Special white oil for SEBS thermoplastic elastomers and its preparation method and application

Abstract

The present invention relates to the field of petrochemical technology and is a white oil specifically for SEBS-type thermoplastic elastomers, and its preparation method and application. The white oil is obtained according to the following steps: a paraffin-based distillate oil is subjected to a hydrotreating stage reaction with hydrogen, the resulting hydrotreating product oil is mixed with hydrogen to undergo a hydroisomerization reaction, the resulting hydroisomerized product oil is mixed with hydrogen to undergo a hydrogenation supplementary refining reaction, the resulting three-stage hydrogenated product oil is subjected to vacuum fractionation to obtain a distillate oil with a boiling point greater than 320°C, which is mixed with hydrogen to undergo a hydrogenation deep aromatic saturation reaction to obtain a white oil specifically for SEBS-type thermoplastic elastomers. The white oil has a suitable cycloalkane content, good compatibility with SEBS-type 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.

Description

Technical Field

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

[0002] Thermoplastic elastomer (TPE) is a polymer material with properties between rubber and thermoplastic plastics. It has the dual nature and broad properties of rubber and plastics. It has the high elasticity of rubber at room temperature and the high elasticity of vulcanized rubber at room temperature. At high temperatures, it is easy to process and shape like thermoplastic plastics. It is a polymer material with the properties of both vulcanized rubber and thermoplastic plastics.

[0003] White oil is typically added to TPE material formulations as a plasticizer, primarily to enhance fluidity, plasticize, and adjust hardness. The higher the oil content, the lower the hardness of the TPE. White oils used in thermoplastic elastomers (TPEs) primarily include naphthenic oil and paraffin oil. White oils are categorized into industrial, food, cosmetic, and pharmaceutical grades, depending on the needs of different industries.

[0004] SEBS-based thermoplastic elastomers (SEBS) boast excellent aging resistance, weathering resistance, chemical resistance, and good processability, and are widely used in numerous fields. In the production of SEBS-based thermoplastic elastomers, white oil, as a key plasticizer, significantly impacts their performance. However, existing conventional white oils, when used in SEBS-based thermoplastic elastomers, suffer from poor compatibility with SEBS, prone to oil release, high volatility, and reduced physical properties of the finished product, making them unable to meet the high-performance requirements of SEBS-based thermoplastic elastomers.

[0005] Chinese patent publication CN102021032B discloses a naphthenic filler oil for soft rubber toys and its preparation method. This method uses naphthenic distillate oil as the raw material and utilizes a combination of medium-pressure hydrogenation and furfural refining to produce the toy oil. However, the furfural refining extraction column has poor selectivity, resulting in an excessively high aromatic content in the refined oil after extraction. The medium-pressure hydrogenation pressure is too low, preventing full saturation of aromatics and cracking of naphthenes to the desired content, making it impossible to produce white oil. Furthermore, the aromatics and naphthenes in the oil affect the physical and chemical properties, mechanical properties, and yellowing resistance of SEBS rubber products.

[0006] Chinese patent publication CN117304976A discloses a white oil specifically formulated for SEBS-based thermoplastic elastomers, its preparation method, and its application. Using naphthenic distillate as the feedstock, the process sequentially undergoes solvent extraction, hydrogenation, isomerization and pour point reduction, and hydrogenation refining. The fraction at 300°C to 500°C is collected to produce the SEBS-specific naphthenic white oil product. The SEBS-specific naphthenic white oil prepared in this invention has a high viscosity index and a certain naphthenic content, making it suitable as a rubber softening filler for specialty SEBS products. However, this method uses naphthenic feedstock, which has a low flash point, resulting in high volatility in the resulting white oil, which is detrimental to the product's stability and service life. Furthermore, this technology lacks a deep dearomatization process, resulting in poor storage stability for the white oil.

[0007] The above methods all use cycloalkane distillate oil as raw material and adopt a combined process of solvent refining and hydrogenation. The process flow is long and the product yield is low. There is a solvent refining process in the production process, which involves the treatment of waste solvents. It does not meet the current green production needs and is highly polluting and not environmentally friendly. In addition, polycyclic aromatic hydrocarbons are removed through solvent refining, which reduces the production efficiency of the product.

[0008] A Chinese patent document with authorization publication number CN114479934B discloses a method for preparing a white oil specifically for polystyrene and a white oil specifically for polystyrene. The method for preparing a white oil specifically for polystyrene provided by the present invention comprises the following steps: 1) dewaxing and refining a paraffin-based distillate oil using a ketone-benzene dewaxing unit to obtain a dewaxed refined oil; 2) subjecting the dewaxed refined oil to hydrogenation treatment, hydroisomerization and pour point decompression, and hydrogenation supplementary refining to obtain a three-stage hydrogenation product oil; 3) subjecting the three-stage hydrogenation product oil to normal and vacuum distillation, and collecting fractions with a distillation range of 430°C or greater to obtain a white oil specifically for polystyrene. However, in this method, the raw paraffin-based distillate oil has a distillation range of 420°C to 540°C, and the process is a combined solvent refining and hydrogenation process, and no hydrogenation deep dearomatization refining is performed after the distillation, which affects the storage stability of the product.

