An aromatic rubber plasticizer with high aromatic hydrocarbons and a preparation method thereof

Abstract

The present invention relates to an aromatic rubber plasticizer with high aromatics and a preparation method thereof. The preparation method comprises the following steps: (1) subjecting the solvent-extracted oil of naphthenic or intermediate-base vacuum distillate oil to a hydrotreating reaction, removing the light fractions from the obtained hydrogenated oil, and the remaining heavy fraction is the first treated oil; (2) subjecting the naphthenic vacuum distillate oil to a hydrotreating reaction, removing the light fractions from the obtained hydrogenated oil, and the remaining heavy fraction is the second treated oil; (3) mixing the first treated oil and the second treated oil to obtain the aromatic rubber plasticizer with high aromatics. The preparation method of the present invention has a simple process, obtains high-value-added products from low-value-added raw materials, expands the raw material sources, and the obtained rubber plasticizer has the characteristics of high viscosity, high aromatics content and high yield, and can prepare A1820 or A2530 series products meeting the index requirements of GB / T 33322-2016.

Description

Technical Field

[0001] The present invention relates to the technical field of rubber plasticizers, and particularly relates to an aromatic rubber plasticizer with high aromatic hydrocarbons and a preparation method thereof. Background Art

[0002] Aromatic rubber plasticizers are mainly applied to the synthetic rubber and rubber products industries. According to the actual usage methods and characteristics, they are generally called rubber filling oils and rubber processing oils. For synthetic rubber manufacturers, during the production process of rubber compounds, a certain amount of mineral oil is filled to co-condense and produce oil-extended rubber. This kind of mineral oil is generally called rubber filling oil, and the general addition amount is 20%-30%. For rubber product processing enterprises, such as tire manufacturers, in order to improve the processability of rubber compounds and the dispersibility of reinforcing agents and fillers, an appropriate amount of mineral oil must be added in the open mill, internal mixer, and extruder to uniformly mix various ingredients with rubber so that the rubber compound can be processed into a rubber product with practical value. This kind of mineral oil is generally called rubber processing oil, and the general addition amount is 2%-17%.

[0003] The processing oil used in the tire manufacturing process generally selects aromatic oil and high-aromatic aromatic rubber plasticizers. Aromatic oil is a non-environmental protection oil product. With the increasingly strict environmental protection requirements for tires, the demand for high-aromatic aromatic rubber plasticizers in the tire manufacturing industry is becoming increasingly strong. And high-viscosity high-aromatic rubber plasticizers have relatively excellent performance during tire processing due to their high aromatic hydrocarbon content.

[0004] At present, the technologies for producing high-aromatic rubber plasticizers mostly involve solvent refining processes, such as solvent deasphalting processes or furfural refining processes. Since the solvent refining process belongs to a separation process of physical extraction, it is prone to problems such as low yield of the main product, low value of by-products, and high processing costs, ultimately resulting in poor economic benefits of the entire process. At the same time, due to the gradual reduction of naphthenic raw materials, the main raw material source of naphthenic vacuum gas oil for producing high-aromatic rubber plasticizers will also become less and less. Therefore, broadening the raw materials for high-aromatic rubber plasticizers and improving the utilization rate of naphthenic raw materials have great practical significance.

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

[0006] CN112940782A discloses a preparation method of an environmentally friendly rubber plasticizer. The disclosed preparation method includes the following steps: a) subjecting a petroleum fraction raw material to hydrofining, hydrodewaxing, and hydro-upgrading in sequence to obtain a hydrogenated liquid product; b) subjecting the hydrogenated liquid product to vacuum distillation, collecting fractions, and obtaining a rubber plasticizer.

[0007] The rubber plasticizer product obtained by the above process has a low C A value. If the C A value is increased, the product yield will be relatively low and the process flow will be relatively complex.

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

[0009] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a high-aromatic aryl rubber plasticizer and a preparation method thereof. The preparation method has a simple process, obtains a high-value-added product from low-value-added raw materials, expands the raw material sources, 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 index requirements of GB / T33322-2016.

