A high aromatic aromatic rubber plasticizer and preparation method thereof

Abstract

The present invention relates to a high aromatic aromatic rubber plasticizer and a preparation method thereof, wherein the preparation method comprises the following steps: using solvent extraction oil of cycloalkyl or intermediate vacuum distillate oil and mixed oil of cycloalkyl vacuum distillate oil as raw materials, mixing the two, and then performing a shallow hydrogenation refining process to obtain the high aromatic aromatic rubber plasticizer. The preparation method of the present invention has a simple process, obtains high value-added products with low value-added raw materials, expands the source of raw materials, and the obtained rubber plasticizer has the characteristics of high viscosity, high aromatic content and high yield, and can prepare A1820 or A2530 series products that meet the requirements of GB / T 33322-2016 indicators.

Description

Technical Field

[0001] The invention relates to the technical field of rubber plasticizers, in particular to a high-aromatic aromatic rubber plasticizer and a preparation method thereof. Background Art

[0002] Aromatic rubber plasticizers are mainly used in the synthetic rubber and rubber products industries. According to the actual usage and characteristics, they are generally called rubber filler oil and rubber operating oil. For synthetic rubber manufacturers, a certain amount of mineral oil is added during the rubber production process to make it co-condense to produce oil-filled rubber. This mineral oil is generally called rubber filler oil, and the general addition amount is 20%-30%. For rubber product processing companies, such as tire manufacturers, in order to improve the processability of the rubber, the dispersion of reinforcing agents and fillers, it is necessary to add an appropriate amount of mineral oil to the open mill, internal mixer, and extruder to evenly mix various ingredients with rubber so that the rubber can be processed into rubber products with practical value. This mineral oil is generally called rubber operating oil, and the general addition amount is 2%-17%.

[0003] The operating oil used in the tire manufacturing process is generally aromatic oil and high aromatic aromatic rubber plasticizer. Aromatic oil is not environmentally friendly oil. As the environmental protection requirements of tires become increasingly stringent, the tire manufacturing industry has an increasingly strong demand for high aromatic aromatic rubber plasticizers. High viscosity high aromatic rubber plasticizers have excellent performance in the tire processing process due to their high aromatic content.

[0004] At present, the technology of producing high aromatic rubber plasticizer mostly involves solvent refining process, such as solvent deasphalting process or furfural refining process. Since the solvent refining process belongs to the separation process of physical extraction, it is easy to cause the main product yield to be low, the by-product value to be low, the processing cost to be high, and finally the economic benefits of the whole process are not good. At the same time, the raw materials for producing high aromatic rubber plasticizer are affected by the gradual reduction of cycloalkyl raw materials, and the main raw material source cycloalkyl vacuum wax oil will also be less and less. Therefore, it is of great practical significance to broaden the raw materials of high aromatic rubber plasticizer and improve the utilization rate of cycloalkyl raw materials.

[0005] CN105969420A discloses a method for preparing a rubber plasticizer with a low content of condensed aromatic hydrocarbons, wherein the preparation method uses a mixed oil of vacuum distillate oil and aromatic oil rich in aromatic hydrocarbons obtained by a process including but not limited to solvent refining, catalytic cracking, visbreaking, thermal cracking or hydrocracking as raw materials, and obtains a rubber plasticizer product through a solvent refining process. However, the rubber plasticizer product C obtained by this method A The value is not high.

[0006] CN104694157A discloses a method for producing high-aromatic environmentally friendly rubber oil, which utilizes the extracted oil by a solvent extraction method. The solvent used is one of furfural, N-methylpyrrolidone and phenol, and the raw material is the extracted oil produced in the lubricating oil refining process within the distillation range of 350-600°C. First, the solvent and the extracted oil are mixed at a certain temperature according to a certain mass ratio of the solvent oil, and then allowed to stand for a certain time to precipitate two layers, and the upper precipitate is taken for solvent extraction. Under certain process conditions, the raffinate oil obtained can be used as environmentally friendly rubber oil.

[0007] The rubber plasticizer product obtained by the above process has C A If the value is low, such as C A An increase in the value will result in a lower product yield and a more complicated process flow.