[0009] A Chinese patent document with authorization announcement number CN106479565B discloses a white oil specifically for polystyrene and a method for preparing the same. The method for preparing the white oil specifically for polystyrene comprises the following steps: 1) subjecting a distillate of cycloalkyl crude oil to solvent refining in an extraction tower, obtaining an extract at the bottom of the tower and a refined liquid at the top, and recovering the solvent to obtain refined oil; 2) subjecting the refined oil to a hydrogenation process and distillation cutting to obtain the white oil specifically for polystyrene; the hydrogenation process includes hydrogenation treatment, catalytic dewaxing, hydrorefining, and hydrogenation for deep aromatic saturation. However, this method employs a furfural refining → hydrogenation treatment → catalytic dewaxing → hydrorefining → deep hydrogenation saturation → fractionation process, and the raw material is cycloalkyl distillate oil. The resulting white oil specifically for polystyrene has a high cycloalkane content.

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

[0011] The present invention provides a white oil specially used for SEBS-type thermoplastic elastomers, a preparation method thereof, and an application thereof, which overcome the deficiencies of the above-mentioned prior art and can effectively solve the problems of conventional common white oil as a plasticizer, such as poor compatibility with SEBS-type thermoplastic elastomers, easy oil release, high volatility, and resulting deterioration of the physical properties of the product.

[0012] One of the technical solutions of the present invention is achieved by the following measures: A method for preparing a white oil special for SEBS-type thermoplastic elastomer is carried out according to the following steps:

[0013] S1, paraffin-based distillate oil is mixed with hydrogen and enters a hydroprocessing reactor, contacts a hydroprocessing catalyst, and undergoes a hydroprocessing stage reaction to obtain a hydroprocessed product oil, wherein the hydroprocessing stage reaction includes a hydrorefining reaction and a hydrocracking reaction, and the hydroprocessing catalyst includes a hydrorefining catalyst and a hydrocracking catalyst in 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 C N The value is less than 25%;

[0014] S2, the hydrotreated product oil obtained in step S1 is mixed with hydrogen and enters a hydroisomerization reactor, where it contacts an isodewaxing catalyst to undergo a hydroisomerization reaction to obtain a hydroisomerization product oil;

[0015] S3, mixing the hydroisomerized oil obtained in step S2 with hydrogen and entering the reactor for hydrorefining, contacting the reactor with a hydrorefining catalyst, causing a hydrorefining reaction to produce a three-stage hydrorefining oil, and then entering a normal vacuum distillation tower for vacuum fractionation to obtain a distillate having a boiling point higher than 320°C;

[0016] S4, mixing the distillate oil with a boiling point higher than 320° C. obtained in step S3 with hydrogen and entering the reactor for hydrogenation deep dearomatization, where a hydrogenation deep dearomatization catalyst is used to cause a hydrogenation deep aromatic saturation reaction to obtain a white oil specifically for SEBS thermoplastic elastomers.

[0017] The following is a further optimization and / or improvement of one of the above-mentioned technical solutions:

[0018] In the above step S1, the reaction process conditions of the hydrotreating stage include: hydrogen partial pressure of 14MPa to 20MPa, hydrogen-to-oil volume ratio of 800 to 1200:1, hydrotreating reaction temperature of 342°C to 380°C, volume space velocity of 0.53h -1 to 0.67h -1 , hydrocracking reaction temperature 340℃ to 370℃, volume space velocity 1.0h -1 to 1.6 hours -1 , and the hydrofining reaction temperature is 2°C to 10°C higher than the hydrocracking reaction temperature.

[0019] In the above step S2, the hydroisomerization reaction process conditions include: hydrogen partial pressure of 15MPa to 20MPa, reaction temperature of 310℃ to 350℃, volume space velocity of 0.5h -1 Up to 1.5 hours -1 , hydrogen-oil volume ratio 500 to 800:1.

[0020] In the above step S3, the hydrogenation supplementary refining reaction process conditions include: hydrogen partial pressure of 15MPa to 20MPa, reaction temperature of 200℃ to 240℃, volume space velocity of 0.8h -1 Up to 1.5 hours -1 , hydrogen-oil volume ratio 500 to 800:1.

[0021] In the above step S4, the process conditions for the deep aromatic saturation reaction by hydrogenation include: hydrogen partial pressure of 10 MPa to 20 MPa, reaction temperature of 200°C to 240°C, volume space velocity of 0.5 h -1 to 2.0h -1 , hydrogen-oil volume ratio 500 to 800:1.

[0022] In the above step S1, the hydrorefining catalyst uses an activated alumina and titanium oxide composition as a carrier, the active metals in the hydrorefining catalyst are two or more of Ni, W, Co and Mo, and the active metal content accounts for 15% to 30% of the mass of the hydrorefining catalyst based on the mass of the active oxide.

[0023] In the above step S1, the hydrocracking catalyst is supported by amorphous silica-alumina and one of β molecular sieve or Y molecular sieve, and the active metal in the hydrocracking catalyst is two or more of W, Ni, Co and Mo, and the active metal content accounts for 10% to 20% of the mass of the hydrocracking catalyst based on the mass of the active oxide.

