Rubber plasticizer and two-stage solvent extraction method thereof

Abstract

The invention provides a rubber plasticizer and a two-stage solvent extraction method thereof, and relates to the technical field of petrochemical engineering, and the two-stage solvent extraction method comprises the following steps: (1) carrying out solvent deasphalting on naphthenic base and / or intermediate base vacuum residue to obtain deasphalted oil; and (2) performing solvent deasphalting on the deasphalted oil to obtain deoiled asphalt as high aromatic oil for green tires, and obtaining light deoiled rubber plasticizer with CA value greater than or equal to 12%. According to the method, an asphalt product with a low additional value is converted into a rubber oil product with a high additional value, the additional value of the product can be greatly improved, the high market competitiveness is achieved, the BaP content of the high aromatic oil product for the green tire is smaller than or equal to 1 mg / kg, the PAHs content is smaller than or equal to 10 mg / kg, and the CA value is larger than 30%; the total yield of the high aromatic hydrocarbon oil product for the green tire and the rubber plasticizer product with the CA value larger than 12% can reach 75% or above.

Description

Technical Field

[0001] The present invention relates to the technical field of petrochemical industry, and particularly relates to a rubber plasticizer and a two-stage solvent extraction method thereof. Background Art

[0002] Rubber products are closely related to human life and directly affect people's physical health. With the increasingly stringent environmental protection regulations, the environmental protection of high-aromatic rubber oil, one of the important raw materials of rubber products, has also attracted much attention. The EU REACH regulation stipulates that the total content of 8 specific aromatic hydrocarbons in rubber oil directly put on the market or rubber oil used to manufacture tires is less than 10 mg / kg (the 8 specific aromatic hydrocarbons are benz[a]pyrene, benz[a]anthracene, benz[k]fluoranthene, benz[e]pyrene, benz[j]fluoranthene, dibenzo[a,h]anthracene, and benz[b]fluoranthene, abbreviated as PAHs), and the content of benz[a]pyrene is less than 1 mg / kg. The limit substance requirements for environmentally friendly processing oils in the "Technical Specification for the Evaluation of Green Design Products - Automotive Tires" are that the BaP content ≤ 1 mg / kg and the PAHs content ≤ 10 mg / kg. High-aromatic rubber plasticizers have a high aromatic hydrocarbon content, are safe and environmentally friendly, and have excellent environmental protection and use performance during tire processing.

[0003] Currently, the production of environmentally friendly rubber plasticizers mainly has two processes, namely solvent refining and hydrorefining, and their combined processes. The production of high-aromatic rubber plasticizers is mostly a 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 the main product, a large amount of by-products with low added value, high processing costs, and environmental pollution risks during processing, resulting in low overall economic benefits. Therefore, developing a production process for high-value aromatic-based environmentally friendly rubber plasticizers with low costs has great practical significance. A

[0004] For the production of high-aromatic rubber plasticizers, in the prior art, naphthenic reduced third-line fraction oil is used 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, resulting in a low yield of the main product. A production method of a heavy environmentally friendly rubber oil disclosed in the prior art obtains an environmentally friendly rubber oil that meets the requirements of the EU REACH regulation through a two-stage propane solvent extraction process. The environmentally friendly rubber oil obtained by this process has a C A ​The value is only 10% - 20%, and the product yield is relatively low; a preparation method of an environmentally friendly rubber oil disclosed in the prior art is to perform primary propane deasphalting on naphthenic vacuum residue to obtain deasphalted oil, then perform secondary propane deasphalting on the deasphalted oil, and mix the obtained heavy deasphalted oil with naphthenic oil to obtain an environmentally friendly rubber oil (rubber plasticizer), and the obtained product C A has a low value. In the prior art, there is also a method that uses inferior naphthenic heavy wax oil as the raw material. First, the propane deasphalting process is used to obtain the tower top refined liquid, and then different combined processes (such as hydrofining, single-stage furfural refining, and two-stage furfural refining) are used respectively to obtain an environmentally friendly rubber oil. The rubber plasticizer sample C A obtained by the hydrofining and single-stage furfural refining processes has a low value (only 12% - 18%). Moreover, the propane deasphalting and two-stage furfural refining processes have a long flow path, which will produce more by-products, resulting in a low yield of the main product. In the prior art, there is also a method that uses naphthenic distillate oil as the raw material and produces C A by a hydrotreating and two-stage solvent extraction process. The environmentally friendly rubber plasticizer with a C value of 19% - 26% has good compatibility with rubber and excellent processing performance, but the entire process flow is long, and a low-value furfural extract oil is produced as a by-product. In the prior art, there is also a method that uses vacuum distillate oil as the raw material, obtains pre-treated oil by hydrotreating, then obtains extract oil through a furfural refining process, and obtains a high-aromatic-content environmentally friendly rubber oil after hydrogenation. The rubber oil obtained by this process has a high aromatic content, but the process flow is long, more by-products are generated, and the yield of the main product is low.