[0008] In view of the above situation, it is very necessary to provide a method for preparing a high-viscosity and high-aromatic rubber plasticizer with simple process, high product quality and high yield. Summary of the invention

[0009] In view of the deficiencies in the prior art, the object of the present invention is to provide a high-aromatic aromatic rubber plasticizer and a preparation method thereof. The preparation method has a simple process, and a high-value-added product is obtained with low-value-added raw materials, thereby expanding the source of raw materials. The obtained rubber plasticizer has the characteristics of high viscosity, high aromatic content and high yield, and can be used to prepare A1820 or A2530 series products that meet the requirements of GB / T 33322-2016.

[0010] To achieve this object, the present invention adopts the following technical solutions:

[0011] In a first aspect, the present invention provides a method for preparing a high-aromatic aromatic rubber plasticizer, the preparation method comprising the following steps: using solvent-extracted oil of cycloalkyl or intermediate-base vacuum distillate oil and a mixed oil of cycloalkyl vacuum distillate oil as raw materials, mixing the two, and then subjecting the mixture to a shallow hydrogenation refining process to obtain the high-aromatic aromatic rubber plasticizer.

[0012] In the present invention, solvent-extracted oil of cycloalkyl or intermediate vacuum distillate oil and mixed oil of cycloalkyl vacuum distillate oil are used as raw materials because: the advantages of aromatic components are complementary; using only solvent-extracted oil of cycloalkyl or intermediate vacuum distillate oil will lead to excessive content of three-ring and above polycyclic aromatic hydrocarbons (PCA); using only cycloalkyl vacuum distillate oil will lead to excessive content of product C A The value is too low and the resulting product is not compatible with rubber.

[0013] The preparation method of the present invention has a simple process and obtains high value-added products with low value-added raw materials, namely, high-yield A1820 aromatic rubber plasticizer and A2530 aromatic rubber plasticizer. These two types of high aromatic aromatic rubber plasticizers have excellent processing performance in the tire processing process, are non-toxic green products, reduce the dependence on cycloalkyl vacuum wax oil, make full use of high-quality cycloalkyl crude oil resources, expand the source of raw materials, and have high overall economic benefits of the technology. The rubber plasticizer obtained by the preparation method has a high aromatic content and good compatibility with rubber, and has the ability to give the tire a more superior anti-slip performance during the tire processing process.

[0014] In the present invention, the "intermediate base vacuum distillate oil" refers to: intermediate base vacuum distillate oil is a vacuum distillate oil obtained from crude oil with a characteristic factor K of 11.5-12.1 (for example, 11.6, 11.8, 12.0, etc.), excluding 11.5; "cycloalkyl vacuum distillate oil" refers to: a vacuum distillate oil obtained from crude oil with a characteristic factor K of 10.5-11.5 (for example, 10.6, 10.8, 11.0, 11.2, 11.4, etc.).

[0015] In the present invention, the "shallow hydrorefining process" refers to a process in which the hydrogenation conditions are mild so as to reduce or avoid hydrocracking reactions as much as possible.

[0016] Preferably, the solvent used in the solvent-extracted oil includes any one of furfural, N-methylpyrrolidone, phenol or dimethyl sulfoxide, or a combination of at least two of them, wherein typical but non-limiting combinations include: a combination of furfural and N-methylpyrrolidone, a combination of N-methylpyrrolidone, phenol and dimethyl sulfoxide, a combination of furfural, N-methylpyrrolidone, phenol and dimethyl sulfoxide, etc.

[0017] Preferably, the kinematic viscosity of the solvent-extracted oil at 100°C is ≥ 20 mm 2 / s, for example 22mm 2 / s, 24mm 2 / s, 26mm 2 / s, 28mm 2 / s, 30mm 2 / s, 32mm 2 / s, 34mm 2 / s, 36mm 2 / s, 38mm 2 / s, 40mm 2 / s, 44mm 2 / s etc.

[0018] Preferably, the refractive index of the solvent-extracted oil at 20° C. is ≥ 1.5300, such as 1.5400, 1.5500, 1.5600, etc.

[0019] Preferably, the cycloalkyl or intermediate base vacuum distillate oil is obtained by regular vacuum distillation of cycloalkyl or intermediate base crude oil.