[0024] In the above, in step S2, the isodewaxing catalyst is supported by at least one of the molecular sieves SAPO-11 and ZSM-22 / ZSM-48, 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, and the active metal content accounts for 0.4% to 1.0% of the mass of the isodewaxing catalyst.

[0025] In the above step S3, the hydrorefining catalyst is supported by at least one of the molecular sieves ZSM-5 / ZSM-11 / ZSM-12, the active metal in the hydrorefining catalyst is one of Pt and Pd, and the active metal content accounts for 0.2% to 0.6% of the mass of the hydrorefining catalyst.

[0026] In the above step S4, the hydrogenation deep dearomatization catalyst uses at least one of the molecular sieves ZSM-5 / ZSM-22 / ZSM-48 as a carrier, the carrier accounts for 99.4% to 99.8% of the mass of the hydrogenation deep dearomatization catalyst, the active metal in the hydrogenation deep dearomatization catalyst is one of Pt or Pd, and the active metal content accounts for 0.2% to 0.6% of the mass of the hydrogenation deep dearomatization catalyst.

[0027] The physical and chemical properties of the above-mentioned white oil for SEBS thermoplastic elastomers include:

[0028] Measured by ASTM 2140, C A The value is 0;

[0029] Measured by ASTM 2140, C N The value is 30% to 35%;

[0030] Determined by Q / SY1440 method, UV stability +30;

[0031] Determined by Q / SY1439 method, thermal stability +30;

[0032] Measured by ASTM D92, the open flash point is greater than 215°C and the evaporation loss is less than 1.0%.

[0033] The second technical solution of the present invention is achieved through the following measures: a preparation method of a special white oil for SEBS type thermoplastic elastomer to obtain the special white oil for SEBS type thermoplastic elastomer.

[0034] The third technical solution of the present invention is achieved through the following measures: application of a white oil special for SEBS-type thermoplastic elastomer in SEBS-type thermoplastic elastomer raw materials.

[0035] The invention has a suitable cycloalkane content and good compatibility with SEBS-type 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. DETAILED DESCRIPTION

[0036] The present invention is not limited to the following embodiments, and specific implementation methods can be determined based on the technical solutions of the present invention and actual conditions. Unless otherwise specified, the various chemical reagents and chemicals mentioned in the present invention are all chemical reagents and chemicals known and used in the prior art.

[0037] The present invention will be further described below in conjunction with the embodiments:

[0038] Example 1: The preparation method of the white oil for SEBS thermoplastic elastomer is carried out according to the following steps:

[0039] S1, paraffin-based distillate oil is mixed with hydrogen and enters a hydroprocessing reactor, contacts a hydroprocessing catalyst, and undergoes a hydroprocessing stage reaction to obtain a hydroprocessed product oil, wherein the hydroprocessing stage reaction includes a hydrorefining reaction and a hydrocracking reaction, and the hydroprocessing catalyst includes a hydrorefining catalyst and a hydrocracking catalyst in 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 C N The value is less than 25%;

[0040] S2, the hydrotreated product oil obtained in step S1 is mixed with hydrogen and enters a hydroisomerization reactor, where it contacts an isodewaxing catalyst to undergo a hydroisomerization reaction to obtain a hydroisomerization product oil;

[0041] S3, mixing the hydroisomerized oil obtained in step S2 with hydrogen and entering the reactor for hydrorefining, contacting the reactor with a hydrorefining catalyst, causing a hydrorefining reaction to produce a three-stage hydrorefining oil, and then entering a normal vacuum distillation tower for vacuum fractionation to obtain a distillate having a boiling point higher than 320°C;

[0042] S4, mixing the distillate oil with a boiling point higher than 320° C. obtained in step S3 with hydrogen and entering the reactor for hydrogenation deep dearomatization, where a hydrogenation deep dearomatization catalyst is used to cause a hydrogenation deep aromatic saturation reaction to obtain a white oil specifically for SEBS thermoplastic elastomers.

[0043] In the present invention, paraffin-based distillate oil with an initial distillation point of 360°C to 390°C and an end distillation point of 460°C to 500°C is used as raw material, and a full hydrogen process is adopted. This not only solves the problems of solvent treatment difficulties 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 stage.

[0044] At the same time, the present invention adopts two catalyst gradations (hydrorefining and hydrocracking) instead of a single catalyst. By adjusting the gradation ratio of the two catalysts and controlling the reaction temperature difference, the problem of the original hydrogenation process being difficult to retain cycloparaffinic carbon can be effectively solved, and the product yield can be further improved.

[0045] Moreover, by controlling the reaction temperature difference in the hydroprocessing section, the problem of the original hydrogenation process being difficult to retain cycloparaffinic carbon can be effectively solved. After hydrorefining, fractionation is carried out and then deep hydrogenation is performed to saturate aromatics, ensuring that the oil product will not become unstable when heated in the distillation section.

[0046] In the present invention, the distillate oil has a high saturated hydrocarbon content and a high flash point. As a raw material for white oil special for SEBS-type thermoplastic elastomers, it has better advantages in ensuring the high flash point, low volatility and good light and heat stability of the product.

