Method for increasing content of naphthenic hydrocarbon in special white oil raw material for thermoplastic elastomer

Abstract

The invention relates to the technical field of petrochemical engineering, in particular to a method for increasing the content of cycloalkane in a white oil raw material special for a thermoplastic elastomer, which comprises the following steps: mixing paraffin-based distillate oil with hydrogen, feeding into a hydrofining reaction zone, carrying out contact reaction with a hydrofining catalyst, removing impurities, and carrying out aromatic hydrocarbon saturation to obtain hydrofined oil; mixing the hydrofined generated oil with hydrogen, feeding the mixture into a hydro-upgrading reaction zone, and carrying out a contact reaction with a hydro-upgrading catalyst to obtain hydro-upgrading generated oil; and carrying out atmospheric and vacuum distillation on the hydro-upgrading generated oil to obtain distillate oil with a boiling point higher than 420 DEG C. The preparation method disclosed by the invention is simple and environment-friendly in process and mild in reaction condition, the production efficiency of the product can be improved while the content of the cycloalkane is effectively improved, and the obtained special white oil raw material for the thermoplastic elastomer with the high content of the cycloalkane has a good application prospect in preparation of the elastomer white oil. Good compatibility with high polymer materials and safety performance in the processing process are guaranteed, and the use performance of rubber and plastic products is also guaranteed.

Description

Technical Field

[0001] The present invention relates to the technical field of petrochemical engineering, and is a method for increasing the naphthene content of a special white oil raw material for thermoplastic elastomers. Background Art

[0002] Lubricating oil base oil is a technical product with functions such as lubricity, auxiliary cooling, rust prevention, and cleaning. It is usually obtained by deeply processing crude oil fractions or waste lubricating oil to remove impurities and improve performance, and its quality directly affects the final performance and use effect of lubricating oil. The special white oil for thermoplastic elastomers is a colorless and transparent oily liquid with a suitable hydrocarbon structure and good compatibility with SEBS, which is prepared by multi-stage hydrogenation of a suitable fraction oil obtained by petroleum fractionation. It has excellent physical properties such as high flash point, good ultraviolet light stability, and thermal stability. The special white oil for thermoplastic elastomers is an important additive in the elastomer processing process, which can improve the processing performance, flexibility, and aging resistance of elastomers. The naphthene content is a key index affecting the performance of white oil. White oil with a high naphthene value has better compatibility with elastomers and can significantly improve the flexibility and low-temperature performance of thermoplastic elastomers. However, in the traditional white oil production process, the naphthene content is relatively low, making it difficult to meet the requirements of high-end elastomer processing. In the prior art, naphthenic fraction oil is the main raw material for preparing high-C N value white oil, but it has a low flash point and large evaporation loss, which cannot meet the safety operation during elastomer processing and the performance stability of rubber and plastic products. Using paraffin-based fraction oil can solve the problems of low flash point and large evaporation loss, but the products produced by the existing process have a low naphthene content. Therefore, in order to ensure the naphthene content of the product and also have the advantages of high flash point and low evaporation loss, it is of great significance to develop a method for increasing the naphthene content using paraffin-based fraction oil as the raw material.

[0003] Thermoplastic elastomer (TPE) is a polymer material with characteristics between rubber and thermoplastic plastics, having the dual properties and broad characteristics of rubber and plastic. It has high elasticity of rubber at room temperature, shows the high elasticity of vulcanized rubber at room temperature, and is easy to process and form like thermoplastic plastics at high temperatures, and is a polymer material with the characteristics of both vulcanized rubber and thermoplastic plastics.

[0004] The Chinese patent document with the authorization announcement number CN102021032B discloses a naphthenic base filling oil for soft rubber toys and its preparation method. The naphthenic base crude oil is cut by atmospheric and vacuum distillation to obtain a fraction oil with an acid value less than 0.5mgKOH / g and a distillation range of 350°C to 500°C. The fraction oil is subjected to hydrotreating. The catalyst is a bifunctional catalyst containing molecular sieve with Al2O3 as the carrier and adding active nickel-tungsten or cobalt-molybdenum components to obtain a hydrotreated component with a distillation range of 300 to 400°C; the hydrotreated component is subjected to solvent refining with a solvent ratio of 1:1 to 2:1 and an extraction temperature of 45°C to 70°C to obtain a raffinate oil; the raffinate oil is further subjected to hydrofinishing with a refining catalyst using a nickel-tungsten or nickel-molybdenum system as the active component and Al2O3 as the carrier; a naphthenic base filling oil with a polycyclic aromatic hydrocarbon content less than 0.5%, a Saybolt color greater than +30, a thermal stability Saybolt color greater than +20, and an open flash point greater than 160°C is obtained. However, the furfural refining extraction tower has poor selectivity, the aromatic hydrocarbon content of 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 is impossible to produce white oil. Moreover, the aromatic hydrocarbons and naphthenes in the oil affect the physical and chemical properties, mechanical properties, and yellowing resistance of SEBS rubber products.

