Special white oil for SEBS thermoplastic elastomer as well as preparation method and application of special white oil

Abstract

The invention relates to the technical field of petrochemical engineering, in particular to white oil special for SEBS thermoplastic elastomers and a preparation method and application thereof.The white oil special for the SEBS thermoplastic elastomers is obtained according to the following steps that paraffin-based distillate oil and hydrogen are subjected to a hydrotreating stage reaction, the obtained hydrotreating generated oil is mixed with the hydrogen to be subjected to a hydroisomerization reaction, and the white oil is obtained; and mixing the obtained hydroisomerization generated oil with hydrogen to carry out hydrofinishing reaction, carrying out vacuum fractionation on the obtained third-stage hydrogenated generated oil to obtain distillate oil with the boiling point higher than 320 DEG C, and mixing the distillate oil with hydrogen to carry out hydrogenation deep aromatic saturation reaction to obtain the special white oil for the SEBS thermoplastic elastomer. The low-volatility high-flash-point low-volatility high-flash-point low-volatility high-flash-point low-volatility high-flash-point low-volatility high-flash-point low-volatility high-flash-point low-volatility high-flash-point low-volatility high-flash-point low-volatility high-flash-point low-volatility high-flash-point low-volatility high-flash-point low-volatility high-flash-point low-volatility high-flash-point low-volatility high-flash-point low-

Description

Technical Field

[0001] The present invention relates to the technical field of petrochemical industry, and is a special white oil for SEBS - type thermoplastic elastomers, its preparation method and application. Background Art

[0002] Thermoplastic elastomer (TPE) is a polymer material with characteristics between rubber and thermoplastic. It has the dual properties and broad characteristics of rubber and plastic. At room temperature, it has the high elasticity of rubber, shows the high elasticity of vulcanized rubber at room temperature, and is as easy to process and form as thermoplastic at high temperature. It is a polymer material with the characteristics of both vulcanized rubber and thermoplastic.

[0003] The TPE material formula generally adds white oil as a plasticizer, which mainly plays the roles of enhancing fluidity, enhancing plasticization and adjusting hardness. The higher the oil content, the lower the hardness of TPE. The white oil products used for thermoplastic elastomer TPE mainly include naphthenic oil and paraffin oil. According to the requirements of different industries, the white oil used is divided into industrial grade, food grade, cosmetic grade and pharmaceutical grade.

[0004] SEBS - type thermoplastic elastomers have excellent aging resistance, weather resistance, chemical corrosion resistance and good processing performance, etc., and are widely used in many fields. In the production process of SEBS - type thermoplastic elastomers, white oil, as an important plasticizer, has a significant impact on its performance. When the existing ordinary white oil is used for SEBS - type thermoplastic elastomers, there are problems such as poor compatibility with SEBS, easy oil bleeding, large volatility, resulting in a decline in the physical properties of products, and it cannot meet the high - performance requirements of SEBS - type thermoplastic elastomers.

[0005] The Chinese patent document with the authorization announcement number CN102021032B discloses a naphthenic - based filling oil for soft rubber toys and its preparation method. It uses naphthenic fraction oil as raw material, and adopts the combination of medium - pressure hydrogenation and furfural refining to produce toy oil. The furfural refining extraction tower has poor selectivity, the aromatic hydrocarbon content in the refined oil after extraction is too high, the medium - pressure hydrogenation pressure is too low, it cannot saturate all the aromatic hydrocarbons, nor can it crack the naphthenes to the ideal content, and it cannot produce white oil. Moreover, the aromatic hydrocarbons and naphthenes in the oil product affect the physical and chemical properties, mechanical properties and yellowing resistance of SEBS rubber products.

[0006] The Chinese patent document with the publication number CN117304976A discloses a special white oil for SEBS - type thermoplastic elastomers, its preparation method and application. Using naphthenic fraction oil as the raw material oil, it is successively subjected to solvent extraction, hydrotreating, isomerization dewaxing, and hydro - finishing, and the fraction with a boiling range of 300 °C to 500 °C is collected to obtain the special naphthenic white oil product for SEBS. The special naphthenic white oil for SEBS prepared by this invention has a relatively high viscosity index and a certain naphthene content, and can be used as a rubber softening filler oil for special SEBS products. However, this method uses naphthenic raw material oil, which has a low flash point itself, and the prepared white oil product has a high volatility, which is not conducive to the stability and service life of the products. Moreover, this technology does not undergo a deep dearomatization process, and the storage stability of the white oil is poor.

[0007] The above - mentioned methods all use naphthenic fraction oil as the raw material and adopt a combination process of solvent refining and hydrogenation. The process flow is long, the product yield is low, there is a solvent refining process in the production process, which involves the treatment of waste solvents, does not meet the current green production requirements, has a large pollution and is not environmentally friendly, and the production efficiency of the product is reduced by removing polycyclic aromatic hydrocarbons through solvent refining.

[0008] The Chinese patent document with the authorization announcement number CN114479934B discloses a preparation method of special white oil for polystyrene and the special white oil for polystyrene. The preparation method of the special white oil for polystyrene provided by the present invention includes the following steps: 1) Using a ketone - benzene dewaxing unit to dewax and refine the paraffinic fraction oil to obtain dewaxed and refined oil; 2) The dewaxed and refined oil is successively subjected to hydrotreating, hydroisomerization dewaxing, and hydro - finishing to obtain a three - stage hydrogenated product oil; 3) The three - stage hydrogenated product oil is subjected to atmospheric and vacuum distillation and the fraction with a distillation range greater than or equal to 430 °C is collected to obtain the special white oil for polystyrene. However, in this method, the paraffinic fraction oil used as the raw material has an oil product with a distillation range of 420 °C to 540 °C, and its process is a combination process of solvent refining and hydrogenation, and there is no deep hydro - dearomatization refining after fractionation, which affects the storage stability of the product.

