EPDM filling oil and preparation method thereof
By subjecting petroleum-based vacuum distillate oil to hydrogenation, hydroisomerization, and post-hydrogenation refining, the problems of low flash point, poor oxidation stability, and high aromatic content in EPDM rubber filler oil were solved, resulting in a rubber filler oil with high flash point and low aromatic content, thus improving product quality and yield.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-27
- Publication Date
- 2026-03-27
AI Technical Summary
Existing EPDM rubber filler oils have problems such as low flash point, high volatility, poor oxidation stability, and poor compatibility with rubber, and also have a high aromatic content.
By hydrotreating, hydroisomerizing, and refining petroleum-based vacuum distillate oils, using specific types of hydrotreating and refining catalysts, sulfur and nitrogen are removed, waxy oils are converted into isoalkanes, the pour point is lowered, and rubber filler oils with high flash point and low aromatic content are obtained through fractionation.
A high-yield EPDM rubber filler oil was achieved, which has a high flash point, good oxidation stability, low aromatic content, and excellent product quality.
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Abstract
Description
Technical Field
[0001] This disclosure relates to the field of producing rubber filler oils, specifically to a EPDM rubber filler oil and its preparation method. Background Technology
[0002] EPDM is a terpolymer of ethylene, propylene, and a non-conjugated diene. The diene has a unique structure where one of the two double bonds copolymerizes; the unsaturated double bond primarily serves as a crosslinking site, while the other unsaturated bond does not form the polymer backbone but rather a side chain. The EPDM polymer backbone is completely saturated, a characteristic that makes it resistant to heat, light, oxygen, and especially ozone. EPDM is inherently nonpolar, resistant to polar solutions and chemicals, has low water absorption, and possesses excellent insulating properties. During EPDM production, its properties can be adjusted by changing the amounts of the three monomers, the ethylene-propylene ratio, the molecular weight and its distribution, and the vulcanization method. Specific processing oils are often added, making it an important processing aid in rubber manufacturing.
[0003] Currently, rubber filler oils have the following problems: low flash point, high volatility, presence of unsaturated substances such as aromatics, poor oxidation stability, poor compatibility with rubber, and low oil content. Summary of the Invention
[0004] The purpose of this disclosure is to provide a EPDM rubber filler oil and its preparation method. The method has a high yield, and the obtained EPDM rubber filler oil has a high flash point and good oxidation stability, and low aromatic content.
[0005] To achieve the above objectives, a first aspect of this disclosure provides a method for preparing EPDM rubber filler oil, the method comprising the following steps:
[0006] (1) Petroleum-based vacuum distillate oil is contacted with a hydrogenation catalyst for hydrogenation treatment to obtain a hydrogenated product; the sulfur content of the hydrogenated product is less than 20 ppm and the nitrogen content is less than 5 ppm.
[0007] (2) The hydrogenation product is contacted with a hydroisomerization catalyst to carry out a hydroisomerization reaction to obtain a hydroisomerization product;
[0008] (3) The hydroisomerization product is contacted with the hydrorefining catalyst to carry out the hydrorefining reaction, and the obtained hydrorefining reaction product is fractionated.
[0009] The petroleum-based vacuum distillate oil has a 5% boiling point of 400–500°C, a 95% boiling point of 470–700°C, and a kinematic viscosity of 5.0 mm at 100°C. 2The oil has an aromatic content of 25-60 wt% per second or higher; and the characteristic factor K value of the oil is 12 or higher.
[0010] The hydrogenation catalyst includes hydrogenation catalyst I and hydrogenation catalyst II. Hydrogenation catalyst I contains an auxiliary agent containing one or more auxiliary elements selected from fluorine, boron and phosphorus. Hydrogenation catalyst II does not contain fluorine.
[0011] Optionally, the petroleum-based vacuum distillate oil has a 5% boiling point of 420°C to 480°C, a 95% boiling point of 520°C to 650°C, and a kinematic viscosity of 8.0 mm at 100°C. 2 / s~30.0mm 2 / s, wherein the characteristic factor K of the petroleum-based vacuum distillate is 12 to 12.5.
[0012] Optionally, in step (1), the hydrogenation catalyst comprises, by volume fraction, 15-90% hydrogenation catalyst I and 10-85% hydrogenation catalyst II; preferably, the hydrogenation catalyst comprises 30-80% hydrogenation catalyst I and 20-70% hydrogenation catalyst II.