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

[0011] In the first aspect, the present invention provides a preparation method of a high-aromatic aryl rubber plasticizer, and the preparation method includes the following steps:

[0012] (1) Subjecting the solvent-extracted oil of the naphthenic or intermediate-base vacuum distillate oil to a hydrotreating reaction, and after removing the light fractions from the obtained hydrogenated oil, the remaining heavy fraction is the first treated oil;

[0013] (2) Subjecting the naphthenic-base vacuum distillate oil to a hydrotreating reaction, and after removing the light fractions from the obtained hydrogenated oil, the remaining heavy fraction is the second treated oil;

[0014] (3) Mixing the first treated oil and the second treated oil to obtain the high-aromatic aryl rubber plasticizer.

[0015] The preparation method of the present invention has a simple process, obtaining high-value-added products from low-value-added raw materials, namely A1820 aromatic rubber plasticizer and A2530 aromatic rubber plasticizer with high yields. These two types of aromatic rubber plasticizers with high aromatic hydrocarbon content have excellent processing properties during tire processing, are non-toxic green products, reduce the dependence on naphthenic vacuum gas oil, make full use of high-quality naphthenic crude oil resources, expand the raw material sources, and the overall economic benefit of the technology is relatively high. The rubber plasticizer obtained by the preparation method has a high aromatic hydrocarbon content and good compatibility with rubber, and endows the tire with more excellent wet skid resistance during tire processing.

[0016] In the present invention, the preparation sequence of step (1) and step (2) can be replaced.

[0017] In the present invention, the "intermediate base vacuum distillate" refers to: the intermediate base vacuum distillate is the vacuum distillate obtained from crude oil with a characterization factor K of 11.5 - 12.1 (such as 11.6, 11.8, 12.0, etc.), excluding 11.5; the "naphthenic vacuum distillate" refers to: the vacuum distillate obtained from crude oil with a characterization factor K of 10.5 - 11.5 (such as 10.6, 10.8, 11.0, 11.2, 11.4, etc.).

[0018] Preferably, in step (1), the solvent used in the solvent-extracted oil includes any one or a combination of at least two of furfural, N-methylpyrrolidone, phenol, or dimethyl sulfoxide. Typical but non-limiting combinations include: the combination of furfural and N-methylpyrrolidone, the combination of N-methylpyrrolidone, phenol, and dimethyl sulfoxide, the combination of furfural, N-methylpyrrolidone, phenol, and dimethyl sulfoxide, etc.

[0019] Preferably, the kinematic viscosity of the solvent-extracted oil at 100 °C ≥ 20 mm 2 / s, such as 22 mm 2 / s, 24 mm 2 / s, 26 mm 2 / s, 28 mm 2 / s, 30 mm 2 / s, 32 mm 2 / s, 34 mm 2 / s, 36 mm 2 / s, 38 mm 2 / s, 40 mm 2 / s, 44 mm 2 / s, etc.

[0020] Preferably, the refractive index of the solvent-extracted oil at 20 °C ≥ 1.5300, such as 1.5400, 1.5500, 1.5600, etc.

[0021] Preferably, the naphthenic or intermediate-base vacuum distillate oil is obtained by the atmospheric and vacuum distillation of naphthenic or intermediate-base crude oil.

[0022] Preferably, in step (1), the naphthenic or intermediate-base vacuum distillate oil includes any one or a combination of at least two of the second-line vacuum distillate oil, third-line vacuum distillate oil, or fourth-line vacuum distillate oil. Typical but non-limiting combinations include: the combination of the second-line vacuum distillate oil and the third-line vacuum distillate oil, the combination of the third-line vacuum distillate oil and the fourth-line vacuum distillate oil, the combination of the second-line vacuum distillate oil, the third-line vacuum distillate oil, and the fourth-line vacuum distillate oil, etc.