[0009] The Chinese patent document with the authorization announcement number CN106479565B discloses a special white oil for polystyrene and its preparation method. The preparation method of the special white oil for polystyrene includes the following steps: 1) Solvent - refining the fraction oil of naphthenic crude oil in an extraction tower, obtaining an extract at the bottom of the extraction tower and a refined liquid at the top of the extraction tower, and obtaining refined oil after recovering the solvent; 2) The refined oil is successively subjected to a hydrogenation process and distillation cutting to obtain the special white oil for polystyrene; the hydrogenation process includes successively carried out hydrotreating, catalytic dewaxing, hydro - refining, and hydro - deep saturation of aromatic hydrocarbons. However, in this method, the process of furfural refining → hydrotreating → catalytic dewaxing → hydro - refining → hydro - deep saturation → fractionation is adopted, and the raw material is naphthenic fraction oil, and the special white oil for polystyrene obtained has the characteristic of a high naphthene content.

[0010] Therefore, the development of a special white oil for SEBS - type thermoplastic elastomers is of great significance for improving the performance and quality of SEBS - type thermoplastic elastomers. Summary of the Invention

[0011] The present invention provides a special white oil for SEBS - type thermoplastic elastomers, its preparation method and application, which overcomes the deficiencies of the above - mentioned prior art and can effectively solve the problems of poor compatibility with SEBS - type thermoplastic elastomers, easy oil bleeding, relatively high volatility and resulting in a decline in the physical properties of products when ordinary white oil is used as a plasticizer.

[0012] One of the technical solutions of the present invention is achieved by the following measures: A preparation method of a special white oil for SEBS - type thermoplastic elastomers is carried out according to the following steps: S1, The paraffin - based distillate oil is mixed with hydrogen and enters a hydrotreating reactor, contacts with a hydrotreating catalyst, and undergoes a hydrotreating - section reaction to obtain a hydrotreated product oil. Among them, the hydrotreating - section reaction includes hydrofining reaction and hydrocracking reaction. The hydrotreating catalyst includes a hydrofining catalyst and a hydrocracking catalyst with a mass ratio of 60% to 75%: 25% to 40%. The initial boiling point of the paraffin - based distillate oil is 360°C to 390°C, the final boiling point is 460°C to 500°C, the total mass content of saturated hydrocarbons is greater than 75%, and the C N value is less than 25%; S2, The hydrotreated product oil obtained in step S1 is mixed with hydrogen and enters a hydroisomerization reactor, contacts with an isodewaxing catalyst, and undergoes a hydroisomerization reaction to obtain a hydroisomerized product oil; S3, The hydroisomerized product oil obtained in step S2 is mixed with hydrogen and enters a hydro - finishing reactor, contacts with a hydrofining catalyst, and undergoes a hydro - finishing reaction to obtain a three - stage hydrotreated product oil. Then the three - stage hydrotreated product oil enters a atmospheric and vacuum distillation column, and vacuum distillation is carried out to obtain a distillate oil with a boiling point higher than 320°C; S4, The distillate oil with a boiling point higher than 320°C obtained in step S3 is mixed with hydrogen and enters a deep hydro - de - aromatization reactor, and undergoes a deep hydro - aromatic saturation reaction under the action of a deep hydro - de - aromatization catalyst to obtain a special white oil for SEBS - type thermoplastic elastomers.

[0013] The following is a further optimization or / and improvement of the above - mentioned technical solution of the invention: In the above step S1, the process conditions of the hydrotreating - section reaction include: hydrogen partial pressure is 14MPa to 20MPa, hydrogen - to - oil volume ratio is 800 to 1200:1, the reaction temperature of hydrofining is 342°C to 380°C, and the volume space velocity is 0.53h -1 to 0.67h -1, the reaction temperature of hydrocracking is 340°C to 370°C, and the space velocity is 1.0 h -1 to 1.6 h -1 , and the reaction temperature of hydrofining is 2°C to 10°C higher than that of hydrocracking.

[0014] In the above step S2, the process conditions of hydroisomerization reaction include: hydrogen partial pressure of 15 MPa to 20 MPa, reaction temperature of 310°C to 350°C, and space velocity of 0.5 h -1 to 1.5 h -1 , and hydrogen-oil volume ratio of 500 to 800:1.

[0015] In the above step S3, the process conditions of hydro-upgrading reaction include: hydrogen partial pressure of 15 MPa to 20 MPa, reaction temperature of 200°C to 240°C, and space velocity of 0.8 h -1 to 1.5 h -1 , and hydrogen-oil volume ratio of 500 to 800:1.

[0016] In the above step S4, the process conditions of deep aromatic saturation reaction include: hydrogen partial pressure of 10 MPa to 20 MPa, reaction temperature of 200°C to 240°C, and space velocity of 0.5 h -1 to 2.0 h -1 , and hydrogen-oil volume ratio of 500 to 800:1.

[0017] In the above step S1, the hydrofining catalyst uses a combination of activated alumina and titanium oxide as the carrier. The active metals in the hydrofining catalyst are two or more of Ni, W, Co, and Mo. And calculated by the mass of the active oxide, the content of the active metal accounts for 15% to 30% of the mass of the hydrofining catalyst.

[0018] In the above step S1, the hydrocracking catalyst uses amorphous silica-alumina and one of β-zeolite or Y-zeolite as the carrier. The active metals in the hydrocracking catalyst are two or more of W, Ni, Co, and Mo. And calculated by the mass of the active oxide, the content of the active metal accounts for 10% to 20% of the mass of the hydrocracking catalyst.

