carry out an alkylation reaction between the hydrogenation product-II and olefins in the presence of an acidic catalyst to obtain an alkylated product;

[0087] The distillation tower II is used to perform a second fractionation on the alkylation product to obtain a heavy fraction with a distillation range of ≥400° C. as rubber filler oil.

[0088] According to the present invention, preferably, the distillation tower I and the distillation tower II are each independently selected from a plate tower and / or a packed tower, preferably a packed tower.

[0089] In the present invention, there is a wide range of selection for the types of the hydrogenation reactor I, hydrogenation reactor II and alkylation reactor, all of which are conventional reactor types in the art, and the present invention will not be elaborated herein.

[0090] A schematic diagram of a device for preparing rubber filling oil provided by the present invention is as follows: Figure 1As shown, the device comprises: a distillation tower I1, a hydrogenation reactor I2, a hydrogenation reactor II3, an alkylation reactor 4, and a distillation tower II5 which are connected in sequence;

[0091] The distillation tower I1 is used to perform the first fractionation on the catalytic cracking oil slurry 6 to obtain a light fraction 7, an intermediate fraction 8 and a heavy fraction 9 with a distillation range of 350-450° C.;

[0092] The hydrogenation reactor I 2 is used to carry out a first hydrogenation treatment on the middle distillate 8 and the first hydrogenation catalyst 17 in the presence of hydrogen 16 to obtain a hydrogenated product -I 10;

[0093] The hydrogenation reactor II 3 is used to carry out a second hydrogenation treatment on the hydrogenation product-I 10 and the second hydrogenation catalyst 18 in the presence of hydrogen 16 to obtain the hydrogenation product-II 11;

[0094] The alkylation reactor 4 is used to carry out an alkylation reaction between the hydrogenation product-II 11 and the olefin 12 in the presence of an acidic catalyst 9 to obtain an alkylated product 13;

[0095] The distillation tower II 5 is used to perform a second fractionation on the alkylation product 13 to obtain a heavy fraction 15 having a distillation range of ≥400° C., which is rubber extension oil, and a light fraction 14 .

[0096] The present invention will be described in detail below through examples.

[0097] The first hydrogenation catalyst and the second hydrogenation catalyst were both purchased from Changling Catalyst of Sinopec Catalyst Branch, and were commercially available products with the brand name RL-2 catalyst.

[0098] The alkylation catalyst was aluminum chloride catalyst purchased from Aladdin Reagent Company;

[0099] All olefin raw materials were purchased from Aladdin Reagents.

[0100] The solid content parameters were measured using Q / SH 0742-2018;

[0101] The kinematic viscosity parameters were measured using GB / T 265;

[0102] Refractive index parameters are measured by SH / T 0724;

[0103] The hydrocarbon composition was measured using SH / T 0659;

[0104] Color parameters are measured using CB / T 6540;

[0105] Pour point parameters were measured using GB / T 3535-2008;

[0106] Flash point parameters are measured using GB / T 3536-2008;

[0107] The content of polycyclic aromatic hydrocarbons (PCA) was measured using NB / SH / T 0838;

[0108] The aromatic carbon value (CA value) parameter is measured using SH / T 0725.

[0109] Example 1

[0110] (1) After desolidifying the catalytic cracking slurry, the desolidified catalytic cracking slurry having a solid content of 0.05 wt% is subjected to a first fractionation to obtain an intermediate distillate having a distillation range of 400-520° C. (the specific composition is listed in Table 1);

[0111] (2) In the presence of hydrogen, the middle fraction was subjected to the first hydrogenation treatment with RL-2 catalyst (temperature 340°C, hydrogen partial pressure 12 MPa, volume space velocity 0.8 h -1 , hydrogen to oil volume ratio 1000), to obtain hydrogenation product-I;