[0023] Preferably, in step (1), the kinematic viscosity of the naphthenic or intermediate-base vacuum distillate oil at 100 °C ≥ 4 mm 2 / s, such as 4.5 mm 2 / s, 5 mm 2 / s, 5.5 mm 2 / s, 6 mm 2 / s, 6.5 mm 2 / s, 10 mm 2 / s, 15 mm 2 / s, 20 mm 2 / s, etc.

[0024] Preferably, the C A of the naphthenic or intermediate-base vacuum distillate oil ≥ 15%, such as 16%, 18%, 20%, 22%, 24%, etc.

[0025] Preferably, in step (2), the naphthenic vacuum distillate oil includes any one or a combination of at least two of the second-line vacuum distillate oil, third-line vacuum distillate oil, or fourth-line vacuum distillate oil. Typical but non-limiting combinations include: the combination of the second-line vacuum distillate oil and the third-line vacuum distillate oil, the combination of the third-line vacuum distillate oil and the fourth-line vacuum distillate oil, the combination of the second-line vacuum distillate oil, the third-line vacuum distillate oil, and the fourth-line vacuum distillate oil, etc.

[0026] Preferably, the kinematic viscosity of the naphthenic vacuum distillate oil at 100 °C ≥ 4 mm 2 / s, such as 10 mm 2 / s, 15 mm 2 / s, 18 mm 2 / s, 20 mm 2 / s, 22 mm 2 / s, 24 mm 2 / s, etc.

[0027] Preferably, the C A of the naphthenic vacuum distillate oil ≥ 18%, such as 20%, 22%, 24%, etc.

[0028] In the present invention, when preparing the second treated oil, for CA The value requirement is higher because: C A A value less than 18% will result in a final product C A The reason for not selecting the middle-base vacuum gas oil is that the C of the middle-base vacuum gas oil A has a low value.

[0029] Preferably, in steps (1) and (2), the heavy fractions of the hydrotreated oils obtained from the first hydrotreating reaction zone and the second hydrotreating reaction zone after removing the light fractions are each independently fractions greater than 360 °C (such as 365 °C, 370 °C, 375 °C, etc.).

[0030] Preferably, in steps (1) and (2), the catalysts for the hydrotreating reaction each independently include any one or a combination of at least two of a molybdenum-nickel type hydrotreating catalyst, a tungsten-nickel type hydrotreating catalyst, a molybdenum-cobalt type hydrotreating catalyst, or a molybdenum-tungsten-nickel type hydrotreating catalyst. Among them, typical but non-limiting combinations include: a combination of a molybdenum-nickel type hydrotreating catalyst and a tungsten-nickel type hydrotreating catalyst, a combination of a molybdenum-cobalt type hydrotreating catalyst and a molybdenum-tungsten-nickel type hydrotreating catalyst, a combination of a molybdenum-nickel type hydrotreating catalyst, a tungsten-nickel type hydrotreating catalyst, a molybdenum-cobalt type hydrotreating catalyst, and a molybdenum-tungsten-nickel type hydrotreating catalyst, etc. Preferably, a molybdenum-nickel type hydrotreating catalyst, a tungsten-nickel type hydrotreating catalyst, and a molybdenum-tungsten-nickel type hydrotreating catalyst.

[0031] In the present invention, the most preferred catalyst is a tungsten-nickel type hydrotreating catalyst, followed by a molybdenum-nickel type hydrotreating catalyst and a molybdenum-tungsten-nickel type hydrotreating catalyst, because: compared with a molybdenum-cobalt type hydrotreating catalyst, the tungsten-nickel type hydrotreating catalyst has the best hydrodearomatization performance; the molybdenum-nickel type hydrotreating catalyst and the molybdenum-tungsten-nickel type hydrotreating catalyst have the second-best hydrodearomatization performance.

[0032] Preferably, in step (1), the reaction temperature of the hydrotreating reaction is 280 - 400 °C, such as 290 °C, 300 °C, 310 °C, 320 °C, 330 °C, 340 °C, 350 °C, 360 °C, 370 °C, 380 °C, 390 °C, etc.