[0019] In the above step S2, the isodewaxing catalyst uses at least one of molecular sieve SAPO-11 and ZSM-22 / ZSM-48 as the carrier. The active metals in the isodewaxing catalyst are two of Pt and Pd, and the mass ratio of Pt to Pd in the two metals is 3:1 to 2:1. The content of the active metal accounts for 0.4% to 1.0% of the mass of the isodewaxing catalyst.

[0020] In the above step S3, the hydrofining catalyst uses at least one of molecular sieves ZSM-5 / ZSM-11 / ZSM-12 as the carrier. The active metal in the hydrofining catalyst is one of Pt or Pd, and the content of the active metal accounts for 0.2% to 0.6% of the mass of the hydrofining catalyst.

[0021] In the above step S4, the deep hydrodearomatization catalyst uses at least one of molecular sieves ZSM-5 / ZSM-22 / ZSM-48 as the carrier. The carrier accounts for 99.4% to 99.8% of the mass of the deep hydrodearomatization catalyst. The active metal in the deep hydrodearomatization catalyst is one of Pt or Pd, and the content of the active metal accounts for 0.2% to 0.6% of the mass of the deep hydrodearomatization catalyst.

[0022] The physical and chemical properties of the above-mentioned SEBS-based thermoplastic elastomer special white oil include: Measured by the method of ASTM2140, the C A value is 0; Measured by the method of ASTM2140, the C N value is 30% to 35%; Measured by the method of Q / SY1440, the ultraviolet light stability is +30; Measured by the method of Q / SY1439, the thermal stability is +30; Measured by the method of ASTM D92, the open flash point is greater than 215 °C, and the evaporation loss is less than 1.0%.

[0023] The second technical solution of the present invention is achieved by the following measures: SEBS-based thermoplastic elastomer special white oil obtained by a preparation method of SEBS-based thermoplastic elastomer special white oil.

[0024] The third technical solution of the present invention is achieved by the following measures: An application of a SEBS-based thermoplastic elastomer special white oil in SEBS-based thermoplastic elastomer raw materials.

[0025] The present invention has a suitable naphthene content, has good compatibility with SEBS-based thermoplastic elastomers, can effectively improve the physical properties of the product, and due to its low volatility and high flash point, can also meet the standard index requirements of cosmetic-grade white oil. At the same time, the process is simple and environmentally friendly, the product yield is high, and it is easy to industrialize. Specific Embodiments

[0026] The present invention is not limited by the following embodiments, and specific implementation manners can be determined according to the technical solution of the present invention and the actual situation. All chemical reagents and chemical supplies mentioned in the present invention are well-known and commonly used chemical reagents and chemical supplies in the prior art unless otherwise specified.

[0027] The present invention will be further described in conjunction with the embodiments as follows: Embodiment 1: The preparation method of the special white oil for SEBS - type thermoplastic elastomers is carried out according to the following steps: S1, The paraffin - based distillate oil is mixed with hydrogen and enters the hydrotreating reactor, contacts with the hydrotreating catalyst, and undergoes the reaction in the hydrotreating section to obtain the hydrotreated product oil. Among them, the reaction in the hydrotreating section includes hydrofining reaction and hydrocracking reaction. The hydrotreating catalyst includes a hydrofining catalyst and a hydrocracking catalyst with a mass ratio of 60% to 75%: 25% to 40%. The initial boiling point of the paraffin - based distillate oil is 360°C to 390°C, the final boiling point is 460°C to 500°C, the total mass content of saturated hydrocarbons is greater than 75%, and the C N value is less than 25%; S2, The hydrotreated product oil obtained in step S1 is mixed with hydrogen and enters the hydroisomerization reactor, contacts with the isodewaxing catalyst, and undergoes hydroisomerization reaction to obtain the hydroisomerized product oil; S3, The hydroisomerized product oil obtained in step S2 is mixed with hydrogen and enters the hydrofinishing reactor, contacts with the hydrofining catalyst, and undergoes hydrofinishing reaction to obtain the three - stage hydrotreated product oil. Then the three - stage hydrotreated product oil enters the atmospheric - vacuum fractionating column, and the fractionating oil with a boiling point higher than 320°C is obtained by vacuum fractionation; S4, The fractionating oil with a boiling point higher than 320°C obtained in step S3 is mixed with hydrogen and enters the deep hydrodearomatization reactor, and undergoes deep hydroaromatic saturation reaction under the action of the deep hydrodearomatization catalyst to obtain the special white oil for SEBS - type thermoplastic elastomers.

[0028] In the present invention, using the paraffin - based distillate oil with an initial boiling point of 360°C to 390°C and a final boiling point of 460°C to 500°C as the raw material and adopting the all - hydrogen process not only solves the problems of difficult solvent treatment and environmental pollution in the preparation of special white oil, but also greatly improves the product yield and reduces the loss of product yield in the solvent refining section.

[0029] At the same time, the present invention uses the grading of two catalysts (hydrofining and hydrocracking), rather than a single catalyst. By adjusting the grading ratio of the two catalysts and controlling the reaction temperature difference, the problem that the original hydrogenation process is difficult to retain naphthenic carbon can be effectively solved, and the product yield can be further improved.

[0030] Moreover, by controlling the reaction temperature difference in the hydrotreating section, the problem that the original hydrogenation process is difficult to retain naphthenic carbon can be effectively solved. After hydrofining, fractionation is carried out and then deep hydroaromatic saturation is carried out to ensure that the oil product will not be unstable due to heating in the fractionation section.