[0112] In the presence of hydrogen, the hydrogenated product-I was subjected to a second hydrogenation treatment with RL-2 catalyst (temperature 300°C, hydrogen partial pressure 8MPa, volume space velocity 1h -1 , hydrogen to oil volume ratio 1000), to obtain hydrogenated product-II, wherein the physical properties of hydrogenated product-II are listed in Table 2;

[0113] (3) in the presence of aluminum chloride catalyst, the hydrogenation product II is subjected to an alkylation reaction with octene (temperature is 80° C., time is 30 min) to obtain an alkylated product;

[0114] Wherein, the weight ratio of hydrogenated product-II to octene is 1:0.5, and the weight ratio of aluminum chloride catalyst to octene is 0.2:1;

[0115] (4) The alkylation product is subjected to a second fractionation to obtain a heavy fraction with a distillation range of 450-540° C. as rubber extender oil. The physical properties of the rubber extender oil are listed in Table 2.

[0116] Table 1

[0117]

[0118]

[0119] Example 2

[0120] (1) After desolidifying the catalytic cracking slurry, the desolidified catalytic cracking slurry having a solid content of 0.1 wt% is subjected to a first fractionation to obtain an intermediate distillate having a distillation range of 400-520° C. (the specific composition is listed in Table 1);

[0121] (2) In the presence of hydrogen, the middle fraction was subjected to the first hydrogenation treatment with RL-2 catalyst (temperature 360°C, hydrogen partial pressure 14 MPa, volume space velocity 1 h -1 , hydrogen to oil volume ratio 1200), to obtain hydrogenation product-I;

[0122] In the presence of hydrogen, the hydrogenated product-I was subjected to a second hydrogenation treatment with RL-2 catalyst (temperature 290°C, hydrogen partial pressure 6MPa, volume space velocity 0.5h -1 , hydrogen to oil volume ratio 1200), to obtain hydrogenated product-II, wherein the physical properties of hydrogenated product-II are listed in Table 2;

[0123] (3) in the presence of aluminum chloride catalyst, the hydrogenation product II was subjected to an alkylation reaction with hexene (temperature of 60° C., time of 60 min) to obtain an alkylated product;

[0124] Wherein, the weight ratio of hydrogenation product-II to hexene is 1:1, and the weight ratio of aluminum chloride catalyst to hexene is 0.1:1;

[0125] (4) The alkylation product is subjected to a second fractionation to obtain a heavy fraction with a distillation range of 450-540° C. as rubber extender oil. The physical properties of the rubber extender oil are listed in Table 2.

[0126] Example 3

[0127] (1) After desolidifying the catalytic cracking slurry, the desolidified catalytic cracking slurry having a solid content of 0.03 wt% is subjected to a first fractionation to obtain an intermediate distillate having a distillation range of 400-520° C. (the specific composition is listed in Table 1);

[0128] (2) In the presence of hydrogen, the middle fraction was subjected to the first hydrogenation treatment with RL-2 catalyst (temperature 390°C, hydrogen partial pressure 17 MPa, volume space velocity 1 h -1 , hydrogen to oil volume ratio 1000), to obtain hydrogenation product-I;

[0129] In the presence of hydrogen, the hydrogenated product-I was subjected to a second hydrogenation treatment with RL-2 catalyst (temperature 360°C, hydrogen partial pressure 14 MPa, volume space velocity 1 h -1 , hydrogen to oil volume ratio 1200), to obtain hydrogenated product-II, wherein the physical properties of hydrogenated product-II are listed in Table 2;

[0130] (3) in the presence of aluminum chloride catalyst, the hydrogenation product II is subjected to an alkylation reaction with octene (temperature is 80° C., time is 30 min) to obtain an alkylated product;

[0131] Wherein, the weight ratio of hydrogenated product-II to octene is 1:0.5, and the weight ratio of aluminum chloride catalyst to octene is 0.1:1;

[0132] (4) The alkylation product is subjected to a second fractionation to obtain a heavy fraction with a distillation range of 450-540° C. as rubber extender oil. The physical properties of the rubber extender oil are listed in Table 2.