[0033] Preferably, in the hydrotreating reaction, the volume ratio of hydrogen to the naphthenic or middle-base vacuum gas oil is (600 - 1500):1, where 600 - 1500 can be 800, 1000, 1200, 1400, etc.

[0034] Preferably, in the hydrotreating reaction, the volume space velocity of the hydrotreating is 0.2 - 2.0 h -1 , such as 0.4 h -1 , 0.6 h -1 , 0.8 h -1 , 1 h -1, 1.2 h -1 , 1.4 h -1 , 1.5 h -1 , 1.6 h -1 , 1.7 h -1 , 1.8 h -1 , 1.9 h -1 etc.

[0035] Preferably, in the hydrotreating reaction, the hydrogen partial pressure > 10 MPa, such as 10.5 MPa, 11 MPa, 11.5 MPa, 12 MPa, etc.

[0036] Preferably, in step (2), the reaction temperature of the hydrotreating reaction is 280 - 380 °C, such as 290 °C, 300 °C, 310 °C, 320 °C, 330 °C, 340 °C, 350 °C, 360 °C, 370 °C, etc.

[0037] Preferably, in the hydrotreating reaction, the volume fraction ratio of hydrogen to the naphthenic vacuum gas oil is (600 - 1500):1, where 600 - 1500 can be 800, 1000, 1200, 1400, etc.

[0038] Preferably, in the hydrotreating reaction, the volume hourly space velocity of the hydrotreating is 0.2 - 2.0 h -1 , such as 0.4 h -1 , 0.6 h -1 , 0.8 h -1 , 1 h -1 , 1.2 h -1 , 1.4 h -1 , 1.5 h -1 , 1.6 h -1 , 1.7 h -1 , 1.8 h -1 , 1.9 h -1 etc.

[0039] Preferably, in the hydrotreating reaction, the hydrogen partial pressure > 8 MPa, such as 8.5 MPa, 9 MPa, 9.5 MPa, 10 MPa, etc.

[0040] Preferably, in step (3), the mass ratio of the first treated oil to the second treated oil is (0.11 - 9):1, where 0.11 - 9 can be 2, 3, 4, 5, 6, 7, 8, etc.

[0041] Preferably, the temperature of the mixing is 40 - 200 °C, such as 60 °C, 80 °C, 100 °C, 120 °C, 140 °C, 160 °C, 180 °C, etc.

[0042] Preferably, the mixing time ≥ 10 min, such as 15 min, 20 min, 25 min, 30 min, etc.

[0043] In a second aspect, the present invention provides an aromatic rubber plasticizer with high aromatic hydrocarbons, which is obtained by the preparation method described in the first aspect and is an A1820 or A2530 product meeting the index requirements of GB / T 33322-2016.

[0044] Preferably, the C A value of the aromatic rubber plasticizer with high aromatic hydrocarbons ≥ 18%, such as 20%, 22%, 24%, 26%, 28%, etc.

[0045] Compared with the prior art, the present invention has the following beneficial effects:

[0046] (1) The rubber plasticizer obtained by the preparation method of the present invention is non-toxic, has a low carcinogenic substance content, and a high aromatic hydrocarbon content. At the same time, the C A value of the rubber plasticizer of the present invention can reach more than 18%, indicating that the rubber plasticizer of the present invention has a high aromatic hydrocarbon content and good compatibility with rubber, and has more excellent wet skid resistance performance when used in tire processing.

[0047] (2) The preparation method of the present invention has a simple process, and high-value-added products are obtained from low-value-added raw materials, namely, A1820 aromatic rubber plasticizer and A2530 aromatic rubber plasticizer with high yields. These two types of aromatic rubber plasticizers with high aromatic hydrocarbons have excellent processing performance during tire processing, are non-toxic green products, reduce the dependence on naphthenic vacuum gas oil, make full use of high-quality naphthenic crude oil resources, expand the raw material sources, and the overall economic benefit of the technology is relatively high.