[0020] Preferably, the cycloalkyl or intermediate base vacuum distillate oil comprises any one of a minus second-line distillate oil, a minus third-line distillate oil or a minus fourth-line distillate oil, or a combination of at least two of them, wherein typical but non-limiting combinations include: a combination of a minus second-line distillate oil and a minus third-line distillate oil, a combination of a minus third-line distillate oil and a minus fourth-line distillate oil, a combination of a minus second-line distillate oil, a minus third-line distillate oil and a minus fourth-line distillate oil, etc.

[0021] Preferably, the kinematic viscosity of the cycloalkyl or intermediate vacuum distillate oil at 100°C is ≥4 mm 2 / s, for example 4.5mm 2 / s, 5mm 2 / s、5.5mm 2 / s, 6mm 2 / s, 6.5mm 2 / s, 10mm 2 / s, 15mm 2 / s, 20mm 2 / s, etc.

[0022] Preferably, the C of the cycloalkyl or intermediate vacuum distillate A ≥15%, for example, 16%, 18%, 20%, 22%, 24%, etc.

[0023] Preferably, the 100°C kinematic viscosity of the cycloalkane vacuum distillate oil is ≥4 mm 2 / s, for example 10mm 2 / s, 15mm 2 / s, 18mm 2 / s, 20mm 2 / s, 22mm 2 / s, 24mm 2 / s, etc.

[0024] Preferably, the C of the cycloalkyl vacuum distillate oil is A ≥18%, for example, 18%, 20%, 22%, 24%, etc.

[0025] In the present invention, the cycloalkyl vacuum distillate oil is further preferably C A ≥18%, especially for cycloalkane vacuum distillate oil used alone, because it is necessary to ensure that the raw material contains sufficient aromatics, so as to ensure that the final product after hydrogenation has a high C A value.

[0026] Preferably, in the mixed oil, the mass ratio of the solvent extracted oil of the cycloalkyl or intermediate base vacuum distillate oil to the cycloalkyl vacuum distillate oil is (0.11-9):1, wherein 0.11-9 can be 2, 3, 4, 5, 6, 7, 8, etc.

[0027] In the present invention, the mass ratio of the solvent extracted oil of the cycloalkyl or intermediate vacuum distillate oil to the cycloalkyl vacuum distillate oil is preferably (0.11-9):1. The reason for controlling the mass ratio is that the raw material has a sufficient aromatic content, so as to ensure that the final product C after hydrogenation is A The value is high; the mass ratio of the two is too high, which will make it difficult to reduce the PCA content in the hydrogenation product and it will be difficult to coordinate PCA and C during the hydrogenation process. A The contradictory relationship between the values ​​and the low quality ratio of the two will lead to the C A The value is low.

[0028] Preferably, the mixing temperature is 40-200°C, for example, 60°C, 80°C, 100°C, 120°C, 140°C, 160°C, 180°C, etc.

[0029] Preferably, the mixing time is ≥10 min, such as 15 min, 20 min, 25 min, 30 min, etc.

[0030] Preferably, the reaction temperature of the shallow hydrotreating process is 280-400°C, for example, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, etc.

[0031] Preferably, in the shallow hydrotreating process, the volume fraction ratio of hydrogen to the cycloalkyl or intermediate base vacuum distillate oil is (600-1500):1, wherein 600-1500 can be 800, 1000, 1200, 1400, etc.

[0032] Preferably, in the shallow hydrotreating process, the volume space velocity of the hydrotreating is 0.2-2h -1 , for example 0.4h -1 , 0.6h -1 、0.8h -1 , 1h -1 , 1.2h -1 , 1.4h -1 , 1.6h -1 , 1.8h -1 wait.

[0033] Preferably, in the shallow hydrotreating process, the hydrogen partial pressure is greater than 8 MPa, such as 8.5 MPa, 9 MPa, 9.5 MPa, 10 MPa, etc.

[0034] Preferably, after the shallow hydrotreating process is completed, the hydrogenated oil is further fractionated to obtain a distillate oil with a temperature greater than 360°C (eg, 365°C, 370°C, 375°C, 380°C, etc.).