[0005] The Chinese patent document with the publication number CN117304976A discloses a special naphthenic base white oil for SEBS and its preparation method. The special naphthenic base white oil for SEBS is obtained by the following method: using naphthenic base fraction oil as the feedstock, after centrifugal extraction of the feedstock and the extraction solvent together, the aromatic hydrocarbons and polar compounds in the feedstock are removed to obtain a low-aromatic hydrocarbon oil; the low-aromatic hydrocarbon oil is subjected to hydrotreating to obtain a hydrotreated product oil; the hydrotreated product oil is subjected to isomerization and dewaxing to obtain an isomerization and dewaxing product oil; the obtained isomerization and dewaxing product oil is subjected to hydrofinishing to obtain a hydrofinished product oil; the fraction of 300°C to 500°C is collected to obtain the special naphthenic base white oil product for SEBS. The special naphthenic base white oil prepared by it has a high viscosity index and a certain naphthene content, and can be used as a rubber softening filling oil for special SEBS products. However, the method uses naphthenic base feedstock oil with a low flash point of the feedstock itself, and the prepared white oil product has high volatility, which is not conducive to the stability and service life of the product. And this technology has not undergone a deep de-aromatization process, and the storage stability of the white oil is poor.

[0006] It can be seen that the above methods all use naphthenic base fraction oil as the raw material and adopt a combination process of solvent refining and hydrogenation, and the obtained white oil has poor physical and chemical properties, mechanical properties, and stability. Therefore, it is necessary to develop a new method to increase the naphthene content of the raw material for the special white oil of thermoplastic elastomer. Summary of the Invention

[0007] The present invention provides a method for increasing the naphthene content of the special white oil raw material for thermoplastic elastomers, overcoming the deficiencies of the above-mentioned prior art, and effectively solving the problems of poor physical and chemical properties, mechanical properties and stability of the white oil obtained from the naphthenic fraction oil as the raw material oil, as well as high volatility, low product yield and complex production process of the white oil product.

[0008] The technical solution of the present invention is achieved by the following measures: A method for increasing the naphthene content of the special white oil raw material for thermoplastic elastomers is carried out according to the following steps: S1, Mix the paraffin-based fraction oil with hydrogen and enter the hydrofining reaction zone, contact and react with the hydrofining catalyst to remove impurities and carry out aromatics saturation to obtain the hydrofined product oil. Among them, the distillation range of the paraffin-based fraction oil is 360°C to 530°C, the density is 860 kg / m 3 to 875 kg / m 3 , the total naphthene content is 40% to 50%, and the C N value is less than 25%; S2, Mix the hydrofined product oil with hydrogen and enter the hydro-upgrading reaction zone, contact and react with the hydro-upgrading catalyst to obtain the hydro-upgraded product oil; S3, Subject the hydro-upgraded product oil to atmospheric and vacuum distillation to obtain a fraction oil with a boiling point higher than 420°C, which is the special white oil raw material for thermoplastic elastomers with a high naphthene content.

[0009] The following is a further optimization or / and improvement of one of the above-mentioned technical solutions of the invention: In the above step S1, the hydrofining catalyst is loaded in the upper part of the reactor bed; in step S2, the hydro-upgrading catalyst is loaded in the lower part of the reactor bed.

[0010] In the above step S1, the hydrofining catalyst uses a combination of activated alumina and titanium oxide as the carrier, and the active metal components in the hydrofining catalyst are at least one of W, Co, Mo and Ni. The content of the active metal components accounts for 15% to 30% of the mass of the hydrofining catalyst in terms of the mass of the oxide. Among them, the mass of nickel oxide in the oxide is 8% to 12%.

