Preparation method of high-aromatic-hydrocarbon environment-friendly tire oil

Abstract

The invention is suitable for the technical field of tire rubber oil preparation, and provides a preparation method of high-aromatic-hydrocarbon environment-friendly tire oil, which comprises the following steps of: firstly, preparing high-aromatic-hydrocarbon naphthenic base oil by using naphthenic heavy oil vacuum distillate oil as a raw material through a hydrotreating process or a solvent refining combined process; heavy oil catalytic cracking oil slurry, naphthenic heavy oil vacuum residue or propane deoiled asphalt subjected to solid removal treatment are used as raw materials, and molecular distillation topping treatment is performed to obtain heavy component oil with low saturated hydrocarbon content; and finally, blending the high-aromatic-hydrocarbon naphthenic base oil with the heavy component oil which is subjected to molecular distillation topping treatment and has low saturated hydrocarbon content according to a specific mass ratio to obtain the high-aromatic-hydrocarbon-content tire rubber oil. By optimizing raw material selection and process parameters, the prepared product not only meets the requirements of environmental protection laws and regulations, but also has the characteristics of high aromatic hydrocarbon content and good compatibility with rubber, and can replace TDAE type environment-friendly tire oil which is commonly used at present.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of tire rubber oil preparation, and particularly relates to a high-aromatics environment-friendly tire oil preparation method. BACKGROUND

[0002] China is a large country in the world in terms of tire production, but with the implementation of the EU's “Ban on the Use of Toxic Plasticizers Containing Excessive Polycyclic Aromatic Hydrocarbons in Tire Production”, toxic plasticizers are completely prohibited in tire production, and environment-friendly tire rubber oil (benzo(a)pyrene content is not more than 1 mg / kg, and the content of eight specific aromatic hydrocarbons (benzo(a)pyrene, benzo(e)pyrene, benzo(a)anthracene, diphenyl anthracene, benzo(b)fluoranthene, benzo(j)fluoranthene, benzo(k)fluoranthene and chrysene) is not more than 10 mg / kg) is used, and the traditional high-cost lubricating oil solvent refined extracted oil (DAE) cannot meet the requirement due to the high content of polycyclic aromatic hydrocarbons, so that part of the tires exported to foreign countries must use environment-friendly tire rubber oil to survive in the market.

[0003] At present, there are mainly the following four kinds of environment-friendly tire rubber oil on the market: 1. the polycyclic aromatic hydrocarbon content of environment-friendly tire rubber oil (TDAE) obtained by twice solvent refining of extracted oil (DAE), 2. high-viscosity environment-friendly tire rubber oil (RAE) obtained by twice solvent refining of solvent deasphalted oil, 3. tire rubber oil (MES) with a polycyclic aromatic hydrocarbon content meeting the requirement obtained by shallow refining of paraffin-based or intermediate-based vacuum distillate oil, and 4. naphthenic-based tire rubber oil (NAP) with a polycyclic aromatic hydrocarbon content meeting the requirement obtained by shallow refining of naphthenic-based vacuum distillate oil. A Among them, TDAE and RAE have high aromatic content (C A value < 16%) in the carbon type composition, and the wet skid resistance of the filled rubber is insufficient, so that DAE cannot be replaced and applied to the tread rubber, and can only be partially applied to the rubber in other parts of the tire.

[0004] Therefore, in view of the above status, it is urgent to develop a high-aromatics environment-friendly tire oil preparation method to overcome the deficiencies in the current actual application. SUMMARY

[0005] The purpose of the embodiment of the application is to provide a high-aromatics environment-friendly tire oil preparation method, and aims to solve the problems in the background art.

[0006] To achieve the above purpose, the application provides the following technical scheme:

[0007] The application discloses a preparation method of a high-aromatics environment-friendly tire oil, and particularly relates to the following steps.

