High-CA-value rubber plasticizer as well as preparation method and application thereof

Abstract

The invention provides a high-CA-value rubber plasticizer and a preparation method and application thereof, and relates to the technical field of petrochemical engineering, and the preparation method comprises the following steps: carrying out a solvent deasphalting reaction on naphthenic base and / or intermediate base vacuum residue to obtain deasphalted oil, and carrying out a vacuum deep drawing process on the deasphalted oil to obtain the high-CA-value rubber plasticizer. The cut fraction with the cutting temperature higher than 500 DEG C is used as the high-CA-value rubber plasticizer. According to the method, the technological process is short, the yield and the additional value of the obtained product are high, the yield can reach 70% or above, and the asphalt product with the low additional value is converted into the aromatic hydrocarbon oil with the high additional value for the green tire; the CA value of the rubber plasticizer is greater than or equal to 30%, and the rubber plasticizer has better compatibility with rubber and carbon black in the tire preparation process, and can endow tires with more excellent use performance.

Description

Technical Field

[0001] The present invention relates to the technical field of petrochemical industry, and in particular to a high-C A value rubber plasticizer, a preparation method thereof, and an application thereof. Background Art

[0002] At present, the production of high-aromatic rubber plasticizers mostly adopts solvent refining methods, such as furfural refining, solvent deasphalting and their combined processes. Solvent refining is a physical extraction process, which has problems such as low yield of main products, a large amount of by-products with low added value, high processing costs, and environmental pollution risks during the processing. Therefore, developing a production process for environmentally friendly rubber plasticizers with high C A value and low cost has great practical significance.

[0003] The prior art discloses a preparation method of an environmentally friendly rubber oil, which is to carry out primary propane deasphalting on naphthenic vacuum residue to obtain deasphalted oil, and then carry out secondary propane deasphalting on the deasphalted oil. The obtained heavy deasphalted oil is then mixed with naphthenic oil to obtain an environmentally friendly rubber oil (rubber plasticizer). The C A value of the product obtained by this method is low; in the prior art, there is also a method that uses inferior naphthenic heavy wax oil as a raw material. First, a propane deasphalting process is used to obtain a tower top refined liquid, and then different combined processes (hydrofining, single-stage furfural refining, and two-stage furfural refining) are used to obtain an environmentally friendly rubber oil. Among them, the C A value of the rubber plasticizer samples obtained by the hydrofining and single-stage furfural refining processes is low (only 12% - 18%), and the process of propane deasphalting plus two-stage furfural refining has a long process flow, and more by-products will be generated during the process, resulting in a low yield of the main product.

[0004] In view of this, the present invention is specifically proposed. Summary of the Invention

[0005] One of the purposes of the present invention is to provide a preparation method of a high-C A value rubber plasticizer, which not only has a short process flow, but also has a high yield and added value of the obtained product. The yield can reach more than 70%, and the low-value asphalt product is converted into an aromatic oil for green tires with high added value.

[0006] Another purpose of the present invention is to provide a high-C A value rubber plasticizer, whose C A value ≥ 30%, and has better compatibility with rubber compounds and carbon black during the tire preparation process.

[0007] The third purpose of the present invention is to provide an application of a high-C A value rubber plasticizer, which is beneficial to endowing the tire with more excellent use performance.

[0008] To achieve the above object of the present invention, the following technical solutions are specifically adopted:

[0009] In a first aspect, a preparation method of a high-C A value rubber plasticizer includes the following steps:

[0010] Perform solvent deasphalting reaction on naphthenic base and / or intermediate base vacuum residue to obtain deasphalted oil. Take the deasphalted oil and perform vacuum deep distillation process to obtain a fraction with a cutting temperature greater than 500 °C as the high-C A value rubber plasticizer.

[0011] Further, the solvent used in the solvent deasphalting reaction includes at least one of pentane, hexane, and heptane.

[0012] Further, the top temperature of the extraction column in the solvent deasphalting reaction is 130 °C to 170 °C, and the bottom temperature is 120 °C to 160 °C.

[0013] Further, the solvent-to-oil ratio used in the solvent deasphalting reaction is 4:1 to 10:1.

[0014] Further, the internal pressure of the extraction column in the solvent deasphalting reaction is 2.0 MPa to 4.5 MPa.

[0015] Further, the distillation temperature of the vacuum deep distillation process is above 500 °C.

[0016] In a second aspect, a rubber plasticizer prepared by the preparation method described in any one of the above.

[0017] Further, the C A value of the rubber plasticizer is ≥ 30%, the kinematic viscosity at 100 °C is ≥ 100 mm 2 / s, the flash point is ≥ 240 °C, and the aniline point is ≤ 75 °C.