[0013] Optionally, the hydrogenation catalyst I comprises the promoter, a first support, and an active metal supported on the first support; based on the weight of the hydrogenation catalyst I, the weight content of the promoter element is 0.2 to 10 wt%; the promoter element preferably includes one or more of phosphorus and fluorine; the active metal includes one or more of nickel, cobalt, molybdenum, and tungsten.
[0014] The hydrogenation catalyst I includes hydrogenation catalyst Ia and hydrogenation catalyst Ib, at least one of which contains the auxiliary element; the total weight content of active metal in hydrogenation catalyst Ib is 10-40% of the total weight content of active metal in hydrogenation catalyst Ia, preferably 15-30%.
[0015] Optionally, step (1) includes: sequentially contacting petroleum-based vacuum distillate oil with stratified hydrogenation catalyst Ib, hydrogenation catalyst Ia and hydrogenation catalyst II to perform the hydrogenation treatment.
[0016] Optionally, in step (1), the conditions for hydrogenation treatment include: a hydrogen partial pressure of 3-28 MPa, preferably 5-20 MPa; a reaction temperature of 300-410℃, preferably 320-380℃; and a volume hourly space velocity of 0.2-3 h⁻¹. -1 Preferably 0.3-2h -1 The hydrogen-to-oil volume ratio is 200-3000, preferably 300-1800.
[0017] Optionally, in step (2), the conditions for the hydroisomerization reaction include: a hydrogen partial pressure of 1-25 MPa, preferably 2-20 MPa; a reaction temperature of 250-400℃, preferably 280-380℃; and a volume hourly space velocity of 0.2-3 h⁻¹. -1 Preferably, it is 0.3-1.8h. -1 The hydrogen-to-oil volume ratio is 200-3000, preferably 300-1800.
[0018] Optionally, in step (2), the hydroisomerization catalyst includes a second support and an active component supported on the second support, the active component comprising a Group VIII metal, the Group VIII metal comprising one or more of nickel, platinum and palladium; the second support comprises one or more of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, SAPO-11 and SAPO-41.
[0019] Optionally, in step (3), the conditions for the purification reaction after hydrogenation include: a hydrogen partial pressure of 1-25 MPa, preferably 5-20 MPa; a reaction temperature of 130-360℃, preferably 150-310℃; and a volume hourly space velocity of 0.2-5 h⁻¹. -1 Preferably, it is 0.3-2.5h. -1 The hydrogen-to-oil volume ratio is 100-3000, preferably 300-1800.
[0020] Optionally, in step (3), the post-hydrogenation refining catalyst includes a third support and a noble metal supported on the third support, wherein the noble metal includes palladium and / or platinum, and the third support includes an alumina-silica support or an alumina support.
[0021] A second aspect of this disclosure provides a EPDM rubber filler oil prepared by the method described in the first aspect of this disclosure, wherein the EPDM rubber filler oil has an initial boiling point above 480°C, a pour point below -15°C, and a kinematic viscosity of 80 mmHg at 40°C. 2 / s or more.
[0022] Through the above technical solution, this disclosure involves first contacting a specific type of petroleum-based vacuum distillate oil with a specific type of hydrogenation catalyst for hydrogenation treatment to remove sulfur and nitrogen, reducing oil cracking; then contacting the hydrogenation treatment product with a hydroisomerization catalyst for hydroisomerization treatment to convert waxy oil in the distillate oil into isoalkanes, lowering the oil's pour point; finally, contacting the hydroisomerization product with a post-hydrogenation refining catalyst for a post-hydrogenation refining reaction, ultimately cutting out a suitable fraction of rubber filler oil. The method of this disclosure has a high yield, and the obtained EPDM rubber filler oil has a high flash point and good oxidation stability, with a low aromatic content.
[0023] Other features and advantages of this disclosure will be described in detail in the following detailed description section. Detailed Implementation
[0024] The following provides a detailed description of specific embodiments of this disclosure. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit this disclosure.
[0025] The first aspect of this disclosure provides a method for preparing EPDM rubber filler oil, the method comprising the following steps:
[0026] (1) Petroleum-based vacuum distillate oil is contacted with a hydrogenation catalyst for hydrogenation treatment to obtain a hydrogenated product; the sulfur content of the hydrogenated product is less than 20 ppm and the nitrogen content is less than 5 ppm.