[0031] In the present invention, the fractionated oil has a high saturated hydrocarbon content and a high flash point. As the raw material for the special white oil of SEBS thermoplastic elastomer, it has better advantages in ensuring the high flash point, low volatility, and good photo-thermal stability of the product.

[0032] Example 2: As an optimization of the above example, in step S1, the reaction process conditions in the hydrotreating section include: the hydrogen partial pressure is 14 MPa to 20 MPa, the hydrogen-oil volume ratio is 800 to 1200:1, the reaction temperature for hydrofining is 342 °C to 380 °C, the volume space velocity is 0.53 h -1 to 0.67 h -1 ; the reaction temperature for hydrocracking is 340 °C to 370 °C, the volume space velocity is 1.0 h -1 to 1.6 h -1 , and the reaction temperature for hydrofining is 2 °C to 10 °C higher than the reaction temperature for hydrocracking.

[0033] In the present invention, the reaction temperatures for hydrofining and hydrocracking are controlled by injecting cold hydrogen.

[0034] Example 3: As an optimization of the above example, in step S2, the reaction process conditions for hydroisomerization include: the hydrogen partial pressure is 15 MPa to 20 MPa, the reaction temperature is 310 °C to 350 °C, the volume space velocity is 0.5 h -1 to 1.5 h -1 , and the hydrogen-oil volume ratio is 500 to 800:1.

[0035] Example 4: As an optimization of the above example, in step S3, the reaction process conditions for hydrofinishing include: the hydrogen partial pressure is 15 MPa to 20 MPa, the reaction temperature is 200 °C to 240 °C, the volume space velocity is 0.8 h -1 to 1.5 h -1 , and the hydrogen-oil volume ratio is 500 to 800:1.

[0036] Example 5: As an optimization of the above example, in step S4, the reaction process conditions for deep aromatic saturation by hydrogenation include: the hydrogen partial pressure is 10 MPa to 20 MPa, the reaction temperature is 200 °C to 240 °C, the volume space velocity is 0.5 h -1 to 2.0 h -1 , and the hydrogen-oil volume ratio is 500 to 800:1.

[0037] Example 6: As an optimization of the above example, in step S1, the hydrofining catalyst uses a carrier composed of activated alumina and titanium oxide. The active metals in the hydrofining catalyst are two or more of Ni, W, Co, and Mo. And calculated by the mass of the active oxide, the content of the active metal accounts for 15% to 30% of the mass of the hydrofining catalyst. The hydrofining catalyst needs to be pretreated by in-situ presulfidation before use.

[0038] Example 7: As an optimization of the above embodiments, in step S1, the hydrocracking catalyst uses amorphous silica-alumina and one of β zeolite or Y zeolite as the carrier. The active metals in the hydrocracking catalyst are two or more of W, Ni, Co, and Mo. And calculated by the mass of the active oxide, the content of the active metal accounts for 10% to 20% of the mass of the hydrocracking catalyst. The hydrocracking catalyst needs to be pretreated by in-situ sulfidation before use.

[0039] Example 8: As an optimization of the above embodiments, in step S2, the isodewaxing catalyst uses at least one of molecular sieve SAPO-11 and ZSM-22 / ZSM-48 as the carrier. The active metals in the isodewaxing catalyst are two of Pt and Pd, and the mass ratio of Pt to Pd in the two metals is 3:1 to 2:1. The content of the active metal accounts for 0.4% to 1.0% of the mass of the isodewaxing catalyst. The isodewaxing catalyst needs to be reduced and activated by low-pressure hydrogen before use, and the hydrogen reduction pressure is 0.3 MPa to 1.0 MPa.

[0040] Example 9: As an optimization of the above embodiments, in step S3, the hydrofining catalyst uses at least one of molecular sieves ZSM-5 / ZSM-11 / ZSM-12 as the carrier. The active metal in the hydrofining catalyst is one of Pt or Pd, and the content of the active metal accounts for 0.2% to 0.6% of the mass of the hydrofining catalyst. The hydrofining catalyst needs to be reduced and activated by low-pressure hydrogen before use, and the hydrogen reduction pressure is 0.3 MPa to 1.0 MPa.

[0041] Example 10: As an optimization of the above embodiments, in step S4, the hydrodeep dearomatization catalyst uses at least one of molecular sieves ZSM-5 / ZSM-22 / ZSM-48 as the carrier. The carrier accounts for 99.4% to 99.8% of the mass of the hydrodeep dearomatization catalyst. The active metal in the hydrodeep dearomatization catalyst is one of Pt or Pd, and the content of the active metal accounts for 0.2% to 0.6% of the mass of the hydrodeep dearomatization catalyst. The hydrodeep dearomatization catalyst needs to be reduced and activated by low-pressure hydrogen before use, and the hydrogen reduction pressure is 0.3 MPa to 1.0 MPa.

[0042] Example 11: As an optimization of the above embodiments, the physical and chemical properties of the SEBS-based thermoplastic elastomer special white oil include: Measured by the method of ASTM2140, the C A value is 0; Measured by the method of ASTM2140, the C N value is 30% to 35%; Measured by the method of Q / SY1440, the ultraviolet light stability is +30; Determined by the method of Q / SY1439, the thermal stability is +30; Determined by the method of ASTM D92, the open flash point is greater than 215 °C, the evaporation loss is less than 1.0%, and the yield of the white oil special for SEBS - type thermoplastic elastomers is above 75%, and it has good compatibility with SEBS.

[0043] Example 12: The white oil special for SEBS - type thermoplastic elastomers obtained by the preparation method of the white oil special for SEBS - type thermoplastic elastomers.