[0048] (3) The yield of the rubber plasticizer obtained by the preparation method of the present invention is above 95.2%, the C A value is above 18%, the density at 20 °C is between 0.9478 - 0.9633 g / cm 3 , the kinematic viscosity at 100 °C is above 18.61 mm 2 / s, the flash point is above 220 °C, the aniline point is within 69 °C, the PCA content is within 2.9 mg / kg, the BaP content is within 0.6 mg / kg, and the PAHs are within 8.7 mg / kg. Specific Embodiments

[0049] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0050] In the present invention, the raw materials involved in each embodiment can be obtained from commercial channels without special instructions.

[0051] Naphthenic vacuum distillate oil: Naphthenic third-stage vacuum distillate oil, such as the third-stage vacuum distillate oil of CNOOC Suizhong 36-1.

[0052] Intermediate-base vacuum distillate oil: Intermediate-base third-stage vacuum distillate oil, such as the third-stage vacuum distillate oil of CNOOC Wenchang crude oil.

[0053] Solvent-extracted oil: Such as the third-stage extracted oil of CNOOC Suizhong 36-1, the second-stage extracted oil of CNOOC Suizhong 36-1, and the third-stage extracted oil of Wenchang.

[0054] Molybdenum-nickel type hydrogenation catalyst: Purchased from CNOOC Research Institute of Chemical Industry and New Materials, with the brand number of ZQC-26 hydrotreating catalyst.

[0055] Tungsten-nickel type hydrogenation catalyst: Purchased from CNOOC Research Institute of Chemical Industry and New Materials, with the brand number of ZQC-25 hydrotreating catalyst.

[0056] Molybdenum-cobalt type hydrogenation catalyst: Purchased from CNOOC Research Institute of Chemical Industry and New Materials, with the brand number of ZQC-27.

[0057] Molybdenum-tungsten-nickel type hydrogenation catalyst: Purchased from CNOOC Research Institute of Chemical Industry and New Materials, with the brand number of LR-1.

[0058] Example 1

[0059] This example provides an aromatic rubber plasticizer with high aromatic hydrocarbons. The aromatic rubber plasticizer is obtained by the following preparation method, and the preparation method includes the following steps:

[0060] (1) Using the third-stage extracted oil of CNOOC Suizhong 36-1 as the raw material, adopting the ZQC-25 hydrotreating catalyst, carrying out the hydrotreating reaction in a hydrotreating pilot plant. The reaction temperature is 350 °C, the hydrogen-oil volume ratio is 1000:1, the volume space velocity is 0.5 h -1 , and the hydrogen partial pressure is 15 MPa. After removing the light fraction from the obtained hydrogenated oil, the fraction oil with a temperature higher than 360 °C is obtained as the first treated oil;

[0061] (2) Using the third-stage vacuum distillate oil of CNOOC Suizhong 36-1 as the raw material, adopting the ZQC-25 hydrotreating catalyst, carrying out the hydrotreating reaction in a hydrotreating pilot plant. The reaction temperature is 320 °C, the hydrogen-oil volume ratio is 1000:1, the volume space velocity is 0.3 h -1 , and the hydrogen partial pressure is 15 MPa. After removing the light fraction from the obtained hydrogenated oil, the fraction oil with a temperature higher than 360 °C is obtained as the second treated oil;

[0062] (3) Mix the first treated oil and the second treated oil at a mass ratio of 1:1 for 20 min at 80 °C to obtain the aromatic rubber plasticizer with high aromatic hydrocarbons.

[0063] Example 2

[0064] This example provides an aromatic rubber plasticizer with high aromatic hydrocarbons. The aromatic rubber plasticizer is obtained by the following preparation method, and the preparation method includes the following steps:

[0065] (1) Using the CNOOC Suizhong 36-1 vacuum gas oil cut as raw material, adopt the ZQC-25 hydrotreating catalyst, carry out the hydrotreating reaction in a hydrotreating pilot plant, the reaction temperature is 360 °C, the hydrogen-oil volume ratio is 1000:1, the volume space velocity is 0.25 h -1 , the hydrogen partial pressure is 15 MPa. After removing the light fractions from the obtained hydrogenated oil, the fraction oil with a boiling point higher than 360 °C is obtained as the first treated oil;