[0027] (2) The hydrogenation product is contacted with a hydroisomerization catalyst to carry out a hydroisomerization reaction to obtain a hydroisomerization product;
[0028] (3) The hydroisomerization product is contacted with the hydrorefining catalyst to carry out the hydrorefining reaction, and the obtained hydrorefining reaction product is fractionated.
[0029] The petroleum-based vacuum distillate oil has a 5% boiling point of 400–500°C, a 95% boiling point of 470–700°C, and a kinematic viscosity of 5.0 mm at 100°C. 2 The oil has an aromatic content of 25-60 wt% per second or higher; and the characteristic factor K value of the oil is 12 or higher.
[0030] The hydrogenation catalyst includes hydrogenation catalyst I and hydrogenation catalyst II. Hydrogenation catalyst I contains an auxiliary agent containing one or more auxiliary elements selected from fluorine, boron and phosphorus. Hydrogenation catalyst II does not contain fluorine.
[0031] This disclosure involves first hydrotreating a specific petroleum-based vacuum distillate with a specific type of hydrotreating catalyst to remove sulfur and nitrogen, reducing oil cracking; then, the hydrotreating product is contacted with a hydroisomerization catalyst for hydroisomerization treatment, converting waxy oil in the distillate into isoalkanes and lowering the oil's pour point; finally, the hydroisomerization product is contacted with a post-hydrotreating refining catalyst for post-hydrotreating refining, ultimately yielding a suitable fraction of rubber-filled oil. The method of this disclosure offers high yields, and the resulting EPDM rubber-filled oil exhibits high flash point, good oxidation stability, and low aromatic content.
[0032] In this disclosure, the characteristic factor K value is calculated based on the volume average boiling point and density at 15.6 °C of the vacuum distillate oil.
[0033] According to one embodiment of this disclosure, the petroleum-based vacuum distillate oil has a 5% boiling point of 420°C to 480°C, a 95% boiling point of 520°C to 650°C, and a kinematic viscosity of 8.0 mm at 100°C. 2 / s~30.0mm 2 / s, wherein the characteristic factor K value of the petroleum-based vacuum distillate oil is 12 to 12.5. The above embodiments are beneficial for obtaining EPDM rubber filler oils with high flash point, high oxidation stability, and low aromatic content.
[0034] According to one embodiment of this disclosure, in step (1), the hydrogenation catalyst comprises, by volume fraction, 15-90% hydrogenation catalyst I and 10-85% hydrogenation catalyst II; preferably, the hydrogenation catalyst comprises 30-80% hydrogenation catalyst I and 20-70% hydrogenation catalyst II. The above embodiment is beneficial for improving the yield of filler oil and for obtaining EPDM rubber filler oil with high flash point, high oxidation stability, and low aromatic content.
[0035] According to one embodiment of the present disclosure, step (1) includes: sequentially contacting petroleum-based vacuum distillate oil with layered hydrogenation catalyst I and hydrogenation catalyst II to perform the hydrogenation treatment.
[0036] According to one embodiment of this disclosure, the hydrogenation catalyst I comprises the promoter, a first support, and an active metal supported on the first support; based on the weight of the hydrogenation catalyst I, the weight content of the promoter element is 0.2 to 10 wt%, preferably 0.6 to 7 wt%; the promoter element preferably includes one or more of fluorine and phosphorus; the active metal may include one or more of nickel, cobalt, molybdenum, and tungsten.
[0037] According to one embodiment of this disclosure, the hydrogenation catalyst I comprises hydrogenation catalyst Ia and hydrogenation catalyst Ib, at least one of which contains the auxiliary element; the total weight content of active metal in hydrogenation catalyst Ib is 10-40% of the total weight content of active metal in hydrogenation catalyst Ia, preferably 15-30%. The above embodiment is beneficial for removing sulfur and nitrogen content from vacuum distillate oils, reducing cracking of rubber filler oils, and increasing the viscosity of rubber filler oils.