[0044] Example 13: The application of the white oil special for SEBS - type thermoplastic elastomers in the raw materials of SEBS - type thermoplastic elastomers.

[0045] The white oil special for SEBS - type thermoplastic elastomers obtained by the present invention has a suitable naphthene content, the C N value is 30% to 35%, the yield is above 75%, has good compatibility with SEBS, low volatility, high flash point, and when applied to the raw materials of SEBS - type thermoplastic elastomers, can effectively improve the physical properties of SEBS - type thermoplastic elastomer products and other advantages.

[0046] Example 14: In the preparation method of the white oil special for SEBS - type thermoplastic elastomers, paraffin - based distillate oil (the initial boiling point of the distillation range is 360 °C, and the final boiling point is 460 °C) is used as the raw material, and the main properties of the raw material are shown in Table 1; The raw material is mixed with hydrogen and enters the hydrotreating reactor for hydrotreating section reaction, and the process conditions of the hydrotreating section reaction are shown in Table 2; The loading ratio (mass ratio) of the hydrofining catalyst to the hydrocracking catalyst in the hydrotreating section is 75:25; the active metals in the hydrofining catalyst are Ni, Co, and Mo, and the mass proportion of their oxides is 15%. The carrier of the hydrofining catalyst is a composition of activated alumina and titanium oxide; The active components of the hydrocracking catalyst are Ni and W, and the mass proportion of their oxides is 10%. The carrier of the hydrocracking catalyst is amorphous silica - alumina and beta zeolite; The hydrotreated product oil is mixed with hydrogen and enters the hydroisomerization reactor, and the process conditions of the hydroisomerization reaction are shown in Table 3; The carrier of the isodewaxing catalyst is molecular sieve SAPO - 11 and molecular sieve ZSM - 22, the active metals are Pt and Pd, the mass proportion of the active metals is 0.4%, and the mass ratio of Pt:Pd is 3:1; The hydroisomerized product oil is subjected to hydro - finishing reaction, and the process conditions of the hydro - finishing reaction are shown in Table 4. The carrier of the hydrofining catalyst is molecular sieve ZSM - 5, and the active metal is Pt, with a mass proportion of 0.2%; The obtained three-stage hydrogenated product oil is distilled, and the fraction with a distillation range of 320 °C or higher is cut. Finally, the fraction with a temperature higher than 320 °C is mixed with hydrogen and enters the deep hydrodearomatization reactor. The process conditions for the deep hydrodearomatization reaction are shown in Table 5; The carrier of the deep hydrodearomatization catalyst is zeolite ZSM-5, and the active metal is Pd with a mass ratio of 0.2%. The obtained product oil is the special white oil for SEBS thermoplastic elastomers, and its main properties are shown in Table 6.

[0047] Example 15: In the preparation method of the special white oil for SEBS thermoplastic elastomers, paraffin-based distillate oil (with an initial boiling point of 380 °C and a final boiling point of 480 °C) is used as the raw material, and the main properties of the raw material are shown in Table 1; This raw material is mixed with hydrogen and enters the hydrotreating reactor for the hydrotreating section reaction. The process conditions for the hydrotreating section reaction are shown in Table 2; The filling ratio (mass ratio) of the hydrofining catalyst to the hydrocracking catalyst in the hydrotreating section is 72:28; in the hydrofining catalyst, the active metals are Ni, W, and Mo, and the mass ratio of their oxides is 20%. The carrier of the hydrofining catalyst is a composition of activated alumina and titanium oxide; The active components of the hydrocracking catalyst are Ni and Mo, and the mass ratio of their oxides is 13%. The carrier of the hydrocracking catalyst is amorphous silica-alumina and β zeolite; The hydrotreated product oil is mixed with hydrogen and enters the hydroisomerization reactor. The process conditions for the hydroisomerization reaction are shown in Table 3; The carrier of the isodewaxing catalyst is zeolite SAPO-11 and zeolite ZSM-22, and the active metals are Pt and Pd with a mass ratio of 0.6%, and the mass ratio of Pt:Pd is 3:1; The hydroisomerized product oil is subjected to a hydrofinishing reaction. The process conditions for the hydrofinishing reaction are shown in Table 4. The carrier of the hydrofining catalyst is zeolite ZSM-5, and the active metal is Pt with a mass ratio of 0.4%; The obtained three-stage hydrogenated product oil is distilled, and the fraction with a distillation range of 320 °C or higher is cut. Finally, the fraction with a temperature higher than 320 °C is mixed with hydrogen and enters the deep hydrodearomatization reactor. The process conditions for the deep hydrodearomatization reaction are shown in Table 5; The carrier of the deep hydrodearomatization catalyst is zeolite ZSM-5, and the active metal is Pd with a mass ratio of 0.3%. The obtained product oil is the special white oil for SEBS thermoplastic elastomers, and its main properties are shown in Table 6.