[0133] Example 4

[0134] (1) After desolidifying the catalytic cracking slurry, the desolidified catalytic cracking slurry having a solid content of 0.05 wt% is subjected to a first fractionation to obtain an intermediate distillate having a distillation range of 400-520° C. (the specific composition is listed in Table 1);

[0135] (2) In the presence of hydrogen, the middle fraction was subjected to the first hydrogenation treatment with RL-2 catalyst (temperature 280°C, hydrogen partial pressure 6 MPa, volume space velocity 1 h -1 , hydrogen to oil volume ratio 1000), to obtain hydrogenation product-I;

[0136] In the presence of hydrogen, the above hydrogenated product-I was subjected to a second hydrogenation treatment with RL-2 catalyst (temperature 250°C, hydrogen partial pressure 4MPa, volume space velocity 1h -1 , hydrogen to oil volume ratio 1200), to obtain hydrogenated product-II, wherein the physical properties of hydrogenated product-II are listed in Table 2;

[0137] Among them, since the content of polycyclic aromatic hydrocarbons in the hydrogenation product-II was too high, steps (3)-(4) were not carried out.

[0138] Example 5

[0139] The method of Example 1 is followed, except that in step (3), the weight ratio of hydrogenated product-II to octene is replaced with 1:0.3, and the other conditions are the same to obtain rubber filler oil, wherein the physical properties of the rubber filler oil are listed in Table 2.

[0140] Example 6

[0141] The method of Example 1 is followed, except that in step (3), the conditions of the alkylation reaction are replaced by a temperature of 20° C. and a time of 70 min, and the other conditions are the same to obtain a rubber filler oil, wherein the physical properties of the rubber filler oil are listed in Table 2.

[0142] Comparative Example 1

[0143] The method of Example 1 was followed, except that there was no second hydrogenation treatment. Since the content of condensed aromatic hydrocarbons in the hydrogenated product-I obtained was too high, steps (3)-(4) were not performed.

[0144] Comparative Example 2

[0145] The method of Example 1 is followed, except that step (3) is omitted, i.e., the hydrogenated product-II is directly subjected to a second fractionation, and the other conditions are the same to obtain rubber filler oil, wherein the physical properties of the rubber filler oil are listed in Table 2.

[0146] Comparative Example 3

[0147] The method of Example 1 is different from that in step (4), the alkylation product is subjected to a second fractionation to obtain a heavy fraction with a distillation range of 350-450° C. as rubber filler oil, wherein the physical properties of the rubber filler oil are listed in Table 2.

[0148] Table 2

[0149]

[0150] Table 2

[0151]

[0152] It can be seen from the data in Table 2 that the method provided by the present invention is used to make the refractive index of the hydrogenated product-II less than 1.52 through two-stage hydrogenation treatment, especially limiting the conditions of the first hydrogenation treatment and the second hydrogenation treatment to be within the preferred protection range, and further regulating the refractive index of the hydrogenated product-II; combined with the alkylation treatment, especially limiting the conditions of the alkylation treatment to be within the preferred protection range, to obtain a kinematic viscosity of more than 20 mm 2 / s and rubber extending oil with a polycyclic aromatic hydrocarbon content of less than 3wt%.

[0153] Compared with Example 1, the conditions of the first hydrotreatment and the second hydrotreatment defined in Example 3 are higher than the protection range defined in the present invention, and the obtained rubber filler oil has a lower yield and aromatic carbon value.

[0154] Compared with Example 1, the conditions of the first hydrogenation treatment and the second hydrogenation treatment specified in Example 4 are lower than the protection scope defined in the present invention, and the refractive index of the obtained hydrogenated product-II is higher than 1.52, which cannot be used to prepare rubber filler oil.

[0155] Compared with Example 1, the weight ratio of the hydrogenated product-II to the olefin defined in Example 5 is not within the preferred protection range defined in the present invention, and the obtained rubber extension oil has a lower kinematic viscosity.

