High aromatic rubber plasticizer as well as preparation method and application thereof

Abstract

The invention provides a high aromatic 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 reduced pressure deep distillation on naphthenic base and / or intermediate base reduced pressure residual oil to obtain a deeply-distilled fraction, and carrying out a solvent deasphalting reaction on the deeply-distilled fraction to obtain deasphalted oil as a rubber plasticizer; wherein the temperature of reduced pressure deep drawing is 500 DEG C or above. According to the preparation method, the technological process is short, the obtained product is high in yield and high in additional value, the low-additional-value asphalt product is converted into the high-additional-value aromatic hydrocarbon oil for the green tire, and high market competitiveness is achieved; the CA value of the rubber plasticizer product is greater than or equal to 30%, and the rubber plasticizer product has better compatibility with rubber and carbon black in the tire preparation process, and is beneficial to endowing tires with more excellent use performance.

Description

Technical Field

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

[0002] At present, the technologies for producing environmentally friendly rubber plasticizers mainly include two processes of solvent refining and hydrorefining and their combined processes. The production technology of high-aromatic rubber plasticizers mostly adopts the solvent refining process, such as furfural refining, solvent deasphalting process and their combined processes. Solvent refining is a physical extraction process, which has problems such as low yield of main products, large amounts of by-products with low added value, high processing costs, and environmental pollution risks in the processing process, ultimately resulting in low overall economic benefits. Therefore, developing a production process for environmentally friendly rubber plasticizers with high C A value and low cost has great practical significance.

[0003] For the production of high-aromatic rubber plasticizers, the prior art uses naphthenic reduced third-line fraction oil as a raw material, and after two-stage furfural refining, an environmentally friendly rubber oil with a C A value of 10% - 18% is obtained, and at the same time, some low-value primary extraction oil or secondary extraction oil is produced, which will lead to a low yield of the main product.

[0004] The prior art discloses a production method of heavy environmentally friendly rubber oil, and an environmentally friendly rubber oil meeting the requirements of EU REACH regulations is obtained through a two-stage propane solvent extraction process, but the C A value of the environmentally friendly rubber oil obtained by this process is only 10% - 20%, and the product yield is low; the prior art discloses a preparation method of an environmentally friendly rubber oil, which is to perform one-stage propane deasphalting on naphthenic vacuum residue to obtain deasphalted oil, and then perform two-stage propane deasphalting on the deasphalted oil, and the obtained heavy deasphalted oil is 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; there is also a prior art that uses poor-quality naphthenic heavy wax oil as a raw material, first adopts a propane deasphalting process to obtain a tower-top refined liquid, and then adopts different combined processes (hydrorefining, single-stage furfural refining, and two-stage furfural refining) to obtain an environmentally friendly rubber oil. The C A value of the rubber plasticizer samples obtained by the hydrorefining 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.

[0005] There is also a prior art that uses naphthenic fraction oil as a raw material and produces C AThe environmentally friendly rubber plasticizer with a value of 19% - 26% has good compatibility with rubber and excellent processing performance. However, the entire process flow is relatively long, and a by-product of low-value furfural extract oil is generated. In the prior art, there is also a process that uses vacuum distillate oil as raw material, obtains pre-treatment oil through hydrotreating, then gets extract oil through furfural refining process, and finally gets high-aromatic environmentally friendly rubber oil after hydrogenation. The rubber oil obtained by this process has a relatively high aromatic content, but the process flow is long and produces more by-products, resulting in a relatively low yield of the main product.

[0006] In view of this, the present invention is specifically proposed. Summary of the Invention

[0007] One of the purposes of the present invention is to provide a preparation method of a high-aromatic rubber plasticizer, which not only has a short process flow, but also has a high product yield and high added value, and can convert low-value asphalt products into aromatic oils for green tires with high added value.

[0008] Another purpose of the present invention is to provide a high-aromatic rubber plasticizer with a C A value ≥ 30%, which has better compatibility with rubber compounds and carbon black during tire preparation.

[0009] Another purpose of the present invention is to provide an application of a high-aromatic rubber plasticizer, which is beneficial to endowing tires with more excellent use performance.

[0010] In order to achieve the above purposes of the present invention, the following technical solutions are specifically adopted:

[0011] In the first aspect, a preparation method of a high-aromatic rubber plasticizer includes the following steps:

[0012] Perform vacuum deep distillation on naphthenic-based and / or intermediate-base vacuum residue to obtain deep-distilled fractions, and take the deep-distilled fractions to carry out solvent deasphalting reaction to obtain deasphalted oil as a rubber plasticizer;

[0013] The temperature of the vacuum deep distillation is above 500 °C.

[0014] Further, the solvent used in the solvent deasphalting reaction includes at least one of pentane, hexane, and heptane.

[0015] Further, the top temperature of the extraction column in the solvent deasphalting reaction is 130 °C - 170 °C.

[0016] Further, the bottom temperature of the extraction column in the solvent deasphalting reaction is 120 °C - 160 °C.

[0017] Further, the solvent-to-oil ratio used in the solvent deasphalting reaction is 4:1 - 10:1.