[0048] Example 16: In the preparation method of the special white oil for SEBS thermoplastic elastomers, paraffin-based distillate oil (with an initial boiling point of 390 °C and a final boiling point of 490 °C) is used as the raw material, and the main properties of the raw material are shown in Table 1; The raw material is mixed with hydrogen and enters a hydrotreating reactor for the reaction in the hydrotreating section. The process conditions for the reaction in the hydrotreating section are shown in Table 2; The loading ratio (mass ratio) of the hydrofining catalyst to the hydrocracking catalyst in the hydrotreating section is 70:30; the active metals in the hydrofining catalyst are Ni, W, and Co, and the mass ratio of their oxides is 30%. The carrier of the hydrofining catalyst is a composition of activated alumina and titanium oxide; The active components of the hydrocracking catalyst are Ni, Co, and W, and the mass ratio of their oxides is 15%. The carrier of the hydrocracking catalyst is amorphous silica-alumina and Y-type molecular sieve; The hydrotreated product oil is mixed with hydrogen and enters a hydroisomerization reactor. The process conditions for the hydroisomerization reaction are shown in Table 3; The carrier of the isodewaxing catalyst is molecular sieve SAPO-11 and molecular sieve ZSM-48, the active metals are Pt and Pd, the mass ratio of the active metals is 0.8%, and the mass ratio of Pt:Pd is 2:1; The hydroisomerized product oil is subjected to hydrofinishing reaction. The process conditions for the hydrofinishing reaction are shown in Table 4. The carrier of the hydrofining catalyst is molecular sieve ZSM-11, and the active metal is Pt, with a mass ratio of 0.6%; The three-stage hydrotreated product oil obtained is distilled, and the fraction with a distillation range greater than or equal to 320 °C is cut. Finally, the fraction greater than 320 °C is mixed with hydrogen and enters a hydrodeep dearomatization reactor. The process conditions for the hydrodeep dearomatization reaction are shown in Table 5; The carrier of the hydrodeep dearomatization catalyst is molecular sieve ZSM-22, the active metal is Pd, with a mass ratio of 0.4%. The resulting product oil is the special white oil for SEBS thermoplastic elastomer, and its main properties are shown in Table 6.

[0049] Example 17: In the preparation method of the special white oil for SEBS thermoplastic elastomer, a paraffin-based distillate oil (initial boiling point of the distillation range is 390 °C, final boiling point is 500 °C) is used as the raw material, and the main properties of the raw material are shown in Table 1; The raw material is mixed with hydrogen and enters a hydrotreating reactor for the reaction in the hydrotreating section. The process conditions for the reaction in the hydrotreating section are shown in Table 2; The loading ratio (mass ratio) of the hydrofining catalyst to the hydrocracking catalyst in the hydrotreating section is 65:35; the active metals in the hydrofining catalyst are Ni, Mo, and Co, and the mass ratio of their oxides is 20%. The carrier of the hydrofining catalyst is a composition of activated alumina and titanium oxide; The active components of the hydrocracking catalyst are Ni and W, and the mass ratio of their oxides is 17%. The carrier of the hydrocracking catalyst is amorphous silica-alumina and Y-type molecular sieve; The hydrotreated product oil is mixed with hydrogen and fed into the hydroisomerization reactor. The process conditions for the hydroisomerization reaction are shown in Table 3; The carrier of the isodewaxing catalyst is molecular sieve SAPO-11 and molecular sieve ZSM-48, and the active metals are Pt and Pd. The mass ratio of the active metals is 1.0%, and the mass ratio of Pt:Pd is 2.5:1; The hydroisomerized product oil is subjected to hydrofinishing reaction. The process conditions for the hydrofinishing reaction are shown in Table 4. The carrier of the hydrofinishing catalyst is molecular sieve ZSM-12, and the active metal is Pt with a mass ratio of 0.5%; The three-stage hydrotreated product oil obtained is distilled, and the fraction with a distillation range of 320 °C or higher is cut. Finally, the fraction greater than 320 °C is mixed with hydrogen and fed into the hydrodeep dearomatization reactor. The process conditions for the hydrodeep dearomatization reaction are shown in Table 5; The carrier of the hydrodeep dearomatization catalyst is molecular sieve ZSM-48, and the active metal is Pd with a mass ratio of 0.5%. The obtained product oil is the special white oil for SEBS thermoplastic elastomer, and its main properties are shown in Table 6.

[0050] Example 18: In the preparation method of the special white oil for SEBS thermoplastic elastomer, a paraffin-based distillate oil (initial boiling point of the distillation range is 390 °C, final boiling point is 500 °C) is used as the raw material. The main properties of the raw material are shown in Table 1; This raw material is mixed with hydrogen and fed into the hydrotreating reactor for the hydrotreating section reaction. The process conditions for the hydrotreating section reaction are shown in Table 2; The loading ratio (mass ratio) of the hydrofinishing catalyst to the hydrocracking catalyst in the hydrotreating section is 60:40. The active metals in the hydrofinishing catalyst are Ni, W, and Co, and the mass ratio of their oxides is 27%. The carrier of the hydrofinishing catalyst is a combination of activated alumina and titanium oxide; The active components of the hydrocracking catalyst are Ni and Co, and the mass ratio of their oxides is 20%. The carrier of the hydrocracking catalyst is amorphous silica-alumina and Y-type molecular sieve; The hydrotreated product oil is mixed with hydrogen and fed into the hydroisomerization reactor. The process conditions for the hydroisomerization reaction are shown in Table 3; The carrier of the isodewaxing catalyst is molecular sieve SAPO-11 and molecular sieve ZSM-48, and the active metals are Pt and Pd. The mass ratio of the active metals is 1.0%, and the mass ratio of Pt:Pd is 3:1; The hydroisomerized product oil is subjected to hydrofinishing reaction. The process conditions for the hydrofinishing reaction are shown in Table 4. The carrier of the hydrofinishing catalyst is molecular sieve ZSM-5 and ZSM-12, and the active metal is Pt with a mass ratio of 0.3%; The obtained three-stage hydrogenated product oil is distilled to cut fractions with a distillation range of 320 °C or higher. Finally, the components with a temperature higher than 320 °C are mixed with hydrogen and enter the deep hydrodearomatization reactor. The process conditions for the deep hydrodearomatization reaction are shown in Table 5; The carrier of the deep hydrodearomatization catalyst is zeolite ZSM-5, and the active metal is Pd with a mass ratio of 0.6%. The obtained product oil is the special white oil for SEBS thermoplastic elastomers, and its main properties are shown in Table 6.