[0047] Example 2: As an optimization of the above example, in step S1, the reaction process conditions of the hydrotreating stage include: hydrogen partial pressure of 14 MPa to 20 MPa, hydrogen to oil volume ratio of 800 to 1200:1, hydrotreating reaction temperature of 342°C to 380°C, volume space velocity of 0.53 h -1 to 0.67h -1 , hydrocracking reaction temperature 340℃ to 370℃, volume space velocity 1.0h -1 to 1.6 hours -1 , and the hydrofining reaction temperature is 2°C to 10°C higher than the hydrocracking reaction temperature.

[0048] In the present invention, the hydrofining reaction temperature and the hydrocracking reaction temperature are controlled by injecting cold hydrogen.

[0049] Example 3: As an optimization of the above example, in step S2, the hydroisomerization reaction process conditions include: hydrogen partial pressure of 15MPa to 20MPa, reaction temperature of 310℃ to 350℃, volume space velocity of 0.5h -1 Up to 1.5 hours -1 , hydrogen-oil volume ratio 500 to 800:1.

[0050] Example 4: As an optimization of the above example, in step S3, the hydrogenation supplementary refining reaction process conditions include: hydrogen partial pressure of 15 MPa to 20 MPa, reaction temperature of 200°C to 240°C, volume space velocity of 0.8h-1 Up to 1.5 hours -1 , hydrogen-oil volume ratio 500 to 800:1.

[0051] Example 5: As an optimization of the above example, in step S4, the process conditions for the deep aromatic saturation reaction by hydrogenation include: a hydrogen partial pressure of 10 MPa to 20 MPa, a reaction temperature of 200°C to 240°C, a volume space velocity of 0.5 h -1 to 2.0h -1 , hydrogen-oil volume ratio 500 to 800:1.

[0052] Example 6: As an optimization of the above example, in step S1, the hydrorefining catalyst is supported by a composition of activated alumina and titanium oxide, the active metals in the hydrorefining catalyst are two or more of Ni, W, Co and Mo, and the active metal content accounts for 15% to 30% of the mass of the hydrorefining catalyst based on the mass of the active oxides. The hydrorefining catalyst needs to be pre-sulfurized in-situ before use.

[0053] Example 7: As an optimization of the above example, in step S1, the hydrocracking catalyst is supported by amorphous silica-alumina and one of β molecular sieve or Y molecular sieve, the active metal in the hydrocracking catalyst is two or more of W, Ni, Co and Mo, and the active metal content accounts for 10% to 20% of the mass of the hydrocracking catalyst based on the mass of active oxides. The hydrocracking catalyst needs to be pre-sulfurized in-situ before use.

[0054] Example 8: As an optimization of the above example, in step S2, the isodewaxing catalyst is based on at least one of the 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, and the active metal content 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.

[0055] Example 9: As an optimization of the above example, in step S3, the hydrorefining catalyst is supported by at least one of the molecular sieves ZSM-5 / ZSM-11 / ZSM-12, the active metal in the hydrorefining catalyst is one of Pt or Pd, and the active metal content accounts for 0.2% to 0.6% of the mass of the hydrorefining catalyst. The hydrorefining catalyst needs to be activated by low-pressure hydrogen reduction before use, and the hydrogen reduction pressure is 0.3 MPa to 1.0 MPa.

[0056] Example 10: As an optimization of the above example, in step S4, the deep hydrogenation dearomatization catalyst is supported by at least one of the molecular sieves ZSM-5 / ZSM-22 / ZSM-48, and the support accounts for 99.4% to 99.8% of the mass of the deep hydrogenation dearomatization catalyst. The active metal in the deep hydrogenation dearomatization catalyst is one of Pt or Pd, and the active metal content accounts for 0.2% to 0.6% of the mass of the deep hydrogenation dearomatization catalyst. The deep hydrogenation dearomatization catalyst needs to be activated by low-pressure hydrogen reduction before use, and the hydrogen reduction pressure is 0.3 MPa to 1.0 MPa.

[0057] Example 11: As an optimization of the above example, the physical and chemical properties of the white oil for SEBS thermoplastic elastomer include:

[0058] Measured by ASTM 2140, C A The value is 0;

[0059] Measured by ASTM 2140, C N The value is 30% to 35%;

[0060] Determined by Q / SY1440 method, UV stability +30;

[0061] Determined by Q / SY1439 method, thermal stability +30;

[0062] Measured by ASTM D92 method, the open flash point is greater than 215°C, the evaporation loss is less than 1.0%, and the yield of white oil special for SEBS-type thermoplastic elastomer is above 75%, and it has good compatibility with SEBS.

[0063] Example 12: The preparation method of the special white oil for SEBS type thermoplastic elastomers. The special white oil for SEBS type thermoplastic elastomers is obtained.

[0064] Example 13: Application of the white oil dedicated to SEBS-type thermoplastic elastomer in SEBS-type thermoplastic elastomer raw materials.

[0065] The white oil for SEBS thermoplastic elastomer obtained by the present invention has an appropriate cycloalkane content, C N The value is 30% to 35%, the yield is above 75%, it has good compatibility with SEBS, low volatility, high flash point, and is used in SEBS-type thermoplastic elastomer raw materials, which can effectively improve the physical properties of SEBS-type thermoplastic elastomer products.