[0008] S1: preparing a high-aromatics naphthenic base oil by a hydrotreating process or a solvent refining combined process with naphthenic heavy oil vacuum distillate as raw material;

[0009] S2: obtaining heavy component oil with low saturated hydrocarbon content by molecular distillation head treatment with heavy oil catalytic cracking slurry after solid removal treatment, naphthenic heavy oil vacuum residue or propane deoiled pitch as raw material;

[0010] S3: blending the high-aromatics naphthenic base oil and the heavy component oil with low saturated hydrocarbon content after molecular distillation head treatment according to a specific mass ratio to obtain tire rubber oil with high aromatic content.

[0011] In a further technical solution, the hydrotreating process in S1 adopts a Mo-Ni-W / Al2O3 catalyst, and the reaction conditions are as follows: hydrogen pressure 8-15 MPa, reaction temperature 330-350 DEG C, volume space velocity 0.5 h-1, and hydrogen / oil ratio 800-1000:1. -1 -1h -1 In a further technical solution, the solvent refining combined process in S1 adopts a "hydrogen deacidification-solvent refining-bleaching clay supplementary refining" process, wherein the furfural refining solvent ratio is 1.0-2.0:1.0, the extraction column top temperature is 75-80 DEG C, and the extraction column top temperature is 60-65 DEG C.

[0012] In a further technical solution, the molecular distillation head treatment in S2 is carried out under the conditions of vacuum degree 10-20 Pa and head cutting temperature 260-270 DEG C.

[0013] In a further technical solution, when the heavy component oil is heavy oil catalytic cracking slurry, the blending ratio is 35:65; when the heavy component oil is naphthenic heavy oil vacuum residue or naphthenic propane deoiled pitch, the blending ratio is 70:30.

[0014] In a further technical solution, the tire rubber oil in S has a kinematic viscosity of 25-40 mm 2 / s at 100 DEG C, a C A value of not less than 22% in carbon type composition, an aniline point of not more than 95 DEG C, a benzo(a)pyrene content of not more than 1 mg / kg, and an eight-specific aromatic content of not more than 10 mg / kg.

[0015] Compared with the prior art, the embodiments of the application have the following beneficial effects:

[0016]

[0017] ​The method for preparing high-aromatic environmentally friendly tire oil provided by the present invention optimizes raw material selection and process parameters. The product produced not only meets the requirements of environmental protection regulations, but also has the characteristics of high aromatic content and good compatibility with rubber. It can replace traditional tire rubber oil with high polycyclic aromatic hydrocarbon content, reduce costs, and improve tire performance.

[0018] In order to more clearly illustrate the structural features and effects of the present invention, the present invention is described in detail below with reference to the accompanying drawings and specific embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a table of property test methods for the products of the present invention;

[0020] Figure 2 This is a property test data table of the high aromatic naphthenic base oil in the product of the present invention;

[0021] Figure 3 This is a property test data table of the heavy component with low saturated hydrocarbon content in the product of the present invention after molecular distillation and topping treatment;

[0022] Figure 4 This is a property test data table of the blended high aromatic environmentally friendly tire rubber oil in the product of the present invention. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0024] The specific implementation of the present invention is described in detail below with reference to specific embodiments.

[0025] Example 1

[0026] like Figures 1-4 As shown, an embodiment of the present invention provides a method for preparing high-aromatic environmentally friendly tire oil, wherein high-aromatic cycloalkyl base oil is blended with treated low-saturated hydrocarbon content heavy components to obtain high-aromatic environmentally friendly tire oil, wherein the high-aromatic cycloalkyl base oil is made from cycloalkyl heavy oil vacuum distillate oil as a raw material and is obtained through a combined process of hydrogenation treatment or solvent refining; the low-saturated hydrocarbon content heavy components include desolidified heavy oil catalytic cracking oil slurry, cycloalkyl heavy oil vacuum residue, propane deoiled asphalt, etc.