[0011] In the above step S1, the process conditions in the hydrofining reaction zone include: hydrogen partial pressure of 14 MPa to 20 MPa, hydrogen-oil volume ratio of 800 to 1200:1, hydrofining reaction temperature of 342°C to 380°C, and volume space velocity of 0.53 h -1 to 0.67 h -1 .

[0012] In the above step S2, the hydro-upgrading catalyst uses one of amorphous silica-alumina and β-zeolite or Y-zeolite as the carrier. The active metal components in the hydro-upgrading catalyst are at least two of W, Ni, Co, and Mo, and the content of the active metal components accounts for 15% to 30% of the mass of the catalyst in terms of the mass of the oxide.

[0013] In the above step S2, the process conditions in the hydro-upgrading reaction zone include: hydrogen partial pressure of 14 MPa to 20 MPa, hydrogen-oil volume ratio of 800 to 1200:1, reaction temperature for hydro-upgrading of 340 °C to 370 °C, and volume space velocity of 1.0 h -1 to 1.6 h -1 .

[0014] In the above steps S1 and S2, the loading mass ratio of the hydrofining catalyst to the hydro-upgrading catalyst is 75% to 60%: 25% to 40%, and the hydrofining reaction temperature is 2 °C to 10 °C higher than the hydro-upgrading reaction temperature.

[0015] In the above step S3, in the special white oil raw material for thermoplastic elastomer with high naphthene content obtained, the naphthene content is 65% to 75%, the open flash point is greater than 215 °C, the sulfur content is less than 2 μg / g, the nitrogen content is less than 2 μg / g, and the yield of the prepared elastomer white oil is greater than 80%.

[0016] The preparation method of the present invention has a simple and environmentally friendly process and mild reaction conditions. It can effectively increase the naphthene content while improving the production efficiency of the product. Moreover, when the special white oil raw material for thermoplastic elastomer with high naphthene content obtained is used to prepare elastomer white oil, it ensures both good compatibility with polymer materials and safety performance during the processing, and the service performance of rubber and plastic products. Detailed Embodiments

[0017] The present invention is not limited by the following embodiments, and specific implementation manners can be determined according to the technical solutions of the present invention and actual situations. 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; the percentages in the present invention are mass percentages unless otherwise specified; the solutions in the present invention are aqueous solutions with water as the solvent unless otherwise specified. For example, hydrochloric acid solution is hydrochloric acid aqueous solution; normal temperature and room temperature in the present invention generally refer to the temperature of 15 °C to 25 °C, and are generally defined as 25 °C.

[0018] The present invention will be further described below in conjunction with embodiments: Example 1: The method for increasing the naphthene content of the special white oil raw material for thermoplastic elastomer is carried out according to the following steps: S1. Mix the paraffinic base distillate oil with hydrogen and introduce it into the hydrofining reaction zone. Contact and react with the hydrofining catalyst to remove impurities and carry out aromatic saturation to obtain the hydrofined product oil. Among them, the distillation range of the paraffinic base distillate oil is 360°C to 530°C, the density is 860 kg / m 3 to 875 kg / m 3 , the total naphthene content is 40% to 50%, and the C N value is less than 25%; S2. Mix the hydrofined product oil with hydrogen and introduce it into the hydro-upgrading reaction zone. Contact and react with the hydro-upgrading catalyst to obtain the hydro-upgraded product oil; S3. Subject the hydro-upgraded product oil to atmospheric and vacuum distillation to obtain a distillate oil with a boiling point higher than 420°C, which is the special white oil raw material for thermoplastic elastomers with a high naphthene content.

[0019] The present invention uses paraffinic base distillate oil as the raw material, and through hydrofining reaction and hydro-upgrading reaction, prepares the special white oil raw material for thermoplastic elastomers with a high naphthene content. This raw material has the remarkable advantages of high naphthene content, low volatility, high flash point and excellent compatibility.

[0020] Among them, high naphthene content: Through hydrofining reaction and hydro-upgrading reaction, the hydrotreating process is optimized, and the naphthene content in the raw material is significantly increased, thereby enhancing the compatibility between the white oil and the polymer material, and contributing to improving the physical properties of elastomer products, such as tensile strength, wear resistance and flexibility, etc.

[0021] Low volatility: After the raw material is hydrotreated, the volatility is significantly reduced, ensuring the stability of the white oil during high-temperature or long-term use, reducing the volatilization loss, and extending the service life of the product.