[0066] Example 14: In the preparation method of the white oil for SEBS thermoplastic elastomer, paraffin-based distillate oil (with an initial boiling point of 360°C and an end boiling point of 460°C) is used as a raw material. The main properties of the raw material are shown in Table 1.

[0067] The raw materials are mixed with hydrogen and enter the hydroprocessing reactor for hydroprocessing reaction. The process conditions of the hydroprocessing reaction are shown in Table 2.

[0068] The loading ratio (mass ratio) of the hydrotreating section hydrorefining catalyst to the hydrocracking catalyst is 75:25. The active metals in the hydrorefining catalyst are Ni, Co, and Mo, with their oxides accounting for 15% by mass. The carrier of the hydrorefining catalyst is a combination of activated alumina and titanium oxide.

[0069] The active components of the hydrocracking catalyst are Ni and W, with the mass proportion of their oxides being 10%. The carrier of the hydrocracking catalyst is amorphous silica-alumina and beta molecular sieve.

[0070] The hydrotreated oil is mixed with hydrogen and fed into the hydroisomerization reactor. The hydroisomerization reaction process conditions are shown in Table 3.

[0071] The carriers of the isodewaxing catalyst are molecular sieves SAPO-11 and ZSM-22, and the active metals are Pt and Pd. The active metal accounts for 0.4% by mass, and the mass ratio of Pt:Pd is 3:1.

[0072] The hydroisomerized oil was subjected to a hydrorefining reaction. The process conditions of the hydrorefining reaction are shown in Table 4. The carrier of the hydrorefining catalyst was molecular sieve ZSM-5, and the active metal was Pt, with a mass ratio of 0.2%.

[0073] The obtained three-stage hydrogenation product oil was distilled, and the fraction with a distillation range greater than or equal to 320°C was cut. Finally, the component with a distillation range greater than 320°C was mixed with hydrogen and entered into a hydrodeep dearomatization reactor. The process conditions of the hydrodeep dearomatization reaction are shown in Table 5.

[0074] The carrier of the hydrogenation deep dearomatization catalyst is molecular sieve ZSM-5, and the active metal is Pd, which accounts for 0.2% by mass. The resulting oil is a white oil specially used for SEBS-type thermoplastic elastomers. Its main properties are shown in Table 6.

[0075] Example 15: In the preparation method of the white oil for SEBS thermoplastic elastomer, paraffin-based distillate oil (with an initial boiling point of 380°C and an end boiling point of 480°C) is used as the raw material. The main properties of the raw material are shown in Table 1.

[0076] The raw materials are mixed with hydrogen and enter the hydroprocessing reactor for hydroprocessing reaction. The process conditions of the hydroprocessing reaction are shown in Table 2.

[0077] The loading ratio (mass ratio) of the hydrotreating section hydrorefining catalyst to the hydrocracking catalyst is 72:28. The active metals in the hydrorefining catalyst are Ni, W, and Mo, with their oxides accounting for 20% by mass. The carrier of the hydrorefining catalyst is a combination of activated alumina and titanium oxide.

[0078] The active components of the hydrocracking catalyst are Ni and Mo, with their oxides accounting for 13% by mass. The carrier of the hydrocracking catalyst is amorphous silica-alumina and beta molecular sieve;

[0079] The hydrotreated oil is mixed with hydrogen and fed into the hydroisomerization reactor. The hydroisomerization reaction process conditions are shown in Table 3.

[0080] The carriers of the isodewaxing catalyst are molecular sieves SAPO-11 and ZSM-22, and the active metals are Pt and Pd. The active metal mass ratio is 0.6%, and the mass ratio of Pt:Pd is 3:1.

[0081] The hydroisomerized oil was subjected to a hydrorefining reaction. The process conditions of the hydrorefining reaction are shown in Table 4. The carrier of the hydrorefining catalyst was molecular sieve ZSM-5, and the active metal was Pt, with a mass ratio of 0.4%.

[0082] The obtained three-stage hydrogenation product oil was distilled, and the fraction with a distillation range greater than or equal to 320°C was cut. Finally, the component with a distillation range greater than 320°C was mixed with hydrogen and entered into a hydrodeep dearomatization reactor. The process conditions of the hydrodeep dearomatization reaction are shown in Table 5.

[0083] The carrier of the hydrogenation deep dearomatization catalyst is molecular sieve ZSM-5, and the active metal is Pd, which accounts for 0.3% by mass. The resulting oil is a white oil specially used for SEBS-type thermoplastic elastomers. Its main properties are shown in Table 6.

[0084] Example 16: In the preparation method of the white oil for SEBS thermoplastic elastomer, paraffin-based distillate oil (with an initial boiling point of 390°C and an end boiling point of 490°C) is used as the raw material. The main properties of the raw material are shown in Table 1.

[0085] The raw materials are mixed with hydrogen and enter the hydroprocessing reactor for hydroprocessing reaction. The process conditions of the hydroprocessing reaction are shown in Table 2.

[0086] The loading ratio (mass ratio) of the hydrotreating section hydrorefining catalyst to the hydrocracking catalyst is 70:30. The active metals in the hydrorefining catalyst are Ni, W, and Co, with their oxides accounting for 30% by mass. The carrier of the hydrorefining catalyst is a combination of activated alumina and titanium oxide.