[0018] Further, the BaP content in the rubber plasticizer is ≤ 1 mg / kg, and the PAHs content is ≤ 10 mg / kg.

[0019] In a third aspect, an application of the rubber plasticizer described in any one of the above in green tires.

[0020] Compared with the prior art, the present invention has at least the following beneficial effects:

[0021] The high-C APreparation method of value rubber plasticizer, preparing rubber oil for high-aromatic green tires through a single-stage solvent (pentane) deasphalting process, not only has a short process flow, but also has a high product yield and added value. The yield can reach more than 70%, converting low-value asphalt products into high-value aromatic oils for green tires, with high market competitiveness.

[0022] The high-C A value rubber plasticizer provided by the present invention has a C A value ≥ 30%, has better compatibility with rubber compounds and carbon black during tire preparation, can endow tires with more excellent use performance, and at the same time meets the requirements for limited substances of environmental protection operating oils in the "Technical Specification for Green Design Product Evaluation - Automotive Tires" issued by the China Petroleum and Chemical Industry Federation and the China Rubber Industry Association (i.e., BaP content ≤ 1 mg / kg, PAHs content ≤ 10 mg / kg).

[0023] The application of the high-C A value rubber plasticizer provided by the present invention is beneficial to endowing tires with more excellent use performance. Specific embodiments

[0024] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments.

[0025] According to the first aspect of the present invention, a preparation method of a high-C A value rubber plasticizer is provided, including the following steps:

[0026] Carry out solvent deasphalting reaction on naphthenic base and / or intermediate base vacuum residue to obtain deasphalted oil, and take the deasphalted oil for vacuum deep distillation process to obtain a fraction with a cutting temperature greater than 500 °C as the high-C A value rubber plasticizer.

[0027] The preparation method of the present invention not only has a short process flow, but also has a high product yield and its added value.

[0028] In the present invention, the solvent used in the solvent deasphalting reaction includes but is not limited to at least one of pentane, hexane, and heptane.

[0029] The present invention prepares rubber oil for high-aromatic green tires through a solvent deasphalting process, with a short process flow, and at the same time the obtained product has a high yield and added value. The yield can reach more than 70%, and can convert low-value asphalt products into high-value aromatic oils for green tires.

[0030] In a preferred embodiment, the top temperature of the extraction column in the solvent deasphalting reaction can be 130°C to 170°C, and typical but non-limiting temperatures are, for example, 130°C, 140°C, 150°C, 160°C, 170°C. The bottom temperature can be 120°C to 160°C, and typical but non-limiting temperatures are, for example, 120°C, 130°C, 140°C, 150°C, 160°C.

[0031] In a preferred embodiment, the agent-oil ratio used in the solvent deasphalting reaction can be 4:1 to 10:1, and typical but non-limiting agent-oil ratios are, for example, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1.

[0032] In the present invention, the internal pressure of the extraction column in the solvent deasphalting reaction can be 2.0 MPa to 4.5 MPa, and typical but non-limiting pressures are, for example, 2.0 MPa, 2.5 MPa, 3.0 MPa, 3.5 MPa, 4.0 MPa, 4.5 MPa.

[0033] In a preferred embodiment, the distillation temperature in the vacuum deep-drawing process is above 500°C, and a fraction with a cutting temperature greater than 500°C can be obtained.

[0034] According to the second aspect of the present invention, there is provided a rubber plasticizer prepared by the preparation method described in any one of the above.

[0035] In a preferred embodiment, the C A value of the rubber plasticizer ≥ 30%, and it has better compatibility with the rubber compound and carbon black during the tire preparation process, so it can endow the tire with more excellent use performance.

[0036] The kinematic viscosity of the rubber plasticizer at 100°C ≥ 100 mm 2 / s, the flash point ≥ 240°C, and the aniline point ≤ 75°C.

[0037] Analyzed by the GC-MS method, the BaP content (benzo[a]pyrene content) in the rubber plasticizer ≤ 1 mg / kg, and the PAHs content ≤ 10 mg / kg (PAHs are the contents of 8 aromatic hydrocarbons including benzo[a]pyrene, benzo[e]pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[j]fluoranthene, benzo[k]fluoranthene, and dibenzo[a,h]anthracene).

[0038] According to the third aspect of the present invention, there is provided an application of the rubber plasticizer described in any one of the above in green tires, which is beneficial to endowing the tires with more excellent use performance.

[0039] The present invention will be further described below through examples.