[0022] High flash point: Through hydrotreating of the paraffinic base distillate oil, the flash point of the raw material is significantly increased, improving the safety of the white oil and reducing the fire risk during storage and use.

[0023] Excellent compatibility: The white oil prepared with this raw material has good compatibility with a variety of polymer materials, and can effectively improve the processing performance of elastomer products and the physical properties of the final products.

[0024] In the present invention, the distillate oil with a distillation range of 360°C to 530°C and a density of 860 kg / m 3 to 875 kg / m 3 has the characteristics of high flash point and low volatile matter, is suitable for being used as the raw material of the special white oil for thermoplastic elastomers, and has better advantages for ensuring the flash point, low volatility and photothermal stability of the product.

[0025] Example 2: As an optimization of the above example, in step S1, the hydrofining catalyst is loaded in the upper part of the reactor bed; in step S2, the hydro-upgrading catalyst is loaded in the lower part of the reactor bed.

[0026] Example 3: As an optimization of the above example, in step S1, the hydrofining catalyst uses a composite of activated alumina and titanium oxide as the carrier, and the active metal components in the hydrofining catalyst are at least one of W, Co, and Mo and Ni. The content of the active metal components accounts for 15% to 30% of the mass of the hydrofining catalyst in terms of the mass of the oxides, wherein the mass of nickel oxide in the oxides is 8% to 12%. As needed, this hydrofining catalyst needs to be pretreated by in-situ sulfidation before use.

[0027] Example 4: As an optimization of the above example, in step S1, the process conditions in the hydrofining reaction zone include: hydrogen partial pressure of 14 MPa to 20 MPa, hydrogen-oil volume ratio of 800 to 1200:1, hydrofining reaction temperature of 342 °C to 380 °C, and volume space velocity of 0.53 h -1 to 0.67 h -1 .

[0028] Example 5: As an optimization of the above example, in step S2, the hydro-upgrading catalyst uses one of amorphous silica-alumina and β-zeolite or Y-zeolite as the carrier, and the active metal components in the hydro-upgrading catalyst are at least two of W, Ni, Co, and Mo. The content of the active metal components accounts for 15% to 30% of the mass of the catalyst in terms of the mass of the oxides. As needed, this hydrofining catalyst needs to be pretreated by in-situ sulfidation before use.

[0029] Example 6: As an optimization of the above example, in step S2, the process conditions in the hydro-upgrading reaction zone include: hydrogen partial pressure of 14 MPa to 20 MPa, hydrogen-oil volume ratio of 800 to 1200:1, hydro-upgrading reaction temperature of 340 °C to 370 °C, and volume space velocity of 1.0 h -1 to 1.6 h -1 .

[0030] Example 7: As an optimization of the above example, in steps S1 and S2, the loading mass ratio of the hydrofining catalyst to the hydro-upgrading catalyst is 75% to 60%: 25% to 40%, and the hydrofining reaction temperature is 2 °C to 10 °C higher than the hydro-upgrading reaction temperature.

[0031] Example 8: As an optimization of the above example, in step S3, in the special white oil raw material for thermoplastic elastomer with a high naphthene content obtained, the naphthene content is 65% to 75%, the open flash point is greater than 215 °C, the sulfur content is less than 2 μg / g, the nitrogen content is less than 2 μg / g, and the yield of the prepared elastomer white oil is greater than 80%.

[0032] Example 9: The method for increasing the naphthene content of the special white oil raw material for thermoplastic elastomers obtains the special white oil raw material for thermoplastic elastomers with a high naphthene content. The specific method is as follows: Using the paraffin-based distillate oil with a distillation range of 360°C to 460°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 hydrofining reaction zone, where it contacts and reacts with the hydrofining catalyst. The hydrofining reaction conditions are shown in Table 2; the hydrofined product oil enters the hydro-upgrading reaction zone, where it contacts and reacts with the hydro-upgrading catalyst. The hydro-upgrading reaction conditions are shown in Table 3; among them, the loading ratio (mass ratio) of the hydrofining catalyst to the hydro-upgrading catalyst is 75:25; the hydrofining catalyst uses a combination of activated alumina and titanium oxide as the carrier, and the active metal of the hydrofining catalyst is Ni-Co-Mo, and the mass ratio of its oxide is 18%; the hydro-upgrading catalyst uses amorphous silica-alumina and β-zeolite as the carrier, and the active component of the hydro-upgrading catalyst is Ni-W, and the mass ratio of its oxide is 15%. The obtained hydro-upgraded product oil undergoes atmospheric and vacuum distillation, and the fraction with a temperature higher than 420°C is collected as the special white oil raw material for thermoplastic elastomers with a high naphthene content, and the main properties are shown in Table 4.