[0087] The active components of the hydrocracking catalyst are Ni, Co, and W, with the oxides accounting for 15% by mass. The carrier of the hydrocracking catalyst is amorphous silica-alumina and Y-type molecular sieve;

[0088] The hydrotreated oil is mixed with hydrogen and fed into the hydroisomerization reactor. The hydroisomerization reaction process conditions are shown in Table 3.

[0089] The carriers of the isodewaxing catalyst are molecular sieves SAPO-11 and ZSM-48, and the active metals are Pt and Pd. The mass proportion of active metals is 0.8%, and the mass ratio of Pt:Pd is 2:1.

[0090] The hydroisomerized oil was subjected to a hydrorefining reaction. The process conditions of the hydrorefining reaction are shown in Table 4. The carrier of the hydrorefining catalyst was molecular sieve ZSM-11, and the active metal was Pt, with a mass ratio of 0.6%.

[0091] The obtained three-stage hydrogenation product oil was distilled, and the fraction with a distillation range greater than or equal to 320°C was cut. Finally, the component with a distillation range greater than 320°C was mixed with hydrogen and entered into a hydrodeep dearomatization reactor. The process conditions of the hydrodeep dearomatization reaction are shown in Table 5.

[0092] The carrier of the hydrogenation deep dearomatization catalyst is molecular sieve ZSM-22, and the active metal is Pd, which accounts for 0.4% by mass. The resulting oil is a white oil specially used for SEBS-type thermoplastic elastomers. Its main properties are shown in Table 6.

[0093] Example 17: In the preparation method of the white oil for SEBS thermoplastic elastomer, paraffin-based distillate oil (with an initial boiling point of 390°C and an end boiling point of 500°C) is used as the raw material. The main properties of the raw material are shown in Table 1.

[0094] The raw materials are mixed with hydrogen and enter the hydroprocessing reactor for hydroprocessing reaction. The process conditions of the hydroprocessing reaction are shown in Table 2.

[0095] The loading ratio (mass ratio) of the hydrotreating section hydrorefining catalyst to the hydrocracking catalyst is 65:35. The active metals in the hydrorefining catalyst are Ni, Mo, and Co, with their oxides accounting for 20% by mass. The carrier of the hydrorefining catalyst is a combination of activated alumina and titanium oxide.

[0096] The active components of the hydrocracking catalyst are Ni and W, with the oxides accounting for 17% by mass. The carrier of the hydrocracking catalyst is amorphous silica-alumina and Y-type molecular sieve;

[0097] The hydrotreated oil is mixed with hydrogen and fed into the hydroisomerization reactor. The hydroisomerization reaction process conditions are shown in Table 3.

[0098] The carriers of the isodewaxing catalyst are molecular sieves SAPO-11 and molecular sieves ZSM-48, and the active metals are Pt and Pd. The mass proportion of the active metals is 1.0%, and the mass ratio of Pt:Pd is 2.5:1.

[0099] The hydroisomerized oil was subjected to a hydrorefining reaction. The process conditions of the hydrorefining reaction are shown in Table 4. The carrier of the hydrorefining catalyst was molecular sieve ZSM-12, and the active metal was Pt, with a mass ratio of 0.5%.

[0100] The obtained three-stage hydrogenation product oil was distilled, and the fraction with a distillation range greater than or equal to 320°C was cut. Finally, the component with a distillation range greater than 320°C was mixed with hydrogen and entered into a hydrodeep dearomatization reactor. The process conditions of the hydrodeep dearomatization reaction are shown in Table 5.

[0101] The carrier of the hydrogenation deep dearomatization catalyst is molecular sieve ZSM-48, and the active metal is Pd, which accounts for 0.5% by mass. The resulting oil is a white oil specially used for SEBS-type thermoplastic elastomers. Its main properties are shown in Table 6.

[0102] Example 18: In the preparation method of the white oil for SEBS thermoplastic elastomer, paraffin-based distillate oil (with an initial boiling point of 390°C and an end boiling point of 500°C) is used as a raw material. The main properties of the raw material are shown in Table 1.

[0103] The raw materials are mixed with hydrogen and enter the hydroprocessing reactor for hydroprocessing reaction. The process conditions of the hydroprocessing reaction are shown in Table 2.

[0104] The loading ratio (mass ratio) of the hydrotreating section hydrorefining catalyst to the hydrocracking catalyst is 60:40. The active metals in the hydrorefining catalyst are Ni, W, and Co, with their oxides accounting for 27% by mass. The carrier of the hydrorefining catalyst is a combination of activated alumina and titanium oxide.

[0105] The active components of the hydrocracking catalyst are Ni and Co, with the oxides accounting for 20% by mass. The carrier of the hydrocracking catalyst is amorphous silica-alumina and Y-type molecular sieve;

[0106] The hydrotreated oil is mixed with hydrogen and fed into the hydroisomerization reactor. The hydroisomerization reaction process conditions are shown in Table 3.

[0107] The carriers of the isodewaxing catalyst are molecular sieves SAPO-11 and ZSM-48, and the active metals are Pt and Pd. The mass proportion of the active metals is 1.0%, and the mass ratio of Pt:Pd is 3:1.