[0027] The specific steps include:

[0028] S1: Preparation of high aromatic naphthenic base oil;

[0029] The naphthenic heavy oil vacuum distillate is used as raw material, and a Mo-Ni-W / Al2O3 catalyst is used, and the hydrogenation reaction conditions are as follows: hydrogen pressure is 15 MPa, reaction temperature is 350 ℃, volume space velocity is 0.5 h -1 , , and the hydrogen-oil ratio is 1000:1; high-aromatic naphthenic base oil is obtained through fractionation, and the properties are shown in Figure 2 .

[0030] S2: preparing a heavy component with low saturated hydrocarbon content;

[0031] The solid-removal-treated heavy oil catalytic cracking slurry is used as raw material, and molecular distillation head treatment is performed, the molecular distillation vacuum degree is 15 Pa, the head cutting temperature is 265 ℃, and a heavy component oil with low saturated hydrocarbon content is obtained, and the properties are shown in Figure 4 .

[0032] S3: blending;

[0033] The high-aromatic naphthenic base oil and the heavy component oil subjected to molecular distillation head treatment are blended in a mass ratio of 35:65, and a high-aromatic-content tire rubber oil is obtained, and the properties are shown in Figure 4 .

[0034] Example 2

[0035] As shown in Figures 1-4 , the embodiment of the present application provides a high-aromatic environmentally-friendly tire oil preparation method, which specifically comprises the following steps:

[0036] S1: preparing high-aromatic naphthenic base oil;

[0037] The naphthenic heavy oil vacuum distillate is used as raw material, and a Mo-Ni-W / Al2O3 catalyst is used, and the hydrogenation reaction conditions are as follows: hydrogen pressure is 15 MPa, reaction temperature is 330 ℃, volume space velocity is 0.5 h -1 , , and the hydrogen-oil ratio is 800:1; high-aromatic naphthenic base oil is obtained through fractionation, and the properties are shown in Figure 2 .

[0038] S2: preparing a heavy component with low saturated hydrocarbon content;

[0039] The solid-removal-treated naphthenic heavy oil vacuum residue is used as raw material, and molecular distillation head treatment is performed, the molecular distillation vacuum degree is 20 Pa, the head cutting temperature is 270 ℃, and a heavy component oil with low saturated hydrocarbon content is obtained, and the properties are shown in Figure 3 .

[0040] S3: blending;

[0041] The high aromatic content tire rubber oil is obtained by blending the high aromatic content naphthenic base oil and the heavy component oil treated by molecular distillation cut-off according to a mass ratio of 70:30, and the properties are shown in Table 1. Figure 4 .

[0042] Example 3

[0043] As shown in the figure, the embodiment of the present application provides a high aromatic content environment-friendly tire oil preparation method, which specifically comprises the following steps: Figures 1-4

[0044] S1: preparing high aromatic content naphthenic base oil;

[0045] The naphthenic heavy oil vacuum distillate is used as raw material, and a Mo-Ni-W / Al2O3 catalyst is used, and the hydrogenation reaction conditions are as follows: hydrogen pressure is 8 MPa, reaction temperature is 350 DEG C, volume space velocity is 0.5 h -1 , -1, and hydrogen / oil ratio is 1000:1; the high aromatic content naphthenic base oil is obtained by fractionation, and the properties are shown in Table 1. Figure 2 .

[0046] S2: preparing low saturated hydrocarbon content heavy component;

[0047] The solid-removed naphthenic propane deoiled asphalt is used as raw material, and molecular distillation cut-off treatment is carried out, the molecular distillation vacuum degree is 10 Pa, and the cut-off cutting temperature is 260 DEG C, so that the low saturated hydrocarbon content heavy component oil is obtained, and the properties are shown in Table 2. Figure 3 .

[0048] S3: blending;

[0049] The high aromatic content tire rubber oil is obtained by blending the high aromatic content naphthenic base oil and the heavy component oil treated by molecular distillation cut-off according to a mass ratio of 70:30, and the properties are shown in Table 1. Figure 4 .