[0035] Preferably, the catalyst of the shallow hydrorefining process includes any one of a molybdenum-nickel hydrogenation catalyst, a tungsten-nickel hydrogenation catalyst, a molybdenum-cobalt hydrogenation catalyst or a molybdenum-tungsten-nickel hydrogenation catalyst, or a combination of at least two thereof, wherein typical but non-limiting combinations include: a combination of a molybdenum-nickel hydrogenation catalyst and a tungsten-nickel hydrogenation catalyst, a combination of a molybdenum-cobalt hydrogenation catalyst and a molybdenum-tungsten-nickel hydrogenation catalyst, a combination of a molybdenum-nickel hydrogenation catalyst, a tungsten-nickel hydrogenation catalyst, a molybdenum-cobalt hydrogenation catalyst and a molybdenum-tungsten-nickel hydrogenation catalyst, etc., preferably a molybdenum-nickel hydrogenation catalyst, a tungsten-nickel hydrogenation catalyst and a molybdenum-tungsten-nickel hydrogenation catalyst.

[0036] In the present invention, the catalyst is most preferably a tungsten-nickel type hydrogenation catalyst, followed by a molybdenum-nickel type hydrogenation catalyst and a molybdenum-tungsten-nickel type hydrogenation catalyst. The reason is that: relative to the molybdenum-cobalt type hydrogenation catalyst, the tungsten-nickel type hydrogenation catalyst has the best hydrogenation-dearomatization performance; the molybdenum-nickel type hydrogenation catalyst and the molybdenum-tungsten-nickel type hydrogenation catalyst have the second best hydrogenation-dearomatization performance.

[0037] In a second aspect, the present invention provides a high aromatic aromatic rubber plasticizer, which is prepared by the preparation method described in the first aspect and is an A1820 or A2530 product that meets the requirements of GB / T 33322-2016.

[0038] The high aromatic aromatic rubber plasticizer C A >18%, for example 20%, 25%, 30%, 35%, etc.

[0039] In the present invention, the high aromatic aromatic rubber plasticizer may be an A1820 or A2530 product that meets the requirements of GB / T 33322-2016.

[0040] Compared with the prior art, the present invention has the following beneficial effects:

[0041] (1) The rubber plasticizer obtained by the preparation method of the present invention is non-toxic, has a low content of carcinogens, and a high content of aromatic hydrocarbons. A The value can reach more than 18%, indicating that the rubber plasticizer of the present invention has a high aromatic content and good compatibility with rubber, and can give the tire a more superior anti-wet skid performance during tire processing.

[0042] (2) The preparation method of the present invention is simple in process and can obtain high value-added products with low value-added raw materials, namely, high-yield A1820 aromatic rubber plasticizer and A2530 aromatic rubber plasticizer. These two types of high-aromatic aromatic rubber plasticizers have excellent processing performance in the tire processing process and are non-toxic green products. They reduce the dependence on cycloalkyl vacuum wax oil, make full use of high-quality cycloalkyl crude oil resources, expand the source of raw materials, and have high overall economic benefits.

[0043] (3) The yield of the rubber plasticizer obtained by the preparation method of the present invention is above 93.1%, C A The value is above 18.72%, and the density at 20℃ is 0.9398-0.9623g / cm 3 The kinematic viscosity at 100℃ is 18.72mm 2 / s or above, flash point is above 220℃, aniline point is within 68℃, PCA content is within 2.9mg / kg, BaP content is within 0.8mg / kg, and PAHs is within 9.4mg / kg. DETAILED DESCRIPTION

[0044] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0045] In the present invention, the raw materials involved in each embodiment, unless otherwise specified, can be obtained from commercial sources.

[0046] Cycloalkane vacuum distillate oil: Cycloalkane vacuum distillate oil with three-line reduction, such as CNOOC Suizhong 36-1 vacuum distillate oil with three-line reduction.

[0047] Intermediate base vacuum distillate oil: intermediate base minus three-line distillate oil, such as CNOOC Wenchang crude oil minus three-line distillate oil.

[0048] Solvent extracted oil: such as CNOOC Suizhong 36-1 minus three-line extracted oil, CNOOC Suizhong 36-1 minus two-line extracted oil, Wenchang minus three-line extracted oil.