[0066] (2) Using the CNOOC Suizhong 36-1 vacuum gas oil cut as raw material, adopt the ZQC-25 hydrotreating catalyst, carry out the hydrotreating reaction in a hydrotreating pilot plant, the reaction temperature is 320 °C, the hydrogen-oil volume ratio is 1000:1, the volume space velocity is 0.6 h -1 , the hydrogen partial pressure is 15 MPa. After removing the light fractions from the obtained hydrogenated oil, the fraction oil with a boiling point higher than 360 °C is obtained as the second treated oil;

[0067] (3) Mix the first treated oil and the second treated oil at a mass ratio of 6:4 for 15 min at 70 °C to obtain the aromatic rubber plasticizer with high aromatic hydrocarbons.

[0068] Example 3

[0069] This example provides an aromatic rubber plasticizer with high aromatic hydrocarbons. The aromatic rubber plasticizer is obtained by the following preparation method, and the preparation method includes the following steps:

[0070] (1) Using the Wenchang vacuum gas oil cut as raw material, adopt the ZQC-25 hydrotreating catalyst, carry out the hydrotreating reaction in a hydrotreating pilot plant, the reaction temperature is 280 °C, the hydrogen-oil volume ratio is 600:1, the volume space velocity is 1 h -1 , the hydrogen partial pressure is 20 MPa. After removing the light fractions from the obtained hydrogenated oil, the fraction oil with a boiling point higher than 360 °C is obtained as the first treated oil;

[0071] (2) Using the CNOOC Suizhong 36-1 vacuum gas oil cut as raw material, adopt the ZQC-25 hydrotreating catalyst, carry out the hydrotreating reaction in a hydrotreating pilot plant, the reaction temperature is 380 °C, the hydrogen-oil volume ratio is 1500:1, the volume space velocity is 1.5 h -1, with a hydrogen partial pressure of 15 MPa. After removing the light fraction from the obtained hydrogenated oil, a fraction oil with a boiling point above 360 °C was obtained as the second treated oil;

[0072] (3) Mix the first treated oil and the second treated oil at a mass ratio of 9:1 at 50 °C for 65 min to obtain the high-aromatic-aromatic-based rubber plasticizer.

[0073] Example 4

[0074] This example provides a high-aromatic-aromatic-based rubber plasticizer, which is obtained by the following preparation method. The preparation method includes the following steps:

[0075] (1) Using the CNOOC Suizhong 36-1 second reduced-line extract oil as the raw material, and adopting the ZQC-25 hydrotreating catalyst, a hydrotreating reaction was carried out 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 2 h -1 , with a hydrogen partial pressure of 12 MPa. After removing the light fraction from the obtained hydrogenated oil, a fraction oil with a boiling point above 360 °C was obtained as the first treated oil;

[0076] (2) Using the CNOOC Suizhong 36-1 third reduced-line fraction oil as the raw material, and adopting the ZQC-25 hydrotreating catalyst, a hydrotreating reaction was carried out in a hydrotreating pilot plant. The reaction temperature was 280 °C, the hydrogen-oil volume ratio was 600:1, and the volume space velocity was 2 h -1 , with a hydrogen partial pressure of 15 MPa. After removing the light fraction from the obtained hydrogenated oil, a fraction oil with a boiling point above 360 °C was obtained as the second treated oil;

[0077] (3) Mix the first treated oil and the second treated oil at a mass ratio of 7:3 at 100 °C for 25 min to obtain the high-aromatic-aromatic-based rubber plasticizer.

[0078] Example 5

[0079] The difference between this example and Example 1 is that the ZQC-25 hydrotreating catalyst in steps (1) and (2) is replaced with an equal mass of LR-1 hydrofining catalyst, and the rest are the same as in Example 1.