[0018] Further, the internal pressure of the solvent deasphalting reaction in the extraction column is 2.0 MPa to 4.5 MPa.

[0019] In a second aspect, a rubber plasticizer prepared by the preparation method according to any one of the above.

[0020] Further, the C A value of the rubber plasticizer is ≥ 30%.

[0021] Further, the kinematic viscosity of the rubber plasticizer at 100 °C is ≥ 100 mm 2 / s, the flash point is ≥ 240 °C, and the aniline point is ≤ 75 °C;

[0022] The content of BaP in the rubber plasticizer is ≤ 1 mg / kg, and the content of PAHs is ≤ 10 mg / kg.

[0023] In a third aspect, an application of the rubber plasticizer according to any one of the above in green tires.

[0024] Compared with the prior art, the present invention has at least the following beneficial effects:

[0025] The preparation method of the high-aromatic rubber plasticizer provided by the present invention not only has a short process flow, but also has a high product yield and high added value; specifically, the present invention prepares a rubber oil for high-aromatic green tires through a single-stage solvent (pentane) deasphalting process, with a short process flow. At the same time, the product yield can reach more than 70%, converting low-value asphalt products into high-value aromatic oils for green tires, with high market competitiveness.

[0026] The high-aromatic rubber plasticizer provided by the present invention meets the limited substance requirements for environmentally friendly processing 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., the content of BaP is ≤ 1 mg / kg, and the content of PAHs is ≤ 10 mg / kg); at the same time, the C A value of the product is ≥ 30%, and it has better compatibility with rubber compounds and carbon black during tire preparation, and can endow the tires with more excellent use performance.

[0027] The application of the high-aromatic rubber plasticizer provided by the present invention is beneficial to endowing the tires with more excellent use performance. Specific Embodiments

[0028] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0029] According to the first aspect of the present invention, a preparation method of a high-aromatic rubber plasticizer is provided, comprising the following steps:

[0030] Subject the naphthenic and / or intermediate-base vacuum residue to vacuum deep distillation to obtain a deep-distilled fraction, and subject this deep-distilled fraction to a solvent deasphalting reaction to obtain deasphalted oil as the rubber plasticizer;

[0031] Among them, the temperature of the vacuum deep distillation is above 500 °C.

[0032] The preparation method of the present invention not only has a short process flow, but also the obtained product has a high yield and high added value.

[0033] In a preferred embodiment, the solvent used in the solvent deasphalting reaction includes but is not limited to at least one of pentane, hexane, and heptane.

[0034] The present invention prepares a rubber oil for high-aromatic green tires through a single-stage solvent (pentane) deasphalting process. The process flow is short, and at the same time, the yield of the obtained product can reach more than 70%. It converts low-value asphalt products into high-value aromatic oils for green tires, and has high market competitiveness.

[0035] In a preferred embodiment, the top temperature of the extraction column in the solvent deasphalting reaction can be 130 °C to 170 °C, and its typical but non-limiting temperatures are for example 130 °C, 140 °C, 150 °C, 160 °C, 170 °C.

[0036] In a preferred embodiment, the bottom temperature of the extraction column in the solvent deasphalting reaction can be 120 °C to 160 °C, and its typical but non-limiting temperatures are for example 120 °C, 130 °C, 140 °C, 150 °C, 160 °C.

[0037] In the present invention, the solvent-to-oil ratio used in the solvent deasphalting reaction can be 4:1 to 10:1, and its typical but non-limiting solvent-to-oil ratios are for example 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1.

[0038] In a preferred embodiment, the internal pressure of the extraction column in the solvent deasphalting reaction can be 2.0 MPa to 4.5 MPa, and its 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.

[0039] A typical preparation method of a high-aromatic rubber plasticizer includes the following steps:

[0040] (1) Treat the naphthenic and / or intermediate-base vacuum residue through a vacuum deep distillation process to obtain a deep-distilled fraction;

[0041] Among them, the distillation temperature in the vacuum deep-cutting process is above 500 °C;

[0042] (2) Using the deep-cutting distillate obtained in step (1) as the raw material, through solvent deasphalting reaction treatment, deasphalted oil is obtained, which is the high-aromatic rubber plasticizer (C A value ≥ 30%);

[0043] Among them, the solvent used in the solvent deasphalting reaction is one or more of pentane, hexane or heptane;

[0044] In the solvent deasphalting reaction, the top temperature of the extraction column is 130 °C to 170 °C, the bottom temperature is 120 °C to 160 °C, and the solvent-to-oil ratio is 4:1 to 10:1;

[0045] In the solvent deasphalting reaction, the internal pressure of the extraction column is 2.0 MPa to 4.5 MPa.

[0046] 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.

[0047] In a preferred embodiment, the C A value of the rubber plasticizer of the present invention is ≥ 30%.

[0048] At the same time, the kinematic viscosity of the rubber plasticizer of the present invention at 100 °C is ≥ 100 mm 2 / s, the flash point is ≥ 240 °C, and the aniline point is ≤ 75 °C.