[0049] Molybdenum-nickel type hydrogenation catalyst: purchased from CNOOC Chemical and New Materials Science Research Institute, brand ZQC-26 hydrogenation treatment catalyst.

[0050] Tungsten-nickel type hydrogenation catalyst: purchased from CNOOC Chemical and New Materials Science Research Institute, brand ZQC-25 hydrogenation treatment catalyst.

[0051] Molybdenum-cobalt type hydrogenation catalyst: purchased from CNOOC Chemical and New Materials Science Research Institute, brand name ZQC-27.

[0052] Molybdenum-tungsten-nickel type hydrogenation catalyst: purchased from CNOOC Chemical and New Materials Science Research Institute, brand LR-1.

[0053] Example 1

[0054] This embodiment provides a high aromatic aromatic rubber plasticizer, wherein the aromatic rubber plasticizer is obtained by the following preparation method, and the preparation method comprises the following steps:

[0055] (1) The solvent extraction oil of CNOOC Suizhong 36-1 minus three-line distillate oil and Suizhong 36-1 minus three-line distillate oil were mixed at a mass ratio of 1:1 at 80° C. for 30 minutes to obtain a mixed oil;

[0056] (2) Using mixed oil as raw material, ZQC-25 hydrotreating catalyst was used to carry out shallow hydrotreating refining in a hydrotreating pilot unit. The reaction temperature was 350°C, the hydrogen-oil volume ratio was 1000:1, and the volume space velocity was 0.5 h -1 , the hydrogen partial pressure is 15 MPa, and the obtained hydrogenated oil is subjected to reduced pressure distillation to obtain a fraction oil greater than 360° C. to obtain the high aromatic aromatic rubber plasticizer.

[0057] Example 2

[0058] This embodiment provides a high aromatic aromatic rubber plasticizer, wherein the aromatic rubber plasticizer is obtained by the following preparation method, and the preparation method comprises the following steps:

[0059] (1) The solvent extraction oil of CNOOC Suizhong 36-1 minus three-line distillate oil and Suizhong 36-1 minus three-line distillate oil were mixed at a mass ratio of 2:1 at 100° C. for 20 minutes to obtain a mixed oil;

[0060] (2) Using mixed oil as raw material, ZQC-25 hydrotreating catalyst was used to carry out shallow hydrotreating refining in a hydrotreating pilot plant. The reaction temperature was 360°C, the hydrogen-oil volume ratio was 1000:1, and the volume space velocity was 0.4h -1 , the hydrogen partial pressure is 15 MPa, and the obtained hydrogenated oil is subjected to reduced pressure distillation to obtain a fraction oil greater than 360° C. to obtain the high aromatic aromatic rubber plasticizer.

[0061] Example 3

[0062] This embodiment provides a high aromatic aromatic rubber plasticizer, wherein the aromatic rubber plasticizer is obtained by the following preparation method, and the preparation method comprises the following steps:

[0063] (1) The solvent extracted oil of the Wenchang three-line extraction oil and the Suizhong 36-1 three-line extraction oil were mixed at a mass ratio of 4:1 at 60° C. for 2 h to obtain a mixed oil;

[0064] (2) Using mixed oil as raw material, ZQC-25 hydrotreating catalyst was used to carry out shallow hydrotreating refining in a hydrotreating pilot unit. The reaction temperature was 280°C, the hydrogen-oil volume ratio was 600:1, and the volume space velocity was 0.2h -1 , the hydrogen partial pressure is 18 MPa, and the obtained hydrogenated oil is subjected to reduced pressure distillation to obtain a fraction oil greater than 360° C., thereby obtaining the high aromatic aromatic rubber plasticizer.