[0038] According to one embodiment of this disclosure, the hydrogenation catalyst Ia comprises the additive, a first support, and an active metal a supported on the first support; the first support comprises one or more of alumina and silica-alumina; the active metal a comprises one or more of nickel, cobalt, molybdenum, and tungsten. The above embodiment is beneficial for removing sulfur and nitrogen content from vacuum distillate oils, reducing cracking of rubber-filled oils, and increasing the viscosity of rubber-filled oils.
[0039] According to one embodiment of this disclosure, the hydrogenation catalyst Ib comprises a support b, an active metal b supported on the support b, and an additive b, with or without the additive b; the additive b contains one or more of fluorine, boron, phosphorus, and alkaline earth metals; the support b contains an inorganic oxide support, which includes one or more of alumina and silica-alumina. Based on the hydrogenation catalyst Ib, the content of the active metal b, calculated as metal oxide, is 0.5–9% by weight; in a further embodiment, the active metal b is nickel and / or cobalt, and the content of the active metal b, calculated as metal oxide, is 0.5–4% by weight, preferably 1.0–3% by weight; the active metal b is molybdenum and / or tungsten, and the content of the active metal b, calculated as metal oxide, is 2.5–9% by weight, preferably 3.5–6.5% by weight. The above embodiments are beneficial for removing sulfur and nitrogen content from vacuum distillate oils, reducing cracking of rubber filler oils, and increasing the viscosity of rubber filler oils.
[0040] According to one embodiment of this disclosure, step (1) includes: sequentially contacting petroleum-based vacuum distillate oil with a layered packing of hydrogenation catalyst Ib, hydrogenation catalyst Ia, and hydrogenation catalyst II to perform the hydrogenation treatment. The above embodiment is beneficial for removing sulfur and nitrogen content from the vacuum distillate oil, reducing cracking of the rubber-filled oil, and increasing the viscosity of the rubber-filled oil.
[0041] According to one embodiment of this disclosure, in step (1), the conditions for hydrogenation treatment include: a hydrogen partial pressure of 3-28 MPa, preferably 5-20 MPa; a reaction temperature of 300-410°C, preferably 320-380°C; and a volume hourly space velocity of 0.2-3 h⁻¹. -1 Preferably 0.3-2h -1 The hydrogen-to-oil volume ratio is 200-3000, preferably 300-1800. The above embodiments are beneficial for removing sulfur and nitrogen content from vacuum distillate oils, reducing cracking of rubber filler oils, and increasing the viscosity of rubber filler oils.
[0042] According to one embodiment of this disclosure, in step (2), the conditions for the hydroisomerization reaction include: a hydrogen partial pressure of 1-25 MPa, preferably 2-20 MPa; a reaction temperature of 250-400°C, preferably 280-380°C; and a volume hourly space velocity of 0.2-3 h⁻¹. -1 Preferably, it is 0.3-1.8h. -1 The hydrogen-to-oil volume ratio is 200-3000, preferably 300-1800. The above embodiments facilitate the conversion of wax oil in the hydrogenation product into isoalkanes and help lower the pour point of the EPDM rubber filler oil.
[0043] According to one embodiment of this disclosure, in step (2), the hydroisomerization catalyst can be a molecular sieve catalyst with a mesopore size well known to those skilled in the art. For example, the hydroisomerization catalyst includes a second support and an active component supported on the second support. The active component contains a Group VIII metal, which includes one or more of nickel, platinum, and palladium. The second support may include one or more of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, SAPO-11, and SAPO-41. The above embodiment is beneficial for converting the wax oil in the hydrotreated product into isoalkanes and for lowering the pour point of the EPDM rubber filler oil.
[0044] According to one embodiment of this disclosure, in step (3), the conditions for the purification reaction after hydrogenation include: a hydrogen partial pressure of 1-25 MPa, preferably 5-20 MPa; a reaction temperature of 130-360°C, preferably 150-310°C; and a volume hourly space velocity of 0.2-5 h⁻¹. -1 Preferably, it is 0.3-2.5h. -1 The hydrogen-to-oil volume ratio is 100-3000, preferably 300-1800. The above embodiments facilitate the saturation of olefins and aromatics contained in the hydroisomerization products, and improve the oxidative stability of the EPDM rubber filler oil.