[0040] Example 1

[0041] A high-C A preparation method of value rubber plasticizer, comprising the following steps:

[0042] (1) Treat the vacuum residue produced by the refinery under the jurisdiction of CNOOC, Suizhong 36-1, through solvent deasphalting reaction to obtain deasphalted oil A1;

[0043] Among them, the solvent used in the solvent deasphalting reaction is pentane, and the volume ratio of the solvent to the oil is 8:1; meanwhile, the top temperature of the extraction column in the solvent deasphalting reaction is 155 °C, the bottom temperature is 145 °C, and the operating pressure is 4.0 MPa;

[0044] (2) Using the deasphalted oil A1 obtained in step (1) as the raw material, through vacuum deep distillation process treatment, the distillation temperature in the vacuum deep distillation process is above 500 °C, and a fraction B1 with a cutting temperature greater than 500 °C is obtained, which is the high-C A value rubber plasticizer.

[0045] The specific properties of the high-C A value rubber plasticizer obtained in this example are shown in Table 1.

[0046] Example 2

[0047] A high-C A preparation method of value rubber plasticizer, comprising the following steps:

[0048] (1) Treat the vacuum residue produced by the refinery under the jurisdiction of CNOOC, Suizhong 36-1, through solvent deasphalting reaction to obtain deasphalted oil A2;

[0049] Among them, the solvent used in the solvent deasphalting reaction is hexane, and the volume ratio of the solvent to the oil is 8:1; meanwhile, the top temperature of the extraction column in the solvent deasphalting reaction is 155 °C, the bottom temperature is 145 °C, and the operating pressure is 4.0 MPa;

[0050] (2) Using the deasphalted oil A2 obtained in step (1) as the raw material, through vacuum deep distillation process treatment, the distillation temperature in the vacuum deep distillation process is above 500 °C, and a fraction B2 with a cutting temperature greater than 500 °C is obtained, which is the high-C A value rubber plasticizer.

[0051] The specific properties of the high-C A value rubber plasticizer obtained in this example are shown in Table 1.

[0052] Comparative Example 1

[0053] The difference between this comparative example and Example 1 is that the vacuum deep distillation process in step (2) is not carried out in this comparative example;

[0054] The remaining steps and their process parameters are the same as those in Example 1.

[0055] Compared with Example 1, the defect of this comparative example is that the contents of BaP and PAHs in the deasphalted oil are relatively high, not meeting the requirements for limited substances of the environmentally friendly processing oil for green tires.

[0056] Comparative Example 2

[0057] The difference between this comparative example and Example 1 is that in the vacuum deep distillation process of step (2) in this comparative example, the distillation temperature is below 450 °C;

[0058] The remaining steps and their process parameters are the same as those in Example 1.

[0059] Compared with Example 1, the defect of this comparative example is that there will still be some residues of eight carcinogenic aromatic hydrocarbons in the heavy components, and the contents of BaP and PAHs in the final product do not meet the requirements for limited substances of the environmentally friendly processing oil for green tires.

[0060] Table 1

[0061]

[0062] As can be seen from Table 1, the present invention can obtain a high-aromatic oil for green tires with a high yield, which is a non-toxic green product, has a relatively high aromatic content, has excellent processing performance during tire processing, and is beneficial to improving the overall production economic benefits.

[0063] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A preparation method of a rubber plasticizer with a high C A value, characterized in that It includes the following steps: The naphthenic-based and / or intermediate-base vacuum residue is subjected to a solvent deasphalting reaction to obtain deasphalted oil. The deasphalted oil is taken for a vacuum deep distillation process, and the fraction with a cutting temperature greater than 500 °C is obtained as a high-C A value rubber plasticizer.

2. The preparation method according to claim 1, characterized in that, The solvent used in the solvent deasphalting reaction includes at least one of pentane, hexane, and heptane.

3. The preparation method according to claim 2, characterized in that, In the solvent deasphalting reaction, the top temperature of the extraction tower is 130°C to 170°C, and the bottom temperature is 120°C to 160°C.

4. The preparation method according to claim 3, wherein In the solvent deasphalting reaction, the ratio of solvent to oil used is 4:1 to 10:

1.

5. The preparation method according to claim 4, characterized in that, In the solvent deasphalting reaction, the internal pressure of the extraction tower is 2.0 MPa to 4.5 MPa.

6. The preparation method according to any one of claims 1-5, characterized in that, The distillation temperature of the vacuum deep distillation process is above 500°C.

7. A rubber plasticizer prepared by the preparation method according to any one of claims 1-6.

8. The rubber plasticizer according to claim 7, wherein The C of the rubber plasticizer A value ≥ 30%, kinematic viscosity at 100 °C ≥ 100 mm 2 / s, flash point ≥ 240 °C, aniline point ≤ 75 °C.

9. The rubber plasticizer according to claim 8, wherein, The BaP content in the rubber plasticizer is ≤1 mg / kg, and the PAHs content is ≤10 mg / kg.

10. An application of the rubber plasticizer according to any one of claims 7-9 in green tires.

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