[0005] In view of this, the present invention is specifically proposed. Summary of the Invention

[0006] One of the purposes of the present invention is to provide a two-stage solvent extraction method for a rubber plasticizer, which can convert low-value asphalt products into high-value rubber oil products, can greatly improve the product added value, has high market competitiveness, and the combined yield of the high-aromatic oil product for green tires and the rubber plasticizer product with a C A value greater than 12% can reach more than 75%.

[0007] Another purpose of the present invention is to provide a rubber plasticizer, a high-aromatic oil product for green tires and a rubber plasticizer product with a C A value greater than 12%. The high-aromatic oil product for green tires has better compatibility with rubber compounds, carbon black, etc. during the tire preparation process, which is beneficial to endowing the tires with more excellent use performance.

[0008] In order to achieve the above purposes of the present invention, the following technical solutions are specifically adopted:

[0009] In the first aspect, a two-stage solvent extraction method for a rubber plasticizer includes the following steps:

[0010] (1) Solvent deasphalting is carried out on naphthenic-based and / or intermediate-base vacuum residue to obtain deasphalted oil;

[0011] (2) The deasphalted oil is subjected to solvent deasphalting to obtain deoiled asphalt as a high-aromatic oil for green tires and light deoiled oil as a rubber plasticizer with a C A value ≥ 12%.

[0012] Furthermore, in step (1), the solvent used for solvent deasphalting includes at least one of pentane and hexane.

[0013] Furthermore, in step (1), the top temperature of the extraction column in the solvent deasphalting is 130°C to 170°C, the bottom temperature is 120°C to 160°C, and the solvent-to-oil ratio used is 4:1 to 10:1.

[0014] Furthermore, in step (1), the internal pressure of the extraction column in the solvent deasphalting is 2.0 MPa to 4.5 MPa.

[0015] Furthermore, in step (2), the solvent used for solvent deasphalting includes propane.

[0016] Furthermore, in step (2), the top temperature of the extraction column in the solvent deasphalting is 60°C to 85°C, the bottom temperature is 50°C to 75°C, and the solvent-to-oil ratio used is 4:1 to 10:1.

[0017] Furthermore, in step (2), the internal pressure of the extraction column in the solvent deasphalting is 2.0 MPa to 4.5 MPa.

[0018] In a second aspect, a rubber plasticizer prepared by the method according to any one of the above.

[0019] Furthermore, the C A value of the high-aromatic oil for green tires ≥ 30%;

[0020] Preferably, the BaP content of the high-aromatic oil for green tires ≤ 1 mg / kg and the PAHs content ≤ 10 mg / kg;

[0021] Preferably, the kinematic viscosity at 100°C of the high-aromatic oil for green tires ≥ 100 mm 2 / s and the flash point ≥ 240°C.

[0022] Furthermore, the flash point of the rubber plasticizer with a C A value ≥ 12% ≥ 210°C and the aniline point ≤ 95°C;

[0023] Preferably, the C AThe BaP content of the rubber plasticizer with a value ≥ 12% is ≤ 1 mg / kg, the PAHs content is ≤ 10 mg / kg, and the polycyclic aromatic hydrocarbon content is less than 3%.

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

[0025] The two-stage solvent extraction method of the rubber plasticizer provided by the present invention converts low-value asphalt products into high-value rubber oil products, greatly improving the product added value, so it has high market competitiveness; the combined yield of the high-aromatic hydrocarbon oil product for green tires and the rubber plasticizer product with a C A value greater than 12% obtained by the method of the present invention can reach more than 75%.

[0026] The rubber plasticizer provided by the present invention, the high-aromatic hydrocarbon oil product for green tires and the rubber plasticizer product with a C A value greater than 12%. The high-aromatic hydrocarbon oil product for green tires meets the limited substance requirements for environmentally friendly processing oils in the "Technical Specification for the Evaluation of Green Design Products - Automotive Tires" (i.e., BaP content ≤ 1 mg / kg, PAHs content ≤ 10 mg / kg). At the same time, the C A value is greater than 30%, and its compatibility with rubber compounds, carbon black, etc. is more excellent during the tire preparation process, which is beneficial to endowing the tire with more excellent use performance. Detailed Embodiments

[0027] 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.