[0045] According to one embodiment of this disclosure, in step (3), the hydrorefining catalyst used in the post-hydrogenation refining reaction can be any hydrorefining catalyst well known to those skilled in the art. For example, the hydrorefining catalyst may include a third support and a noble metal supported on the third support, wherein the noble metal includes palladium and / or platinum, and the third support includes an alumina-silica support or an alumina support. In the above embodiment, selecting a hydrorefining catalyst with high hydrosaturation is beneficial for reducing the olefin content in rubber filler oil and for improving the oxidation stability of the product.
[0046] The second aspect of this disclosure provides a EPDM rubber filler oil prepared using the method described in the first aspect of this disclosure, wherein the EPDM rubber filler oil has an initial boiling point above 480°C, a pour point below -15°C, and a kinematic viscosity of 80 mmHg at 40°C. 2 The EPDM rubber filler oil disclosed herein is of excellent quality, with a clear and transparent appearance and a high yield.
[0047] The present disclosure will be described in detail below with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present disclosure, but do not limit the present disclosure in any way.
[0048] Unless otherwise specified, all reagents used in this disclosure are commercially available.
[0049] Preparation Example
[0050] The preparation method of the hydrotreating catalyst Ia is a conventional technique in the field. The hydrotreating catalyst Ia includes 0.8 wt% of the promoter P2O5, 2.4 wt% NiO, 2.1 wt% MoO3, 21 wt% WO3 and 73.7 wt% of the silica-alumina support.
[0051] The preparation method of the hydrotreating catalyst Ia-1 is a conventional technique in the field. The hydrotreating catalyst Ia-1 includes 0.8 wt% of the promoter P2O5, 1.5 wt% NiO, 1.5 wt% MoO3, 17 wt% WO3 and 79.2 wt% of the silica-alumina support.
[0052] The preparation method of the hydrotreating catalyst Ia-2 is a conventional technique in the field. The hydrotreating catalyst Ia-2 includes 5.0 wt% of promoter F, 2.4 wt% NiO, 2.3 wt% MoO3, 23 wt% WO3 and 67.3 wt% alumina support.
[0053] The preparation method of the hydrotreating catalyst Ia-3 is a conventional technique in the field. The hydrotreating catalyst Ia-3 includes 6.5 wt% of promoter F, 2.5 wt% NiO, 2.5 wt% MoO3, 25 wt% WO3 and 63.5 wt% alumina support.
[0054] The hydrotreating catalyst Ib used is the commercially available RG-1 catalyst, produced by Changling Catalyst Factory. The hydrotreating catalyst Ib consists of 93.5 wt% alumina support, 5.5 wt% MoO active metal, and 1.0 wt% NiO active metal.
[0055] The preparation method of the hydrotreating catalyst II used includes: weighing 200.0 g of industrial alumina support, impregnating it with 168.0 mL of an aqueous solution containing 59.1 g of ammonium metatungstate, 51.9 g of ammonium paramolybdate, and 3.4 g of phosphoric acid for 1 hour, drying at 120 °C for 6 hours, and calcining at 330 °C for 6 hours to obtain catalyst intermediate Z1; taking half the weight of intermediate Z1, sulfiding it with H2 containing 10.0% H2S by volume at 380 °C and atmospheric pressure for 5 hours to obtain catalyst intermediate Z2. Further impregnating intermediate Z2 with 53.0 mL of an aqueous solution containing 10.8 g of basic nickel carbonate, 3.4 g of basic cobalt carbonate, and 10.1 g of phosphoric acid for 1 hour, and then drying it at 100 °C under nitrogen atmosphere for 8 hours to obtain catalyst C1, which is stored under a nitrogen atmosphere for later use. The weight contents of NiO, CoO, WS2, MoS2 and P2O5 in C1 are 3.2%, 1.1%, 15.1%, 13.6% and 5.0%, respectively. The C1 catalyst does not contain fluorine.
[0056] The preparation method of the hydroisomerization catalyst used includes: mixing 60 g of ZSM-48 molecular sieve with 20 g of alumina, and mixing with 80 g of a solution containing 2% nitric acid. The mixture is then shaped on an extruder. The shaped support is calcined at 600°C for 4 hours. 0.5% Pt is loaded onto the support, and then calcined in air at 400°C and reduced in hydrogen for 4 hours each.