[0108] The hydroisomerized oil was subjected to a hydrorefining reaction. The process conditions of the hydrorefining reaction are shown in Table 4. The carrier of the hydrorefining catalyst is molecular sieve ZSM-5 and ZSM-12, and the active metal is Pt, with a mass ratio of 0.3%;

[0109] The obtained three-stage hydrogenation product oil was distilled, and the fraction with a distillation range greater than or equal to 320°C was cut. Finally, the component with a distillation range greater than 320°C was mixed with hydrogen and entered into a hydrodeep dearomatization reactor. The process conditions of the hydrodeep dearomatization reaction are shown in Table 5.

[0110] The carrier of the hydrogenation deep dearomatization catalyst is molecular sieve ZSM-5, and the active metal is Pd, which accounts for 0.6% by mass. The resulting oil is a white oil specially used for SEBS-type thermoplastic elastomers. Its main properties are shown in Table 6.

[0111] Comparative Example 1: Paraffin-based distillate oil (with an initial boiling point of 390°C and an end boiling point of 500°C) was used as a raw material. The main properties of the raw material are shown in Table 1. This raw material was mixed with hydrogen and introduced into a hydrotreating reactor for a hydrotreating reaction. The process conditions of the hydrotreating reaction are shown in Table 2.

[0112] The hydrotreated oil is mixed with hydrogen and fed into the hydroisomerization reactor. The hydroisomerization reaction process conditions are shown in Table 3.

[0113] The hydroisomerized oil is subjected to a hydrorefining reaction. The process conditions for the hydrorefining reaction are shown in Table 4.

[0114] The three-stage hydrogenation product oil obtained is distilled, and the fraction with a distillation range greater than or equal to 320°C is cut. Finally, the component with a distillation range greater than 320°C is mixed with hydrogen and enters the hydrogenation deep dearomatization reactor. The process conditions of the hydrogenation deep dearomatization reaction are shown in Table 5. The product oil obtained is a white oil specially used for SEBS thermoplastic elastomers. Its main properties are shown in Table 6.

[0115] Comparative Example 2: Furfural was refined from naphthenic distillate (with an initial boiling point of 325°C and an end boiling point of 485°C). The main properties of the feedstock are shown in Table 1. The mass ratio of furfural to feedstock was 1.2:1, and the extraction temperature was 80°C. After phase separation, a low-aromatic oil was obtained with a yield of 72%. The low-aromatic oil was then subjected to a series of hydrogenation reactions, followed by hydroisomerization, and hydrorefining. The three-stage hydrogenation conditions are shown in Tables 2 to 4. The fraction with a boiling range of 380°C to 480°C was collected as a white oil specifically for SEBS-based thermoplastic elastomers. The main properties are shown in Table 6.

[0116] The white oil specially prepared for SEBS-based thermoplastic elastomers of the present invention was used to prepare SEBS-based thermoplastic elastomer products. The changes in physical properties are shown in Table 7.

[0117] Among them, C NThe value can reflect the characteristics of cycloalkyl, suitable cycloalkyl characteristics (C N value) can effectively improve the tensile strength and elongation at break of the elastomers in Table 7, and has good compatibility with SEBS.

[0118] It can be seen from the data in Tables 3 to 7 that the white oil specially used for SEBS-based thermoplastic elastomers of the present invention has certain cycloalkyl characteristics, has good compatibility with SEBS, can be evenly dispersed in SEBS-based thermoplastic elastomers, and effectively improves the mechanical properties and appearance quality of the products.

[0119] Therefore, the special white oil for SEBS-type thermoplastic elastomers of the present invention has the characteristics of high flash point, low volatility, excellent light and heat stability, etc., which improves the stability and service life of the product. The product properties can also meet the index requirements of the cosmetic grade white oil standard NB / SH0007-2015. The preparation method has a simple and environmentally friendly production process, a high product yield, and a significant advantage in production efficiency compared with the existing methods, and is suitable for large-scale industrial production. At the same time, the SEBS-type thermoplastic elastomer products prepared using the special white oil for SEBS-type thermoplastic elastomers of the present invention have a tensile strength increase of 10% to 20%, an elongation at break increase of 15% to 25%, and a hardness reduction of 5HA to 10HA, which effectively improves the flexibility and elasticity of the products.

[0120] In summary, the SEBS-based thermoplastic elastomer-specific white oil of the present invention has a high flash point, a suitable hydrocarbon composition, good compatibility, excellent light stability and thermal stability, better meets the elasticity, oil-proof, processing and molding characteristics of rubber and plastic products, and has a high product yield and better economy.

[0121] The above technical features constitute the embodiments of the present invention, which have strong adaptability and implementation effect. Non-essential technical features can be added or removed according to actual needs to meet the requirements of different situations.

[0122] Table 1

[0123] .

[0124] Table 2

[0125] .

[0126] Table 3

[0127] .

[0128] Table 4

[0129] .

[0130] Table 5

[0131] .

[0132] Table 6

[0133] .

[0134] Table 7

[0135] .