[0028] According to the first aspect of the present invention, a two-stage solvent extraction method for rubber plasticizer is provided, including the following steps:

[0029] (1) Solvent deasphalting of naphthenic and / or intermediate base vacuum residue to obtain deasphalted oil;

[0030] (2) Solvent deasphalting of the obtained deasphalted oil to obtain deoiled asphalt as the high-aromatic hydrocarbon oil for green tires, and obtain light deoiled oil as the rubber plasticizer with a C A value ≥ 12%.

[0031] In the present invention, low-value asphalt products are converted into high-value rubber oil products, greatly improving the product added value, so it has high market competitiveness; at the same time, the combined yield of the high-aromatic hydrocarbon oil product for green tires and the rubber plasticizer product with a C A value greater than 12% obtained can reach more than 75%.

[0032] In a preferred embodiment, in step (1), the solvents used in the solvent deasphalting process include but are not limited to at least one of pentane and hexane, and the pentane content in the used pentane is not less than 99%, and the hexane content in the used hexane is not less than 99%.

[0033] In a preferred embodiment, in step (1), the top temperature of the extraction column in the solvent deasphalting process 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; the bottom temperature 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; meanwhile, the solvent-to-oil ratio used can be 4:1 to 10:1.

[0034] In a preferred embodiment, in step (1), the internal pressure of the extraction column in the solvent deasphalting process 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.

[0035] In a preferred embodiment, in step (2), the solvents used in the solvent deasphalting process include but are not limited to propane, and the purity of the used propane is not less than 99%.

[0036] In a preferred embodiment, in step (2), the top temperature of the extraction column in the solvent deasphalting process can be 60°C to 85°C, and its typical but non-limiting temperatures are for example 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, and the bottom temperature can be 50°C to 75°C, and its typical but non-limiting temperatures are for example 50°C, 55°C, 60°C, 65°C, 70°C, 75°C; meanwhile, the solvent-to-oil ratio used can be 4:1 to 10:1.

[0037] In a preferred embodiment, in step (2), the internal pressure of the extraction column in the solvent deasphalting process 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.

[0038] A typical method for two-stage solvent extraction of a rubber plasticizer, comprising the following steps:

[0039] (1) Using naphthenic and / or intermediate-base vacuum residue as raw materials, through the first solvent deasphalting process, deasphalted oil A is obtained;

[0040] Among them, the naphthenic-based and / or intermediate-base vacuum residue is the vacuum residue produced by an industrial vacuum unit, and the penetration of this vacuum residue is no more than 200 1 / 10 mm;

[0041] The solvent used in the first solvent deasphalting process is a mixture of one or both of pentane and hexane;

[0042] In the first solvent deasphalting process, the top temperature of the extraction column is 130°C to 170°C, the bottom temperature is 120°C to 160°C, the solvent-to-oil ratio used is 4:1 to 10:1, and the internal pressure of the extraction column is 2.0 MPa to 4.5 MPa;

[0043] (2) Using the obtained deasphalted oil A as a raw material, through a second solvent deasphalting process, deoiled asphalt B is obtained, which is the high-aromatic oil for green tires, and at the same time, the light deoiled oil C is obtained, which is a rubber plasticizer with a C A value > 12%;

[0044] Among them, the solvent used in the second solvent deasphalting process is propane;

[0045] In the second solvent deasphalting process, the top temperature of the extraction column is 60°C to 85°C, the bottom temperature is 50°C to 75°C, the solvent-to-oil ratio used is 4:1 to 10:1, and 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 method described in any one of the above.

[0047] In the present invention, the C A value of the high-aromatic oil for green tires is ≥ 30%, the kinematic viscosity at 100°C is ≥ 100 mm 2 / s, the flash point is ≥ 240°C, the BaP content is ≤ 1 mg / kg, and the PAHs content is ≤ 10 mg / kg.

[0048] The high-aromatic oil product for green tires of the present invention meets the requirements of the limited substances of the environmentally friendly processing oil in the "Technical Specification for Green Design Product Evaluation - Automotive Tires" (i.e., the BaP content is ≤ 1 mg / kg and the PAHs content is ≤ 10 mg / kg). At the same time, the C A value is greater than 30%, and its compatibility with rubber compounds, carbon black, etc. during tire preparation is more excellent, which is beneficial to endowing the tire with more excellent use performance.

[0049] In the present invention, the flash point of the rubber plasticizer with a C A value ≥ 12% is ≥ 210°C, the aniline point is ≤ 95°C, the BaP content is ≤ 1 mg / kg, the PAHs content is ≤ 10 mg / kg, and the polycyclic aromatic hydrocarbon (PCA) content is less than 3%.

[0050] The present invention will be further described below by way of examples. Unless otherwise specified, the materials in the examples are prepared according to existing methods or directly purchased from the market.