[0080] Example 6

[0081] The difference between this example and Example 1 is that the ZQC-25 hydrotreating catalyst in steps (1) and (2) is replaced with an equal mass of ZQC-26 hydrotreating catalyst, and the rest are the same as in Example 1.

[0082] Example 7

[0083] The difference between this embodiment and Embodiment 1 is that the ZQC-25 hydrotreating catalyst in steps (1) and (2) is replaced with an equal mass of ZQC-27 hydrotreating catalyst, and the rest are the same as in Embodiment 1.

[0084] Performance Test

[0085] The rubber plasticizers obtained in Embodiments 1-7 were tested as follows:

[0086] (1) Yield (relative to solvent-extracted oil), %;

[0087] (2) Density at 20 °C, g / cm 3 : Tested in accordance with GB / T 1884;

[0088] (3) Kinematic viscosity at 100 °C, mm 2 / s: Tested in accordance with GB / T 265;

[0089] (4) Open flash point, °C: Tested in accordance with GB / T 3536;

[0090] (5) C A value, %: Tested in accordance with SH / T 0725;

[0091] (6) Aniline point, °C: Tested in accordance with GB / T 262;

[0092] (7) PCA content, mg / kg: Tested in accordance with NB / SH / T 0838;

[0093] (8) BaP content, mg / kg: Tested in accordance with the first method of SN / T 1877.3-2007;

[0094] (9) PAHs content, mg / kg: Tested in accordance with the first method of SN / T 1877.3-2007.

[0095] The test results are summarized in Table 1.

[0096] Table 1

[0097]

[0098]

[0099] Analyzing the data in Table 1, it can be seen that the yield of the rubber plasticizer obtained by the preparation method of the present invention is above 95.2%, the C A value is above 18%, the density at 20 °C is between 0.9478-0.9633 g / cm 3 and the kinematic viscosity at 100 °C is 18.61 mm 2 / s or higher, flash point above 220 °C, aniline point within 69 °C, PCA content within 2.9 mg / kg, BaP content within 0.6 mg / kg, and PAHs within 8.7 mg / kg. The preparation method of the present invention has a simple process, obtaining high-value-added products from low-value-added raw materials, namely high-yield A1820 aromatic rubber plasticizer and A2530 aromatic rubber plasticizer (taking Example 1 and Example 2 as examples). These two types of aromatic rubber plasticizers with high aromatic hydrocarbons have excellent processing performance during tire processing, are non-toxic green products, and the overall economic benefit of the technology is relatively high.

[0100] Within the preferred range (taking Examples 1-4 as examples), the yield of the rubber plasticizer obtained by the preparation method of the present invention is above 97.2%, the C A value is above 19.5%, the PCA content is within 1.7 mg / kg, and neither BaP nor PAHs are detected.

[0101] In the present invention, the C A value refers to the aromatic carbon ratio, PCA refers to the content of polycyclic aromatic hydrocarbons with three or more rings, BaP refers to benzo[a]pyrene, and PAHs refers to 8 polycyclic aromatic hydrocarbon compounds, including benzo[a]anthracene, benzo[b]fluoranthene, benzo[j]fluoranthene, benzo[k]fluoranthene, benzo[e]pyrene, benzo[a]pyrene, and dibenzo[a,h]anthracene, 8 polycyclic carcinogenic aromatic hydrocarbons. This detection is mainly to determine the carcinogenic content.

[0102] Analysis of Examples 5-7 and Example 1 shows that Examples 5-7 are inferior to Example 1, proving 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.