[0033] Example 10: The method for increasing the naphthene content of the special white oil raw material for thermoplastic elastomers obtains the special white oil raw material for thermoplastic elastomers with a high naphthene content. The specific method is as follows: Using the paraffin-based distillate oil with a distillation range of 360°C to 460°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 hydrofining reaction zone, where it contacts and reacts with the hydrofining catalyst. The hydrofining reaction conditions are shown in Table 2; the hydrofined product oil enters the hydro-upgrading reaction zone, where it contacts and reacts with the hydro-upgrading catalyst. The hydro-upgrading reaction conditions are shown in Table 3; among them, the loading ratio (mass ratio) of the hydrofining catalyst to the hydro-upgrading catalyst is 73:27; the hydrofining catalyst uses a combination of activated alumina and titanium oxide as the carrier, and the active metal of the hydrofining catalyst is Ni-W-Mo, and the mass ratio of its oxide is 15%; the hydro-upgrading catalyst uses amorphous silica-alumina and β-zeolite as the carrier, and the active component of the hydro-upgrading catalyst is Ni-Mo, and the mass ratio of its oxide is 15%. The obtained hydro-upgraded product oil undergoes atmospheric and vacuum distillation, and the fraction with a temperature higher than 420°C is collected as the special white oil raw material for thermoplastic elastomers with a high naphthene content, and the main properties are shown in Table 4.

[0034] Example 11: The method for increasing the naphthene content of the special white oil raw material for thermoplastic elastomers obtains the special white oil raw material for thermoplastic elastomers with a high naphthene content. The specific method is as follows: Using paraffin-based distillate oil with a boiling range of 360°C to 460°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 hydrofining reaction zone, where it contacts and reacts with the hydrofining catalyst. The hydrofining reaction conditions are shown in Table 2; the hydrofined product oil enters the hydro-upgrading reaction zone, where it contacts and reacts with the hydro-upgrading catalyst. The hydro-upgrading reaction conditions are shown in Table 3; among them, the filling ratio (mass ratio) of the hydrofining catalyst to the hydro-upgrading catalyst is 70:30; the hydrofining catalyst uses a combination of activated alumina and titanium oxide as the carrier, and the active metals of the hydrofining catalyst are Ni-W-Co, and the mass ratio of their oxides is 25%; the hydro-upgrading catalyst uses amorphous silica-alumina and beta zeolite as the carrier, and the active components of the hydro-upgrading catalyst are Ni-Co-W, and the mass ratio of their oxides is 18%. The obtained hydro-upgraded product oil is subjected to atmospheric and vacuum distillation, and the fraction with a temperature higher than 420°C is collected as the special white oil raw material for thermoplastic elastomers with a high naphthene content, and the main properties are shown in Table 4.

[0035] Example 12: The method for increasing the naphthene content of the special white oil raw material for thermoplastic elastomers obtains the special white oil raw material for thermoplastic elastomers with a high naphthene content. The specific method is as follows: Using paraffin-based distillate oil with a boiling range of 390°C to 530°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 hydrofining reaction zone, where it contacts and reacts with the hydrofining catalyst. The hydrofining reaction conditions are shown in Table 2; the hydrofined product oil enters the hydro-upgrading reaction zone, where it contacts and reacts with the hydro-upgrading catalyst. The hydro-upgrading reaction conditions are shown in Table 3; among them, the filling ratio (mass ratio) of the hydrofining catalyst to the hydro-upgrading catalyst is 65:35; the hydrofining catalyst uses a combination of activated alumina and titanium oxide as the carrier, and the active metals of the hydrofining catalyst are Ni-Mo-Co, and the mass ratio of their oxides is 18%; the hydro-upgrading catalyst uses amorphous silica-alumina and Y-type zeolite as the carrier, and the active components of the hydro-upgrading catalyst are Ni-W, and the mass ratio of their oxides is 17%. The obtained hydro-upgraded product oil is subjected to atmospheric and vacuum distillation, and the fraction with a temperature higher than 420°C is collected as the special white oil raw material for thermoplastic elastomers with a high naphthene content, and the main properties are shown in Table 4.