[0050] Example 4

[0051] As shown in the figure, the embodiment of the present application provides a high aromatic content environment-friendly tire oil preparation method, which specifically comprises the following steps: Figures 1-4

[0052] S1: preparing high aromatic content naphthenic base oil;

[0053] The naphthenic heavy oil vacuum distillate is used as raw material, and a Mo-Ni-W / Al2O3 catalyst is used, and the hydrogenation reaction conditions are as follows: hydrogen pressure is 15 MPa, reaction temperature is 350 DEG C, volume space velocity is 1.0 h -1 , -1, and hydrogen / oil ratio is 1000:1; the high aromatic content naphthenic base oil is obtained by fractionation, and the properties are shown in Table 1. Figure 2 . ​​

[0054] S2: Preparation of low-saturated hydrocarbon content heavy component;

[0055] The naphthenic heavy oil vacuum residue after solid removal treatment was used as raw material to carry out molecular distillation head treatment, the molecular distillation vacuum degree was 20 Pa, the head cutting temperature was 270 DEG C, and a heavy component oil with low saturated hydrocarbon content was obtained, the properties were shown in Table 2. Figure 3 .

[0056] S3: Blending.

[0057] The high aromatic naphthenic base oil was blended with the heavy component oil after molecular distillation head treatment according to the mass ratio of 70:30, and a high aromatic content tire rubber oil was obtained, the properties were shown in Table 3. Figure 4 .

[0058] Example 5

[0059] As shown in Figures 1-4 , the embodiment of the present application provides a high aromatic environmental protection tire oil preparation method, which specifically comprises the following steps:

[0060] S1: Preparation of high aromatic naphthenic base oil;

[0061] The naphthenic heavy oil vacuum residue was used as raw material to carry out molecular distillation head treatment, the molecular distillation vacuum degree was 20 Pa, the head cutting temperature was 270 DEG C, and a heavy component oil with low saturated hydrocarbon content was obtained, the properties were shown in Table 2. Figure 2 .

[0062] S2: Preparation of low-saturated hydrocarbon content heavy component;

[0063] The naphthenic heavy oil vacuum residue after solid removal treatment was used as raw material to carry out molecular distillation head treatment, the molecular distillation vacuum degree was 20 Pa, the head cutting temperature was 270 DEG C, and a heavy component oil with low saturated hydrocarbon content was obtained, the properties were shown in Table 2. Figure 3 .

[0064] S3: Blending;

[0065] The high aromatic naphthenic base oil was blended with the heavy component oil after molecular distillation head treatment according to the mass ratio of 70:30, and a high aromatic content tire rubber oil was obtained, the properties were shown in Table 3. Figure 4 .

[0066] Example 6

[0067] As shown in Figure 1 , the embodiment of the present application provides a high aromatic environmental protection tire oil preparation method, which specifically comprises the following steps:

[0068] S1: Preparation of high aromatic naphthenic base oil;

[0069] The high aromatic naphthenic base oil is obtained by using the naphthenic heavy oil vacuum distillate as raw material, adopting the process of "hydrogenation deacidification-furfural refining-clay supplementary refining", the furfural refining conditions are that the solvent ratio (volume) is 1.0:1.0, the extraction tower top temperature is 75 ℃, the extraction tower top temperature is 65 ℃, and the properties of the high aromatic naphthenic base oil obtained after the clay supplementary refining are shown in Table 1. ​ .

[0070] S2: Preparation of heavy component with low saturated hydrocarbon content;

[0071] The heavy component oil with low saturated hydrocarbon content is obtained by using the naphthenic heavy oil vacuum residue after solid removal treatment as raw material and performing molecular distillation head treatment, the molecular distillation vacuum degree is 20 Pa, the head cutting temperature is 270 ℃, and the properties of the heavy component oil with low saturated hydrocarbon content are shown in Table 2. ​ .