[0156] Compared with Example 1, the alkylation reaction conditions defined in Example 6 are not within the preferred protection range defined in the present invention, and the obtained rubber filler oil has a lower kinematic viscosity.

[0157] Therefore, the rubber filler oil prepared by the method provided by the present invention not only meets the environmental protection index and high viscosity characteristics, but also has the advantages of high yield and high aromatic carbon value.

[0158] 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 preparing a rubber filler oil, characterized in that: The method comprises the following steps: (1) subjecting the catalytic cracking slurry to a first fractionation to obtain an intermediate fraction having a distillation range of 350-540° C.; (2) In the presence of hydrogen, the intermediate fraction is subjected to a first hydrogenation treatment with a first hydrogenation catalyst, and the obtained hydrogenation product-I is subjected to a second hydrogenation treatment with a second hydrogenation catalyst to obtain a hydrogenation product-II; wherein the conditions of the first hydrogenation treatment are: temperature of 290-380°C; pressure of 8-16 MPa; volume space velocity of 0.3-2 h -1 ; The volume ratio of hydrogen to oil is 500-1500:1; The conditions of the second hydrotreatment are: temperature 260-350°C; pressure 5-12 MPa; volume space velocity 0.3-2 h -1 ; The volume ratio of hydrogen to oil is 500-1500:1; The refractive index of the hydrogenated product-II at 20°C is 1.49-1.52; (3) In the presence of an acidic catalyst, alkylating the hydrogenated product II with olefins to obtain an alkylated product; wherein the weight ratio of the hydrogenated product II to the olefin is 1:0.5-2; the alkylation reaction conditions are: temperature of 60-120°C; time of 10-60 min; (4) The alkylation product is subjected to a second fractionation to obtain a heavy fraction with a distillation range of 450-540° C. as rubber extender oil.

2. The method according to claim 1, wherein: The distillation range of the intermediate fraction is 400-520°C; And / or, the physical property parameters of the middle distillate satisfy: 100°C kinematic viscosity <16 mm 2 / s; aromatic hydrocarbon content is 50-99.9wt%; condensed ring aromatic hydrocarbon content is 20-99.9wt%; And / or, the method further comprises: before performing the first fractionation, subjecting the catalytic cracking oil slurry to a desolidification treatment; The solid content in the catalytic cracking oil slurry after the desolidification treatment is ≤0.2wt%.

3. The method according to claim 2, wherein: The physical properties of the intermediate fraction are as follows: kinematic viscosity at 100°C is 10-15 mm 2 / s; aromatic hydrocarbon content is 70-95wt%; polycyclic aromatic hydrocarbon content is 50-90wt%; And / or, the solid content in the catalytic cracking oil slurry after the desolidification treatment is 0.02-0.1wt%.

4. The method according to claim 2, wherein: The solid content in the catalytic cracking oil slurry after the desolidification treatment is 0-0.1wt%.

5. The method according to claim 1, wherein: The first hydrogenation catalyst and the second hydrogenation catalyst are each independently a supported catalyst, and each independently comprises a carrier and an active component supported on the carrier; and / or, the carriers in the first hydrogenation catalyst and the second hydrogenation catalyst are each independently selected from alumina / silicon oxide, and the active components are each independently selected from nickel and / or cobalt, and molybdenum and / or tungsten; and / or, in the first hydrogenation catalyst, the nickel / or cobalt content is 0.1-10wt%; the molybdenum and / or tungsten content is 5-35wt%; And / or, in the second hydrogenation catalyst, the nickel / or cobalt content is 0.1-10wt%; the molybdenum and / or tungsten content is 5-35wt%.

6. The method according to claim 5, wherein: In the first hydrogenation catalyst, the nickel / or cobalt content is 0.5-8wt%; the molybdenum and / or tungsten content is 10-30wt%; And / or, in the second hydrogenation catalyst, the nickel / or cobalt content is 0.5-8wt%; the molybdenum and / or tungsten content is 10-30wt%.