[0036] Example 13: The method for increasing the naphthene content of the special white oil raw material for thermoplastic elastomers obtains the special white oil raw material for thermoplastic elastomers with a high naphthene content. The specific method is as follows: Using paraffin-based distillate oil with a boiling range of 390°C to 530°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 hydrofining reaction zone, where it contacts and reacts with the hydrofining catalyst. The hydrofining reaction conditions are shown in Table 2; the hydrofined product oil enters the hydro-upgrading reaction zone, where it contacts and reacts with the hydro-upgrading catalyst. The hydro-upgrading reaction conditions are shown in Table 3; among them, the filling ratio (mass ratio) of the hydrofining catalyst to the hydro-upgrading catalyst is 60:40; the hydrofining catalyst uses a combination of activated alumina and titanium oxide as the carrier, and the active metals of the hydrofining catalyst are Ni-W-Co, and the mass ratio of their oxides is 30%; the hydro-upgrading catalyst uses amorphous silica-alumina and Y-type molecular sieve as the carrier, and the active components of the hydro-upgrading catalyst are Ni-Co, and the mass ratio of their oxides is 20%. The obtained hydro-upgraded product oil is subjected to atmospheric and vacuum distillation, and the fraction with a temperature higher than 420°C is collected as the special white oil raw material for thermoplastic elastomer with a high naphthene content. The main properties are shown in Table 4.

[0037] Comparative Example 1: Using paraffin-based distillate oil with a boiling range of 360°C to 460°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 reaction zone, where it contacts and reacts with the hydrotreating catalyst. The hydrotreating conditions are shown in Table 2; the active metals of the hydrotreating catalyst are Ni-W-Mo, and the mass ratio of their oxides is 23%. The obtained product oil is subjected to atmospheric and vacuum distillation, and the fraction with a temperature higher than 420°C is collected as the white oil raw material. The main properties are shown in Table 4.

[0038] It can be seen from the data in Tables 2 to 4 that: compared with Comparative Example 1 (using one catalyst), the special white oil raw material for thermoplastic elastomer with a high naphthene content obtained by the method for increasing the naphthene content of the special white oil for thermoplastic elastomer in the present invention (using the grading of two catalysts) has characteristics such as a high naphthene content, a high flash point, and low volatility, which is more conducive to the preparation of excellent special white oil for elastomers.

[0039] In summary, the preparation method of the present invention has a simple and environmentally friendly process and mild reaction conditions. It can effectively increase the naphthene content while improving the production efficiency of the product. Moreover, the special white oil raw material for thermoplastic elastomer with a high naphthene content obtained ensures good compatibility with polymer materials and safety performance during the processing, as well as the service performance of rubber and plastic products when preparing elastomer white oil, and is suitable for large-scale industrial production.

[0040] The above technical features constitute the embodiments of the present invention, which have strong adaptability and implementation effects. Non-essential technical features can be increased or decreased according to actual needs to meet the requirements of different situations.

[0041] Table 1 。

[0042] Table 2 .

[0043] Table 3 .

[0044] Table 4 .

Claims

1. A method for increasing the naphthene content of the special white oil raw material for thermoplastic elastomers, characterized in that Proceed as follows: S1. Mix the paraffinic base distillate oil with hydrogen and introduce it into the hydrofining reaction zone. Contact and react with the hydrofining catalyst to remove impurities and carry out aromatic saturation to obtain the hydrofined product oil. Among them, the distillation range of the paraffinic base distillate oil is 360°C to 530°C, and the density is 860 kg / m 3 to 875 kg / m 3 , the total naphthene content is 40% to 50%, and the C N value is less than 25%; S2. Mix the hydrofined product oil with hydrogen and introduce it into the hydro-upgrading reaction zone to contact with the hydro-upgrading catalyst for reaction to obtain the hydro-upgraded product oil; S3. Subject the hydro-upgraded product oil to atmospheric and vacuum distillation to obtain a fraction oil with a boiling point higher than 420 °C, which is the special white oil raw material for thermoplastic elastomers with a high naphthene content.