[0057] The preparation method of the hydrogenated refined catalyst used includes: mixing 285 g of pseudoboehmite P1-2 (71% dry basis), 152 g of amorphous silica-alumina (Siral40, containing 40% by weight of SiO2, product of Condea, Germany), and 9 g of guar gum powder; then mixing the mixture with 9 mL of nitric acid (65-68% concentration, analytical grade, Shantou Xilong Chemical Plant) and 275 mL of water; and then kneading the mixture evenly on a twin-screw extruder to obtain support ZH-3. ZH-3 is a plastic material with a silica content of 15% and an alumina content of 85% based on the total amount of silica and alumina in the composition, calculated as oxides. The aforementioned ZH-3 is extruded into butterfly-shaped strips with a diameter of 1.3 mm on a twin-screw extruder. After drying the wet strips at 120°C for 4 hours, they are calcined at 600°C for 3 hours to obtain silica-alumina support SA-3. 12 g of ammonium nitrate (analytical grade) was dissolved in 150 mL of water. 100 g of the SA-3 support was immersed in the solution for 3 hours, then filtered and dried at 60 °C for 8 hours to obtain the ammonium-impregnated support NSA-3. 431 mg of ruthenium chloride and 840 mg of tetraamminepalladium nitrate were dissolved in deionized water to prepare an impregnation solution. 105 g of the NSA-3 support was completely immersed in the impregnation solution for 6 hours, then filtered and dried at 120 °C. The solution was then calcined at 500 °C for 4 hours and reduced with hydrogen at 350 °C for 4 hours at a hydrogen pressure of 0.1 MPa. The resulting purified catalyst after hydrogenation was obtained.
[0058] Example 1
[0059] The properties of the petroleum-based vacuum distillate used in Example 1 are shown in Table 1. The hydrotreating catalyst used in this example is a layered catalyst Ib, Ia, and II. Based on the total volume of Ia, Ib, and II, the content of catalyst Ia is 60%, the amount of catalyst Ib is 10%, and the amount of catalyst II is 30%. The weight content of active metal in hydrotreating catalyst Ib is 25.5% of the weight content of active metal in hydrotreating catalyst Ia. Hydrotreating catalyst Ia contains 0.8% additive P.
[0060] Under a hydrogen atmosphere, petroleum-based vacuum distillate oil is fed into a hydrotreating reactor and reacted sequentially with hydrotreating catalysts Ib, Ia, and II packed in layers to obtain the hydrotreating product. The hydrotreating product has a sulfur content of 10 ppm and a nitrogen content of 2 ppm.
[0061] The obtained hydrotreated product is stripped to remove fractions below C4, and then fed into a hydroisomerization reactor to react with a hydroisomerization catalyst to obtain the hydroisomerized product.
[0062] The obtained hydroisomerization product is fed into a post-hydrotreating reactor, where it reacts with the post-hydrotreating catalyst. The product flowing out of the post-hydrotreating reactor is then fractionated in a vacuum distillation column to obtain rubber filler oil products with a boiling point above 480°C. The specific reaction conditions for Example 1 are shown in Table 3, and the properties and yields of the products are shown in Table 4.
[0063] Table 1
[0064] Raw material name Vacuum distillate oil <![CDATA[Density at 20 °C / (kg / m 3 )]]> 946.3 <![CDATA[100℃ kinematic viscosity / (mm 2 / s)]]> 21.78 Pour point / °C ＞45 Carbon residue value / % 1.89 <![CDATA[w(C7 insolubles) / (mg / kg)]]> ＜50 w(sulfur) / % 3.09 w(nitrogen) / % 0.13 Simulated distillation range / ℃ Initial boiling point 392.5 5 / ％ 440.3 50 / ％ 515.9 95％ 564.0 97％ 570.2 Final boiling point 586.5 K value 12.1 Aromatic content / % 52.6
[0065] Example 2
[0066] The method in this embodiment is the same as in Embodiment 1, except that the catalyst used in the hydrogenation process in this embodiment includes: catalyst I, based on the total volume of Ia, Ib, and II. a The content of catalyst Ib is 85%, the amount of catalyst Ib is 5%, and the amount of catalyst II is 10%.
[0067] Example 3
[0068] The method in this embodiment is the same as in embodiment 1, except that hydrogenation catalyst Ia-1 is used instead of hydrogenation catalyst Ia, and the weight content of active metal in hydrogenation catalyst Ib is 32.5% of the weight content of active metal in hydrogenation catalyst Ia-1.