[0049] In the present invention, analyzed by the GC-MS method, the BaP content (benzo[a]pyrene content) in the rubber plasticizer is ≤ 1 mg / kg, and the PAHs content is ≤ 10 mg / kg (PAHs is the content 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).

[0050] In summary, the high-aromatic rubber plasticizer of the present invention meets the limited substance requirements for environmentally friendly processing 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., the BaP content is ≤ 1 mg / kg, and the PAHs content is ≤ 10 mg / kg); at the same time, its C A value is ≥ 30%, so it has better compatibility with rubber compounds and carbon black during tire preparation, which can endow the tire with more excellent use performance.

[0051] 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.

[0052] The application of the high-aromatic rubber plasticizer of the present invention is beneficial to endowing tires with more excellent service performance.

[0053] The present invention will be further described below through examples. Unless otherwise specified, the materials in the examples are prepared according to existing methods or directly purchased from the market.

[0054] Example 1

[0055] A preparation method of a high-aromatic rubber plasticizer includes the following steps:

[0056] (1) Treat the Sui-Zhong 36-1 vacuum residue produced by a refinery under the control of CNOOC through a vacuum deep-drawing process to obtain the deep-drawn fraction A1;

[0057] Among them, the distillation temperature in the vacuum deep-drawing process is above 500 °C;

[0058] (2) Using the deep-drawn fraction A1 obtained in step (1) as the raw material, through solvent deasphalting reaction treatment, obtain deasphalted oil B1, which is the high-aromatic rubber plasticizer (C A value ≥ 30%), and it is a high-aromatic oil for green tires;

[0059] Among them, the solvent used in the solvent deasphalting reaction is pentane;

[0060] In the solvent deasphalting reaction, the top temperature of the extraction tower is 160 °C, the bottom temperature is 150 °C, and the solvent-to-oil ratio is 8:1;

[0061] In the solvent deasphalting reaction, the internal pressure of the extraction tower is 4.0 MPa.

[0062] The specific properties of the deasphalted oil B1 obtained in this example are shown in Table 1.

[0063] Example 2

[0064] A preparation method of a high-aromatic rubber plasticizer includes the following steps:

[0065] (1) Treat the Sui-Zhong 36-1 vacuum residue produced by a refinery under the control of CNOOC through a vacuum deep-drawing process to obtain the deep-drawn fraction A2;

[0066] Among them, the distillation temperature in the vacuum deep-drawing process is above 500 °C;

[0067] (2) Using the deep-drawn fraction A2 obtained in step (1) as the raw material, through solvent deasphalting reaction treatment, obtain deasphalted oil B2, which is the high-aromatic rubber plasticizer (CA value ≥ 30%), and it is a high-aromatic oil for green tires;

[0068] Among them, the solvent used in the solvent deasphalting reaction is hexane;

[0069] In the solvent deasphalting reaction, the top temperature of the extraction column is 160 °C, the bottom temperature is 150 °C, and the solvent-to-oil ratio is 8:1;

[0070] The internal pressure of the extraction column in the solvent deasphalting reaction is 4.0 MPa.

[0071] The specific properties of the deasphalted oil B2 obtained in this example are shown in Table 1.

[0072] Comparative Example 1

[0073] The difference between this comparative example and Example 1 is that the vacuum deep distillation process in step (1) is not carried out in this comparative example;

[0074] The remaining steps and their process parameters are the same as those in Example 1.

[0075] 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 of the limited substances for the environmentally friendly processing oil for green tires.

[0076] Comparative Example 2

[0077] The difference between this comparative example and Example 1 is that the distillation temperature in the vacuum deep distillation process in step (1) of this comparative example is below 450 °C;

[0078] The remaining steps and their process parameters are the same as those in Example 1.

[0079] 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 of the limited substances for the environmentally friendly processing oil for green tires.

[0080] Table 1

[0081]

[0082] As can be seen from Table 1, the preparation method of 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.

[0083] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than 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 described 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 high-aromatic rubber plasticizer, characterized in that, Comprising the following steps: Subjecting naphthenic-based and / or intermediate-base vacuum residue to vacuum deep distillation to obtain a deep-distilled fraction, and subjecting the deep-distilled fraction to a solvent deasphalting reaction to obtain deasphalted oil as a rubber plasticizer; The temperature of the vacuum deep distillation is above 500 °C.

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, The top temperature of the extraction column in the solvent deasphalting reaction is 130 °C to 170 °C.

4. The preparation method according to claim 3, characterized in that, The bottom temperature of the extraction column in the solvent deasphalting reaction is 120 °C to 160 °C.

5. The preparation method according to claim 4, characterized in that, The solvent-to-oil ratio used in the solvent deasphalting reaction is 4:1 to 10:

1.

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

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, characterized in that, The C of the rubber plasticizer A value ≥ 30%.

9. The rubber plasticizer according to claim 8, wherein The kinematic viscosity of the rubber plasticizer at 100 °C is ≥ 100 mm 2 / s, the flash point is ≥ 240 °C, and the aniline point is ≤ 75 °C; 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 a green tire.

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