2. The method for increasing the naphthene content of the white oil raw material special for thermoplastic elastomers according to claim 1, characterized in that In step S1, the hydrofining catalyst uses a combination of activated alumina and titanium oxide as the carrier. The active metal components in the hydrofining catalyst are at least one of W, Co, and Mo and Ni. The content of the active metal components accounts for 15% to 30% of the mass of the hydrofining catalyst based on the mass of the oxides, wherein the mass of nickel oxide in the oxides is 8% to 12%.

3. The method for increasing the naphthene content of the white oil raw material special for thermoplastic elastomers according to claim 1 or 2, characterized in that In step S1, the hydrofining catalyst is loaded in the upper part of the reactor bed; in step S2, the hydro-upgrading catalyst is loaded in the lower part of the reactor bed.

4. The method for increasing the naphthene content of the white oil raw material special for thermoplastic elastomers according to claim 1 or 2, characterized in that In step S1, the process conditions in the hydrofining reaction zone include: hydrogen partial pressure of 14 MPa to 20 MPa, hydrogen-oil volume ratio of 800 to 1200:1, hydrofining reaction temperature of 342 °C to 380 °C, and volume space velocity of 0.53 h -1 to 0.67 h -1 .

5. The method for increasing the naphthene content of the special white oil raw material for thermoplastic elastomers according to claim 3, characterized in that In step S1, the process conditions in the hydrofining reaction zone include: hydrogen partial pressure of 14 MPa to 20 MPa, hydrogen-oil volume ratio of 800 to 1200:1, hydrofining reaction temperature of 342 °C to 380 °C, and volume space velocity of 0.53 h -1 to 0.67 h -1 .

6. The method for increasing the naphthene content of the special white oil raw material for thermoplastic elastomers according to claim 1 or 2 or 5, characterized in that In step S2, the hydro-upgrading catalyst uses amorphous silica-alumina and one of β-zeolite or Y-zeolite as the carrier. The active metal components in the hydro-upgrading catalyst are at least two of W, Ni, Co, and Mo. The content of the active metal components accounts for 15% to 30% of the mass of the catalyst based on the mass of the oxides.

7. The method for increasing the naphthene content of the special white oil raw material for thermoplastic elastomers according to claim 4, wherein In step S2, the hydro-upgrading catalyst uses amorphous silica-alumina and one of β-zeolite or Y-zeolite as the carrier. The active metal components in the hydro-upgrading catalyst are at least two of W, Ni, Co, and Mo. The content of the active metal components accounts for 15% to 30% of the mass of the catalyst based on the mass of the oxides.

8. The method for increasing the naphthene content of the special white oil raw material for thermoplastic elastomers according to claim 1 or 2 or 5 or 7, characterized in that In step S2, the process conditions in the hydro-upgrading reaction zone include: hydrogen partial pressure of 14 MPa to 20 MPa, hydrogen-oil volume ratio of 800 to 1200:1, hydro-upgrading reaction temperature of 340 °C to 370 °C, and volume space velocity of 1.0 h -1 to 1.6 h -1 .

9. The method for increasing the naphthene content of the special white oil raw material for thermoplastic elastomers according to claim 6, characterized in that In step S2, the process conditions in the hydro-upgrading reaction zone include: hydrogen partial pressure of 14 MPa to 20 MPa, hydrogen-oil volume ratio of 800 to 1200:1, hydro-upgrading reaction temperature of 340°C to 370°C, and volume space velocity of 1.0 h -1 to 1.6 h -1 .

10. The method for increasing the naphthene content of the white oil raw material special for thermoplastic elastomers according to claim 1 or 2 or 5 or 7 or 9, characterized in that In steps S1 and S2, the loading mass ratio of the hydrofining catalyst to the hydro-upgrading catalyst is 75% to 60%: 25% to 40%, and the hydrofining reaction temperature is 2 °C to 10 °C higher than the hydro-upgrading reaction temperature.

11. The method for increasing the naphthene content of the special white oil raw material for thermoplastic elastomers according to claim 1 or 2 or 5 or 7 or 9, characterized in that In step S3, in the special white oil raw material for thermoplastic elastomers with a high naphthene content obtained, the naphthene content is 65% to 75%, the open flash point is greater than 215 °C, the sulfur content is less than 2 μg / g, the nitrogen content is less than 2 μg / g, and the yield of the prepared elastomer white oil is greater than 80%.