[0069] Example 4
[0070] The method in this embodiment is the same as in embodiment 1, except that hydrogenation catalyst Ia-2 is used instead of hydrogenation catalyst Ia, the weight content of active metal in hydrogenation catalyst Ib is 23.5% of the weight content of active metal in hydrogenation catalyst Ia-2, and hydrogenation catalyst Ia-2 contains 5% auxiliary agent F.
[0071] Example 5
[0072] The method in this embodiment is the same as in embodiment 1, except that hydrogenation catalyst Ia-3 is used instead of hydrogenation catalyst Ia, the weight content of active metal in hydrogenation catalyst Ib is 21.7% of the weight content of active metal in hydrogenation catalyst Ia-3, and hydrogenation catalyst Ia-3 contains 6.5% promoter F.
[0073] Comparative Example 1
[0074] The method of this comparative example is the same as that of Example 1, except that the properties of the vacuum distillate oil used in Comparative Example 1 are shown in Table 2, the specific reaction conditions are shown in Table 3, and the properties and yield of the product are shown in Table 4.
[0075] Table 2
[0076] Raw material name Vacuum distillate oil <![CDATA[Density at 20℃ / (kg / m 3 )]]> 909.5 <![CDATA[Kinematic viscosity at 100℃ / (mm 2 / s)]]> 4.857 Pour point / ℃ 24 Carbon residue value / % 0.05 w(sulfur) / % 3.05 w(nitrogen) / % 0.11 Simulated distillation range / ℃ Initial boiling point 5 / ％ 380 50 / ％ 403 95％ 466 97％ 496 Aromatic content / % 54.6
[0077] Comparative Example 2
[0078] The method of this comparative example is the same as that of Example 1, except that in the hydrogenation treatment of Comparative Example 2, only the hydrogenation treatment catalyst Ia is used. The specific reaction conditions are shown in Table 3, and the properties and yield of the product are shown in Table 4.
[0079] Table 3
[0080]
[0081] Table 4
[0082]
[0083] According to the data in Table 4, the rubber filler oil product obtained by the method disclosed in this paper has a high yield, and the obtained rubber filler oil product has a high flash point, low evaporation loss, low aromatic content, and good oxidation stability.
[0084] Compared to Comparative Example 1, Example 1 of this disclosure uses a specific vacuum distillate oil, resulting in EPDM rubber filler oil with higher viscosity and yield.
[0085] Compared to Comparative Example 2, Example 1 of this disclosure uses specific hydrogenation catalysts I and II during hydrogenation treatment, resulting in higher viscosity and yield of the EPDM rubber filler oil.
[0086] Compared to Example 2, the content of catalysts Ia, Ib, and II used in Example 1 is within the preferred range of this disclosure, resulting in higher viscosity and yield of the EPDM rubber filler oil.
[0087] Compared to Example 3, the ratio of active metal content in catalysts Ia and Ib used in Example 1 is within the preferred range of this disclosure, resulting in higher viscosity and yield of the EPDM rubber filler oil.
[0088] The preferred embodiments of this disclosure have been described in detail above. However, this disclosure is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this disclosure, various simple modifications can be made to the technical solutions of this disclosure, and these simple modifications all fall within the protection scope of this disclosure.
[0089] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, this disclosure will not describe the various possible combinations separately.
[0090] Furthermore, various different embodiments of this disclosure can be combined in any way, as long as they do not violate the spirit of this disclosure, they should also be regarded as the content disclosed in this disclosure.
Claims
1. A method for preparing EPDM rubber filler oil, characterized in that, The method includes the following steps: (1) Petroleum-based vacuum distillate oil is contacted with a hydrogenation catalyst for hydrogenation treatment to obtain a hydrogenated product; the sulfur content of the hydrogenated product is less than 20 ppm and the nitrogen content is less than 5 ppm. (2) The hydrogenation product is contacted with a hydroisomerization catalyst to carry out a hydroisomerization reaction to obtain a hydroisomerization product; (3) The hydroisomerization product is contacted with the hydrorefining catalyst to carry out the hydrorefining reaction, and the obtained hydrorefining reaction product is fractionated. The petroleum-based vacuum distillate oil has a 5% boiling point of 400–500°C, a 95% boiling point of 470–700°C, and a kinematic viscosity of 5.0 mm at 100°C. 2 The oil has an aromatic content of 25-60 wt% per second or higher; and the characteristic factor K value of the oil is 12 or higher. The hydrogenation catalyst includes hydrogenation catalyst I and hydrogenation catalyst II. Hydrogenation catalyst I contains an auxiliary agent containing one or more auxiliary elements selected from fluorine, boron and phosphorus. Hydrogenation catalyst II does not contain fluorine.