[0051] Comparative Example 1: Using paraffin-based distillate oil (initial boiling point of the distillation range is 390 °C, final boiling point is 500 °C) as the raw material, the main properties of the raw material are shown in Table 1. This raw material is mixed with hydrogen and enters the hydrotreating reactor for the hydrotreating section reaction. The process conditions for the hydrotreating section reaction are shown in Table 2; The hydrotreated product oil is mixed with hydrogen and enters the hydroisomerization reactor. The process conditions for the hydroisomerization reaction are shown in Table 3; The hydroisomerized product oil undergoes a hydrofinishing reaction. The process conditions for the hydrofinishing reaction are shown in Table 4; The obtained three-stage hydrogenated product oil is distilled to cut fractions with a distillation range of 320 °C or higher. Finally, the components with a temperature higher than 320 °C are mixed with hydrogen and enter the deep hydrodearomatization reactor. The process conditions for the deep hydrodearomatization reaction are shown in Table 5, and the obtained product oil is the special white oil for SEBS thermoplastic elastomers, and its main properties are shown in Table 6.

[0052] Comparative Example 2: The raw material oil, naphthenic distillate oil (initial boiling point of the distillation range is 325 °C, final boiling point is 485 °C), is subjected to furfural refining. The main properties of the raw material oil are shown in Table 1. The mass ratio of furfural to the raw material oil is 1.2:1, and the extraction temperature is 80 °C. After phase separation, low-aromatic oil is obtained with a yield of 72%. Using the low-aromatic oil as the raw material, it undergoes hydrotreating reaction, hydroisomerization reaction, and hydrofinishing reaction in sequence. The three-stage hydrogenation conditions are shown in Tables 2 to 4 respectively. The components with a distillation range of 380 °C to 480 °C are collected as the special white oil for SEBS thermoplastic elastomers. The main properties are shown in Table 6.

[0053] The special white oil for SEBS thermoplastic elastomers of the present invention is used to prepare SEBS thermoplastic elastomer products, and the changes in physical properties are shown in Table 7.

[0054] Among them, the C N value can reflect the characteristics of naphthenic base. A suitable naphthenic base characteristic (C N value) can effectively improve the tensile strength and elongation at break of the elastomer in Table 7 and has good compatibility with SEBS.

[0055] It can be seen from the data in Tables 3 to 7 that the special white oil for SEBS-based thermoplastic elastomers of the present invention has certain naphthenic characteristics, has good compatibility with SEBS, can be uniformly dispersed in SEBS-based thermoplastic elastomers, and effectively improves the mechanical properties and appearance quality of products.

[0056] Therefore, the special white oil for SEBS-based thermoplastic elastomers of the present invention has characteristics such as high flash point, low volatility, and excellent photo-thermal stability, improving the stability and service life of products. The product properties can also meet the index requirements of the cosmetic-grade white oil standard NB / SH0007-2015. The production process of this preparation method is simple and environmentally friendly, with a high product yield. The production efficiency has significant advantages compared with existing methods and is suitable for large-scale industrial production. At the same time, for SEBS-based thermoplastic elastomer products prepared using the special white oil for SEBS-based thermoplastic elastomers of the present invention, the tensile strength is increased by 10% to 20%, the elongation at break is increased by 15% to 25%, and the hardness is reduced by 5 HA to 10 HA, effectively improving the flexibility and elasticity of the products.

[0057] In summary, the special white oil for SEBS-based thermoplastic elastomers of the present invention has a high flash point, a hydrocarbon composition suitable for good compatibility, excellent photo-stability and thermal stability, better meeting the characteristics of elasticity, non-oil leakage, and processing and molding of rubber and plastic products, and has a high product yield and better economy.

[0058] The above technical features constitute the embodiments of the present invention, which have strong adaptability and implementation effects. Non-essential technical features can be added or subtracted according to actual needs to meet the requirements of different situations.

[0059] Table 1 。

[0060] Table 2 。

[0061] Table 3 。

[0062] Table 4 。

[0063] Table 5 。

[0064] Table 6 。

[0065] Table 7 。

Claims

1. A preparation method of a special white oil for SEBS - type thermoplastic elastomers, characterized in that It is carried out according to the following steps: S1. The paraffinic distillate oil is mixed with hydrogen and enters the hydrotreating reactor, contacts with the hydrotreating catalyst, and undergoes the reaction in the hydrotreating section to obtain the hydrotreated product oil. Among them, the reaction in the hydrotreating section includes hydrofining reaction and hydrocracking reaction. The hydrotreating catalyst includes a hydrofining catalyst and a hydrocracking catalyst with a mass ratio of 60% to 75%: 25% to 40%. The initial boiling point of the paraffinic distillate oil is 360°C to 390°C, the final boiling point is 460°C to 500°C, the total mass content of saturated hydrocarbons is greater than 75%, and the C N value is less than 25%; S2, the hydrotreating product oil obtained in step S1 is mixed with hydrogen and enters a hydroisomerization reactor, contacts with an isodewaxing catalyst, and undergoes a hydroisomerization reaction to obtain a hydroisomerization product oil; S3, the hydroisomerization product oil obtained in step S2 is mixed with hydrogen and enters a hydrofinishing reactor, contacts with a hydrofinishing catalyst, and undergoes a hydrofinishing reaction to obtain a three-stage hydrotreated product oil. Then, the three-stage hydrotreated product oil enters a atmospheric and vacuum distillation column, and a fraction oil with a boiling point higher than 320 °C is obtained by vacuum distillation; S4, the fraction oil with a boiling point higher than 320 °C obtained in step S3 is mixed with hydrogen and enters a deep hydrodearomatization reactor, and undergoes a deep hydroaromatic saturation reaction under the action of a deep hydrodearomatization catalyst to obtain a special white oil for SEBS thermoplastic elastomers.