Claims

1. A method for preparing a white oil for SEBS thermoplastic elastomer, characterized in that Follow the steps below: S1, paraffin-based distillate oil is mixed with hydrogen and enters a hydroprocessing reactor, contacts a hydroprocessing catalyst, and undergoes a hydroprocessing stage reaction to obtain a hydroprocessed product oil, wherein the hydroprocessing stage reaction includes a hydrorefining reaction and a hydrocracking reaction, and the hydroprocessing catalyst includes a hydrorefining catalyst and a hydrocracking catalyst in 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 C N The value is less than 25%. The reaction process conditions of the hydrotreating stage include: hydrogen partial pressure of 14MPa to 20MPa, hydrogen-to-oil volume ratio of 800 to 1200:1, hydrotreating reaction temperature of 342℃ to 380℃, volume space velocity of 0.53h -1 to 0.67h -1 , hydrocracking reaction temperature 340℃ to 370℃, volume space velocity 1.0h -1 to 1.6 hours -1 , and the hydrofining reaction temperature is 2°C to 10°C higher than the hydrocracking reaction temperature; S2, the hydrotreated product oil obtained in step S1 is mixed with hydrogen and enters the hydroisomerization reactor, contacts with the isomerization dewaxing catalyst, and undergoes a hydroisomerization reaction to obtain a hydroisomerized product oil. The hydroisomerization reaction process conditions include: hydrogen partial pressure of 15MPa to 20MPa, reaction temperature of 310°C to 350°C, volume space velocity of 0.5h -1 Up to 1.5 hours -1 , hydrogen-to-oil volume ratio 500 to 800:1; S3, mixing the hydroisomerized oil obtained in step S2 with hydrogen and entering the hydrorefining reactor, contacting the hydrorefining catalyst, and undergoing a hydrorefining reaction to obtain a three-stage hydrogenated oil, which is then fed into a normal vacuum distillation tower for vacuum fractionation to obtain a distillate with a boiling point higher than 320°C. The hydrorefining reaction process conditions include: a hydrogen partial pressure of 15 MPa to 20 MPa, a reaction temperature of 200°C to 240°C, and a volume space velocity of 0.8 h -1 Up to 1.5 hours -1 , hydrogen-to-oil volume ratio 500 to 800:1; S4, mixing the distillate oil with a boiling point higher than 320° C. obtained in step S3 with hydrogen and entering the reactor for hydrogenation deep dearomatization, and performing a hydrogenation deep aromatic saturation reaction under the action of a hydrogenation deep dearomatization catalyst to obtain a white oil specially used for SEBS thermoplastic elastomer. The process conditions for the hydrogenation deep aromatic saturation reaction include: a hydrogen partial pressure of 10 MPa to 20 MPa, a reaction temperature of 200° C. to 240° C., and a volume space velocity of 0.5 h -1 to 2.0h -1 , the hydrogen-to-oil volume ratio is 500 to 800:1, the deep hydrogenation dearomatization catalyst uses at least one of the molecular sieves ZSM-5 / ZSM-22 / ZSM-48 as a carrier, and the carrier accounts for 70% to 85% of the mass of the deep hydrogenation dearomatization catalyst; the active metal in the deep hydrogenation dearomatization catalyst is one of Pt or Pd, and the active metal content accounts for 0.2% to 0.6% of the mass of the deep hydrogenation dearomatization catalyst.

2. The method for preparing the white oil for SEBS thermoplastic elastomer according to claim 1, characterized in that In step S1, the hydrorefining catalyst uses an activated alumina and titanium oxide composition as a carrier, the active metals in the hydrorefining catalyst are two or more of Ni, W, Co and Mo, and the active metal content accounts for 15% to 30% of the mass of the hydrorefining catalyst based on the mass of the active oxide.

3. The method for preparing the white oil for SEBS thermoplastic elastomer according to claim 1 or 2, characterized in that In step S1, the hydrocracking catalyst is supported by amorphous silica-alumina and one of β molecular sieve or Y molecular sieve, and the active metal in the hydrocracking catalyst is two or more of W, Ni, Co and Mo. The active metal content is 10% to 20% of the mass of the hydrocracking catalyst based on the mass of the active oxide.

4. The method for preparing the white oil for SEBS thermoplastic elastomer according to claim 3, characterized in that In step S2, the isodewaxing catalyst is based on at least one of the 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, and the active metal content accounts for 0.4% to 1.0% of the mass of the isodewaxing catalyst.

5. The method for preparing the white oil for SEBS thermoplastic elastomer according to claim 1, 2 or 4, characterized in that In step S3, the hydrorefining catalyst is supported by at least one of the molecular sieves ZSM-5 / ZSM-11 / ZSM-12, the active metal in the hydrorefining catalyst is one of Pt and Pd, and the active metal content accounts for 0.2% to 0.6% of the mass of the hydrorefining catalyst.

6. The method for preparing the white oil for SEBS thermoplastic elastomer according to claim 5, characterized in that The physical and chemical properties of SEBS thermoplastic elastomer white oil include: Measured by ASTM 2140, C A The value is 0; Measured by ASTM 2140, C N The value is 30% to 35%; Determined by Q / SY1440 method, UV stability +30; Determined by Q / SY1439 method, thermal stability +30; The open flash point measured by ASTM D92 is greater than 215°C.

7. A white oil specially used for SEBS thermoplastic elastomer obtained according to the preparation method according to any one of claims 1 to 6.