2. The method according to claim 1, wherein, The petroleum-based vacuum distillate oil has a 5% boiling point of 420℃~480℃, a 95% boiling point of 520℃~650℃, and a kinematic viscosity of 8.0 mm at 100℃. 2 / s~30.0mm 2 / s, wherein the characteristic factor K of the petroleum-based vacuum distillate is 12 to 12.
5.
3. The method according to claim 1, wherein, In step (1), the hydrogenation catalyst comprises, by volume fraction, 15-90% hydrogenation catalyst I and 10-85% hydrogenation catalyst II; preferably, the hydrogenation catalyst comprises 30-80% hydrogenation catalyst I and 20-70% hydrogenation catalyst II.
4. The method according to claim 1, wherein, The hydrogenation catalyst I comprises the promoter, a first support, and an active metal supported on the first support; based on the weight of the hydrogenation catalyst I, the weight content of the promoter element is 0.2-10 wt%; the promoter element is preferably phosphorus or fluorine; the active metal includes one or more of nickel, cobalt, molybdenum, and tungsten. The hydrogenation catalyst I includes hydrogenation catalyst Ia and hydrogenation catalyst Ib, at least one of which contains the auxiliary element; the total weight content of active metal in hydrogenation catalyst Ib is 10-40% of the total weight content of active metal in hydrogenation catalyst Ia, preferably 15-30%.
5. The method according to claim 4, wherein, Step (1) includes: sequentially contacting petroleum-based vacuum distillate oil with stratified hydrogenation catalyst Ib, hydrogenation catalyst Ia and hydrogenation catalyst II to perform the hydrogenation treatment.
6. The method according to claim 1, wherein, In step (1), the conditions for hydrogenation treatment include: a hydrogen partial pressure of 3-28 MPa, preferably 5-20 MPa; a reaction temperature of 300-410℃, preferably 320-380℃; and a volume hourly space velocity of 0.2-3 h⁻¹. -1 Preferably 0.3-2h -1 The hydrogen-to-oil volume ratio is 200-3000, preferably 300-1800.
7. The method according to claim 1, wherein, In step (2), the conditions for the hydroisomerization reaction include: a hydrogen partial pressure of 1-25 MPa, preferably 2-20 MPa; a reaction temperature of 250-400℃, preferably 280-380℃; and a volume hourly space velocity of 0.2-3 h⁻¹. -1 Preferably, it is 0.3-1.8h. -1 The hydrogen-to-oil volume ratio is 200-3000, preferably 300-1800.
8. The method according to claim 1, wherein, In step (2), the hydroisomerization catalyst includes a second support and an active component supported on the second support. The active component contains a Group VIII metal, which includes one or more of nickel, platinum, and palladium. The second support includes one or more of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, SAPO-11, and SAPO-41.
9. The method according to claim 1, wherein, In step (3), the conditions for the purification reaction after hydrogenation include: a hydrogen partial pressure of 1-25 MPa, preferably 5-20 MPa; a reaction temperature of 130-360℃, preferably 150-310℃; and a volume hourly space velocity of 0.2-5 h⁻¹. -1 Preferably, it is 0.3-2.5h. -1 The hydrogen-to-oil volume ratio is 100-3000, preferably 300-1800.
10. The method according to claim 1, wherein, In step (3), the post-hydrogenation refining catalyst includes a third support and a noble metal supported on the third support, wherein the noble metal includes palladium and / or platinum, and the third support includes an alumina-silica support or an alumina support.
11. The EPDM rubber filler oil prepared by the method according to any one of claims 1 to 10, characterized in that, The EPDM rubber filler oil has an initial boiling point above 480℃, a pour point below -15℃, and a kinematic viscosity of 80 mmHg at 40℃. 2 / s or more.