7. The method according to claim 6, wherein: The first hydrogenation catalyst has a nickel / cobalt content of 1-5wt%; And / or, the nickel / or cobalt content in the second hydrogenation catalyst is 1-5wt%.

8. The method according to claim 1, wherein: The conditions of the first hydrotreatment are: temperature of 320-360°C; pressure of 10-14 MPa; volume space velocity of 0.5-1 h -1 ; The volume ratio of hydrogen to oil is 800-1200:

1.

9. The method according to claim 1, wherein: The conditions of the second hydrotreatment are: temperature 290-320°C; pressure 6-10 MPa; volume space velocity 0.5-1 h -1 ; The volume ratio of hydrogen to oil is 800-1200:

1.

10. The method according to claim 1, wherein: The refractive index of the hydrogenated product-II at 20°C is 1.5-1.515; The kinematic viscosity of the hydrogenated product-II at 100°C is 6-10 mm 2 / s.

11. The method according to claim 10, wherein: The kinematic viscosity of the hydrogenated product-II at 100°C is 7-9 mm 2 / s.

12. The method according to claim 1, wherein: In step (3), The weight ratio of the acid catalyst to the olefin is 0.01-0.5:

1.

13. The method according to claim 12, wherein: The weight ratio of the acid catalyst to the olefin is 0.05-0.3:

1.

14. The method according to claim 1, wherein: The acidic catalyst is selected from at least one of metal halides, hydrogen fluoride, boron trifluoride, concentrated sulfuric acid and an ionic liquid containing a halide anion; And / or, the metal halide is selected from at least one of aluminum chloride, ferric chloride and zinc chloride; And / or, the olefin is a C5-C 18 of linear alpha-olefins and / or internal olefins.

15. The method according to claim 1, wherein: The acidic catalyst is a metal halide; And / or, the metal halide is aluminum chloride; And / or, the olefin is a C6-C 10 of linear alpha-olefins and / or internal olefins.

16. The method according to any one of claims 1 to 15, wherein: The kinematic viscosity of the rubber filler oil at 100°C is ≥ 20 mm 2 / s, condensed aromatic hydrocarbon content <3wt%.

17. The method according to claim 16, wherein: The kinematic viscosity of the rubber filling oil at 100°C is 20-26 mm 2 / s, and the content of condensed aromatic hydrocarbons is 2-2.9wt%.

18. Rubber extending oil obtained by the method according to any one of claims 1 to 17.

19. A device for preparing rubber extension oil by the method according to any one of claims 1 to 17, characterized in that: The device comprises: a distillation tower I, a hydrogenation reactor I, a hydrogenation reactor II, an alkylation reactor, and a distillation tower II which are connected in sequence; The distillation tower I is used to perform a first fractionation on the catalytic cracking slurry to obtain an intermediate fraction with a distillation range of 350-450° C. The hydrogenation reactor I is used to carry out a first hydrogenation treatment on the middle distillate and a first hydrogenation catalyst in the presence of hydrogen to obtain a hydrogenated product-I; The hydrogenation reactor II is used to carry out a second hydrogenation treatment on the hydrogenated product-I and a second hydrogenation catalyst in the presence of hydrogen to obtain a hydrogenated product-II; The alkylation reactor is used to carry out an alkylation reaction between the hydrogenation product-II and olefins in the presence of an acidic catalyst to obtain an alkylated product; The distillation tower II is used to perform a second fractionation on the alkylation product to obtain a heavy fraction with a distillation range of 450-540° C. as rubber filler oil.

20. The device according to claim 19, wherein The distillation column I and the distillation column II are each independently selected from a plate column and / or a packed column.

21. The device according to claim 20, wherein: The distillation tower I and the distillation tower II are each independently a packed tower.

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