2. The preparation method of the special white oil for SEBS-based thermoplastic elastomer according to claim 1, characterized in that In step S1, the reaction process conditions of the hydrotreating section include: the hydrogen partial pressure is 14 MPa to 20 MPa, the hydrogen-oil volume ratio is 800 to 1200:1, the reaction temperature of hydrofining is 342 °C to 380 °C, and the volume space velocity is 0.53 h -1 to 0.67 h -1 , the reaction temperature of hydrocracking is 340 °C to 370 °C, and the volume space velocity is 1.0 h -1 to 1.6 h -1 , and the reaction temperature of hydrofining is 2 °C to 10 °C higher than that of hydrocracking.

3. The preparation method of the special white oil for SEBS-based thermoplastic elastomer according to claim 1 or 2, characterized in that In step S2, the process conditions for the hydroisomerization reaction include: a hydrogen partial pressure of 15 MPa to 20 MPa, a reaction temperature of 310 °C to 350 °C, a volumetric space velocity of 0.5 h -1 to 1.5 h -1 , and a hydrogen-to-oil volume ratio of 500 to 800:

1.

4. The preparation method of the special white oil for SEBS-based thermoplastic elastomers according to claim 3, characterized in that In step S3, the process conditions of the hydrogenation supplementary refining reaction include: hydrogen partial pressure of 15 MPa to 20 MPa, reaction temperature of 200 °C to 240 °C, volume space velocity of 0.8 h -1 to 1.5 h -1 , and hydrogen-oil volume ratio of 500 to 800:

1.

5. The preparation method of the special white oil for SEBS-based thermoplastic elastomer according to claim 1 or 2 or 4, characterized in that In step S4, the process conditions for the hydrogenation deep aromatics saturation reaction include: a hydrogen partial pressure of 10 MPa to 20 MPa, a reaction temperature of 200 °C to 240 °C, a volumetric space velocity of 0.5 h -1 to 2.0 h -1 , and a hydrogen-to-oil volume ratio of 500 to 800:

1.

6. The preparation method of the special white oil for SEBS-based thermoplastic elastomers according to claim 5, characterized in that In step S1, the hydrofinishing catalyst uses a combination of activated alumina and titanium oxide as a carrier. The active metals in the hydrofinishing catalyst are two or more of Ni, W, Co, and Mo. And based on the mass of the active oxide, the content of the active metal accounts for 15% to 30% of the mass of the hydrofinishing catalyst.

7. The preparation method of the special white oil for SEBS-based thermoplastic elastomers according to claim 1 or 2 or 4 or 6, characterized in that In step S1, the hydrocracking catalyst uses one of amorphous silica-alumina and β zeolite or Y zeolite as a carrier. The active metals in the hydrocracking catalyst are two or more of W, Ni, Co, and Mo. And based on the mass of the active oxide, the content of the active metal accounts for 10% to 20% of the mass of the hydrocracking catalyst.

8. The preparation method of the special white oil for SEBS-based thermoplastic elastomers according to claim 7, characterized in that In step S2, the isodewaxing catalyst uses at least one of molecular sieves SAPO-11 and ZSM-22 / ZSM-48 as a carrier. The active metals in the isodewaxing catalyst are two of Pt and Pd, and the mass ratio of Pt to Pd in the two metals is 3:1 to 2:

1. The content of the active metal accounts for 0.4% to 1.0% of the mass of the isodewaxing catalyst.

9. The preparation method of the special white oil for SEBS-based thermoplastic elastomer according to claim 1 or 2 or 4 or 6 or 8, characterized in that In step S3, the hydrofinishing catalyst uses at least one of molecular sieves ZSM-5 / ZSM-11 / ZSM-12 as a carrier. The active metal in the hydrofinishing catalyst is one of Pt or Pd, and the content of the active metal accounts for 0.2% to 0.6% of the mass of the hydrofinishing catalyst.

10. The preparation method of the special white oil for SEBS - based thermoplastic elastomers according to claim 9, characterized in that In step S4, the deep hydrodearomatization catalyst uses at least one of molecular sieves ZSM-5 / ZSM-22 / ZSM-48 as a carrier. The carrier accounts for 70% to 85% of the mass of the deep hydrodearomatization catalyst. The active metal in the deep hydrodearomatization catalyst is one of Pt or Pd, and the content of the active metal accounts for 0.2% to 0.6% of the mass of the deep hydrodearomatization catalyst.

11. The preparation method of the special white oil for SEBS - based thermoplastic elastomers according to claim 1 or 2 or 4 or 6 or 8 or 10, characterized in that The physical and chemical properties of the special white oil for SEBS thermoplastic elastomers include: Determined by the method of ASTM2140, C A value is 0; Measured by the method of ASTM2140, C N value is 30% to 35%; Determined by the method of Q / SY1440, the ultraviolet light stability is +30; Determined by the method of Q / SY1439, the thermal stability is +30; Determined by the method of ASTM D92, the open flash point is greater than 215 °C.

12. A special white oil for SEBS thermoplastic elastomers obtained by the preparation method according to any one of claims 1 to 11.

13. Application of the special white oil for SEBS-based thermoplastic elastomers according to claim 12 in the raw materials of SEBS-based thermoplastic elastomers.