[0103] The present invention uses the above examples to illustrate the detailed method of the present invention, but the present invention is not limited to the above detailed method, that is, it does not mean that the present invention must rely on the above detailed method to be implemented. Those skilled in the art should understand that any improvement to the present invention, equivalent replacement of each raw material 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 preparation method of an aromatic rubber plasticizer with high aromatic hydrocarbons, characterized in that, the preparation method comprises the following steps: (1) Carry out a hydrotreating reaction on the solvent-extracted oil of the naphthenic or intermediate-base vacuum distillate oil. After removing the light fractions from the obtained hydrotreated oil, the remaining heavy fraction is the first treated oil; (2) Carry out a hydrotreating reaction on the naphthenic vacuum distillate oil. After removing the light fractions from the obtained hydrotreated oil, the remaining heavy fraction is the second treated oil; (3) Mix the first treated oil and the second treated oil to obtain the aromatic rubber plasticizer with high aromatic hydrocarbons; In step (1) and step (2), after removing the light fractions from the hydrotreated oils obtained in the first hydrotreating reaction zone and the second hydrotreating reaction zone, the heavy fractions are each independently fractions with a boiling point higher than 360 °C; The C of the aromatic rubber plasticizer with high aromaticity A value ≥ 18%; In step (2), in the hydrotreating reaction, the volume ratio of hydrogen to the naphthenic vacuum distillate oil is (600 - 1500):1; In step (3), the mass ratio of the first treated oil to the second treated oil is (0.11 - 9):

1.

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

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

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

5. The preparation method according to claim 1, characterized in that, the naphthenic or intermediate-base vacuum distillate oil is obtained by atmospheric and vacuum distillation of naphthenic or intermediate-base crude oil.

6. The preparation method according to claim 1, characterized in that, in step (1), the naphthenic or intermediate-base vacuum distillate oil includes any one or a combination of at least two of the second reduced-pressure distillate oil, the third reduced-pressure distillate oil or the fourth reduced-pressure distillate oil.

7. The preparation method according to claim 1, characterized in that, In step (1), the kinematic viscosity of the naphthenic or intermediate base vacuum distillate oil at 100 °C is ≥ 4 mm 2 / s.

8. The preparation method according to claim 1, characterized in that, The C of the naphthenic or intermediate base vacuum distillate oil A ≥ 15%.

9. The preparation method according to claim 1, characterized in that, in step (2), the naphthenic vacuum distillate oil includes any one or a combination of at least two of the second reduced-pressure distillate oil, the third reduced-pressure distillate oil or the fourth reduced-pressure distillate oil.

10. The preparation method according to claim 1, characterized in that, The kinematic viscosity of the naphthenic vacuum distillate at 100 °C is ≥ 4 mm 2 / s.

11. The preparation method according to claim 1, characterized in that, The C of the naphthenic base vacuum distillate oil A ≥ 18%.

12. The preparation method according to claim 1, characterized in that, in step (1) and step (2), the catalysts for the hydrotreating reaction each independently include any one or a combination of at least two of molybdenum-nickel type hydrotreating catalysts, tungsten-nickel type hydrotreating catalysts, molybdenum-cobalt type hydrotreating catalysts or molybdenum-tungsten-nickel type hydrotreating catalysts.

13. The preparation method according to claim 1, characterized in that, in step (1), the reaction temperature of the hydrotreating reaction is 280 - 400 °C.

14. The preparation method according to claim 13, characterized in that, In the hydrotreating reaction, the volume fraction ratio of hydrogen to the naphthenic or intermediate-base vacuum gas oil is (600 - 1500):

1.

15. According to the preparation method described in claim 13, it is characterized in that In the hydrotreating reaction, the volumetric space velocity of hydrotreating is 0.2 - 2.0 h -1 .

16. According to the preparation method described in claim 13, it is characterized in that in the hydrotreating reaction, the hydrogen partial pressure > 10 MPa.

17. According to the preparation method described in claim 1, it is characterized in that in step (2), the reaction temperature of the hydrotreating reaction is 280 - 380 °C.

18. According to the preparation method described in claim 17, it is characterized in that In the hydrotreating reaction, the volumetric space velocity of hydrotreating is 0.2 - 2.0 h -1 .

19. According to the preparation method described in claim 17, it is characterized in that in the hydrotreating reaction, the hydrogen partial pressure > 8 MPa.

20. According to the preparation method described in claim 1, it is characterized in that the temperature of the mixing is 40 - 200 °C.

21. According to the preparation method described in claim 1, it is characterized in that the time of the mixing ≥ 10 min.

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