[0065] Example 4

[0066] This embodiment provides a high aromatic aromatic rubber plasticizer, wherein the aromatic rubber plasticizer is obtained by the following preparation method, and the preparation method comprises the following steps:

[0067] (1) The solvent extraction oil of CNOOC Suizhong 36-1 minus second-line distillate oil and Suizhong 36-1 minus third-line distillate oil were mixed at a mass ratio of 9:1 at 180° C. for 15 minutes to obtain a mixed oil;

[0068] (2) Using mixed oil as raw material, ZQC-25 hydrotreating catalyst was used to carry out shallow hydrotreating refining in a hydrotreating pilot plant. The reaction temperature was 400°C, the hydrogen-oil volume ratio was 1500:1, and the volume space velocity was 2h -1 , the hydrogen partial pressure is 10 MPa, and the obtained hydrogenated oil is subjected to reduced pressure distillation to obtain a fraction oil greater than 360° C., thereby obtaining the high aromatic aromatic rubber plasticizer.

[0069] Example 5

[0070] The difference between this embodiment and embodiment 1 is that the ZQC-25 hydroprocessing catalyst is replaced with an equal mass of LR-1 hydrorefining catalyst, and the rest is the same as embodiment 1.

[0071] Example 6

[0072] The difference between this embodiment and embodiment 1 is that the ZQC-25 hydroprocessing catalyst is replaced with an equal mass of ZQC-26 hydroprocessing catalyst, and the rest is the same as embodiment 1.

[0073] Example 7

[0074] The difference between this embodiment and embodiment 1 is that the ZQC-25 hydroprocessing catalyst is replaced with an equal mass of ZQC-27 hydroprocessing catalyst, and the rest is the same as embodiment 1.

[0075] Comparative Example 1

[0076] The difference between this comparative example and Example 1 is that the solvent extraction oil is not included, and the rest is the same as Example 1.

[0077] Comparative Example 2

[0078] The difference between this comparative example and Example 1 is that the Suizhong 36-1 minus three-line distillate oil is not included, and the rest is the same as Example 1.

[0079] Performance Testing

[0080] The rubber plasticizers obtained from Examples 1-7 and Comparative Examples 1-2 were tested as follows:

[0081] (1) Yield (relative to mixed oil), %;

[0082] (2) Density at 20℃, g / cm 3 : Tested in accordance with GB / T 1884;

[0083] (3) Kinematic viscosity at 100℃, mm 2 / s: Tested in accordance with GB / T 265;

[0084] (4) Open cup flash point, °C: Tested in accordance with GB / T 3536;

[0085] (5)C A Value, %: Tested in accordance with SH / T 0725;

[0086] (6) Aniline point, °C: tested in accordance with GB / T 262;

[0087] (7) PCA content, mg / kg: tested in accordance with NB / SH / T 0838;

[0088] (8) BaP content, mg / kg: tested according to the first method of SN / T 1877.3-2007;

[0089] (9) PAHs content, mg / kg: tested in accordance with SN / T 1877.3-2007 method 1.

[0090] The test results are summarized in Table 1.

[0091] Table 1

[0092]

[0093]

[0094] According to the data in Table 1, the yield of the rubber plasticizer obtained by the preparation method of the present invention is above 93.1%. A The value is above 18.72%, and the density at 20℃ is 0.9398-0.9623g / cm 3 The kinematic viscosity at 100℃ is 18.72mm 2 / s or more, the flash point is above 220°C, the aniline point is within 68°C, the PCA content is within 2.9mg / kg, the BaP content is within 0.8mg / kg, and the PAHs is within 9.4mg / kg. The preparation method of the present invention is simple in process, and high value-added products are obtained with low value-added raw materials, namely, high-yield A1820 aromatic rubber plasticizer and A2530 aromatic rubber plasticizer (taking Examples 1 and 2 as examples). These two types of high-aromatic aromatic rubber plasticizers have excellent processing performance in the tire processing process, are non-toxic green products, and the overall economic benefits of the technology are high.

[0095] In the preferred range (taking Examples 1-4 as an example), the yield of the rubber plasticizer obtained by the preparation method of the present invention is above 93.8%, C A The value was above 19.2%, the PCA content was within 1.8 mg / kg, and the BaP content and PAHs were not detected.

[0096] In the present invention, C A The value refers to the aromatic carbon ratio, PCA refers to the content of three-ring and above polycyclic aromatic hydrocarbons, BaP refers to benzo[a]pyrene, and PAHs refers to 8 kinds of polycyclic aromatic hydrocarbon compounds, including benzo[a]anthracene, There are 8 polycyclic carcinogenic aromatic hydrocarbons, including benzo[b]fluoranthene, benzo[j]fluoranthene, benzo[k]fluoranthene, benzo[e]pyrene, benzo[a]pyrene, and dibenzo[a,h]anthracene. This test is mainly to determine the carcinogenic content.