[0072] S3: Blending;

[0073] The high aromatic naphthenic base oil and the heavy component oil with low saturated hydrocarbon content obtained by molecular distillation head treatment are blended in a mass ratio of 70:30 to obtain the high aromatic content tire rubber oil, and the properties of the high aromatic content tire rubber oil are shown in Table 3. ​ .

[0074] The properties of the high aromatic naphthenic base oil, the heavy component with low saturated hydrocarbon content and the blended high aromatic content tire rubber oil prepared in the above examples are tested, and the test method is tested according to the test standard in GB / T 20828-2007. ​ .

[0075] In examples 1-6, the high aromatic naphthenic base oil obtained by using the naphthenic heavy oil vacuum distillate as raw material and adopting the combined process of hydrogenation treatment or solvent refining is blended with the heavy oil FCC slurry with low saturated hydrocarbon content obtained by molecular distillation head treatment, the naphthenic heavy oil vacuum residue or the propane deoiled pitch in a certain proportion, and the product obtained can meet the performance index requirements of the environmental protection tire oil.

[0076] The high aromatic environmental protection tire oil can be used as rubber oil for tire tread rubber to improve the wet skid resistance and service life of the tire, and at the same time meet the requirements of environmental protection regulations.

[0077] The above only describes the preferred embodiments of the present application, and is not used to limit the present application, any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A process for the preparation of a high aromatic environmentally friendly tire oil characterized in that, Specifically comprising the following steps: S1: taking a naphthenic heavy oil vacuum distillate as a raw material, preparing a high-aromatic naphthenic base oil by a hydrotreating process or a solvent refining combined process; S2: taking a heavy oil catalytic cracking slurry oil, a naphthenic heavy oil vacuum residue or a propane deoiled pitch after solid removal treatment as a raw material, performing molecular distillation head treatment to obtain a heavy component oil with low saturated hydrocarbon content; S3: blending the high-aromatic naphthenic base oil with the heavy component oil with low saturated hydrocarbon content after molecular distillation head treatment according to a specific mass ratio to obtain a high-aromatic content tire rubber oil.

2. The process for preparing a high aromatic environmentally friendly tire oil according to claim 1, characterized in that, The hydrogenation treatment process in S1 uses Mo-Ni-W / Al2O3 catalyst, and the reaction conditions are hydrogen pressure of 8-15 MPa, reaction temperature of 330-350°C, volume space velocity of 0.5h -1 -1h -1 , and hydrogen to oil ratio of 800-1000:

1.

3. The process for preparing a high aromatic environmentally friendly tire oil according to claim 1, characterized in that, In S1, the solvent refining combined process adopts a "hydrogenation deacidification-solvent refining-clay supplemental refining" process, wherein the furfural refining solvent ratio is 1.0-2.0:1.0, the extraction tower top temperature is 75-80℃, and the extraction tower top temperature is 60-65℃.

4. The process for preparing a high aromatic environmentally friendly tire oil according to claim 1, characterized in that, In S2, the molecular distillation head treatment conditions are a vacuum degree of 10-20 Pa and a head cutting temperature of 260-270℃.

5. The process for preparing a high aromatic environmentally friendly tire oil according to claim 1, characterized in that, In S3, when the heavy component oil is a heavy oil catalytic cracking slurry oil, the blending ratio is 35:65, and when the heavy component oil is a naphthenic heavy oil vacuum residue or a naphthenic propane deoiled pitch, the blending ratio is 70:

30.

6. The process for preparing a high aromatic environmentally friendly tire oil according to claim 1, characterized in that, S kinematic viscosity at 100°C of the tyre rubber oil is 25-40 mm 2 / s, C in the carbon type composition A not more than 22%, an aniline point of not more than 95°C, a benzo(a)pyrene content of not more than 1 mg / kg, and an octane-specific aromatic content of not more than 10 mg / kg.

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