[0097] Analysis of Comparative Examples 1-2 and Example 1 shows that Comparative Examples 1-2 are not as good as Example 1. Specifically, C A The value is relatively low, the aniline point is relatively high, and the PCA content of Comparative Example 2 is significantly higher, which proves that the preparation method of the present invention using the solvent-extracted oil of cycloalkyl or intermediate vacuum distillate oil and the mixed oil of cycloalkyl vacuum distillate oil as raw materials is more conducive to the preparation of high aromatic aromatic rubber plasticizer.

[0098] Analysis of Examples 5-7 and Example 1 shows that Examples 5-7 are not as good as Example 1, which proves that the rubber plasticizer formed by the most preferred tungsten-nickel type hydrogenation catalyst in the preparation method of the present invention has better performance.

[0099] The present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing a high aromatic aromatic rubber plasticizer, characterized in that: The preparation method comprises the following steps: using solvent extraction oil of cycloalkyl or intermediate vacuum distillate oil and mixed oil of cycloalkyl vacuum distillate oil as raw materials, mixing the two, and then subjecting the mixture to a shallow hydrogenation refining process to obtain the high aromatic aromatic rubber plasticizer; The catalyst of the shallow hydrorefining process is a tungsten-nickel type hydrogenation catalyst; The kinematic viscosity of the cycloalkyl or intermediate vacuum distillate oil at 100°C is ≥4 mm 2 / s; The cycloalkyl or intermediate base vacuum distillate oil A ≥15%; In the mixed oil, the mass ratio of the solvent-extracted oil of the cycloalkyl or intermediate-base vacuum distillate oil to the cycloalkyl vacuum distillate oil is (0.11-9):1; The reaction temperature of the shallow hydrotreating process is 280-400°C; In the shallow hydrotreating process, the volume ratio of hydrogen to the cycloalkyl or intermediate base vacuum distillate oil is (600-1500):1; In the shallow hydrotreating process, the hydrogen partial pressure is greater than 8 MPa.

2. The preparation method according to claim 1, characterized in that: The solvent used in the solvent-extracted oil includes any one of furfural, N-methylpyrrolidone, phenol or dimethyl sulfoxide, or a combination of at least two of them.

3. The preparation method according to claim 1, characterized in that: The kinematic viscosity of the solvent extracted oil at 100°C is ≥20mm 2 / s.

4. The preparation method according to claim 1, characterized in that: The solvent extracted oil has a refractive index of ≥1.5300 at 20°C.

5. The preparation method according to claim 1, characterized in that: The cycloalkyl or intermediate base vacuum distillate oil is obtained by regular vacuum distillation of cycloalkyl or intermediate base crude oil.

6. The preparation method according to claim 1, characterized in that: The cycloalkyl or intermediate base vacuum distillate oil includes any one of the reduced second-line distillate oil, reduced third-line distillate oil or reduced fourth-line distillate oil, or a combination of at least two of them.

7. The preparation method according to claim 1, characterized in that: The CA of the cycloalkane vacuum distillate oil is ≥18%.

8. The preparation method according to claim 1, characterized in that: The mixing temperature is 40-200°C.

9. The preparation method according to claim 1, characterized in that: The mixing time is ≥10 min.

10. The preparation method according to claim 1, characterized in that: In the shallow hydrotreating process, the volume space velocity of the hydrotreating is 0.2-2 h -1 .

11. The preparation method according to claim 1, characterized in that: After the shallow hydrotreating process is completed, the hydrogenated oil is fractionated to obtain a fraction oil with a temperature greater than 360°C.

12. A high aromatic aromatic rubber plasticizer, characterized in that: The high aromatic aromatic rubber plasticizer is prepared by the preparation method according to any one of claims 1 to 11, and is an A1820 or A2530 product that meets the requirements of GB / T 33322-2016; The high aromatic aromatic rubber plasticizer has a CA>18%.

Images