[0051] Example 1

[0052] A two-stage solvent extraction method for a rubber plasticizer includes the following steps:

[0053] (1) Using the QHD32-6 vacuum residue produced by a refinery under CNOOC as the raw material (penetration not greater than 200 1 / 10 mm), through the first solvent deasphalting process, deasphalted oil A1 is obtained;

[0054] Among them, the solvent used in the first solvent deasphalting process is pentane;

[0055] In the first solvent deasphalting process, the top temperature of the extraction column is 155 °C, the bottom temperature is 145 °C, the solvent-to-oil ratio used is 8:1, and the internal pressure of the extraction column is 4.0 MPa;

[0056] (2) Using the obtained deasphalted oil A1 as the raw material, through the second solvent deasphalting process, deoiled asphalt B1, which is the high-aromatic oil for green tires, is obtained, and at the same time, the light deoiled oil C1, which is the rubber plasticizer with a C A value > 12% is obtained;

[0057] Among them, the solvent used in the second solvent deasphalting process is propane;

[0058] In the second solvent deasphalting process, the top temperature of the extraction column is 72 °C, the bottom temperature is 62 °C, the solvent-to-oil ratio used is 6:1, and the internal pressure of the extraction column is 3.8 MPa.

[0059] The specific properties of the substances in this example are shown in Table 1.

[0060] Example 2

[0061] A two-stage solvent extraction method for a rubber plasticizer includes the following steps:

[0062] (1) Using the QHD32-6 vacuum residue produced by a refinery under CNOOC as the raw material (penetration not greater than 200 1 / 10 mm), through the first solvent deasphalting process, deasphalted oil A2 is obtained;

[0063] Among them, the solvent used in the first solvent deasphalting process is hexane;

[0064] In the first solvent deasphalting process, the top temperature of the extraction column is 155 °C, the bottom temperature is 145 °C, the solvent-to-oil ratio used is 8:1, and the internal pressure of the extraction column is 4.0 MPa;

[0065] (2) Using the obtained deasphalted oil A2 as the raw material, through the second solvent deasphalting process, deoiled asphalt B2 is obtained, which is the high-aromatic oil for green tires, and at the same time, the light deoiled oil C2 obtained is the rubber plasticizer with a A C value > 12%;

[0066] Among them, the solvent used in the second solvent deasphalting process is propane;

[0067] In the second solvent deasphalting process, the top temperature of the extraction tower is 72 °C, the bottom temperature is 62 °C, the solvent-oil ratio used is 6:1, and the internal pressure of the extraction tower is 3.8 MPa.

[0068] The specific properties of the substances in this example are shown in Table 1.

[0069] Table 1

[0070]

[0071] As can be seen from the above examples, the present invention converts low-value asphalt products into high-value rubber oil products, greatly improving the product value-added, obtaining high-aromatic oil for green tires and environmentally friendly rubber plasticizer products with high yields, and the total yield can reach more than 75%. The entire process has high market competitiveness.

[0072] 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 described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A two-stage solvent extraction method for a rubber plasticizer, characterized in that, It includes the following steps: (1) Subjecting naphthenic-based and / or intermediate-base vacuum residue to solvent deasphalting to obtain deasphalted oil; (2) Solvent deasphalting is carried out on the deasphalted oil to obtain deoiled asphalt as a high-aromatic oil for green tires and light deoiled oil as a rubber plasticizer with a C A value ≥ 12%.

2. The method according to claim 1, wherein In step (1), the solvent used for the solvent deasphalting includes at least one of pentane and hexane.

3. The method according to claim 2, characterized in that In step (1), the top temperature of the extraction column in the solvent deasphalting is 130°C to 170°C, the bottom temperature is 120°C to 160°C, and the solvent-to-oil ratio used is 4:1 to 10:

1.

4. The method according to claim 3, characterized in that, In step (1), the internal pressure of the extraction column in the solvent deasphalting is 2.0 MPa to 4.5 MPa.

5. The method according to any one of claims 1-4, characterized in that, In step (2), the solvent used for the solvent deasphalting includes propane.

6. The method according to claim 5, characterized in that, In step (2), the top temperature of the extraction column in the solvent deasphalting is 60°C to 85°C, the bottom temperature is 50°C to 75°C, and the solvent-to-oil ratio used is 4:1 to 10:

1.

7. The method according to claim 6, wherein In step (2), the internal pressure of the extraction column in the solvent deasphalting is 2.0 MPa to 4.5 MPa.

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

9. The rubber plasticizer according to claim 8, characterized in that, The C of the high-aromatic oil for green tires A value ≥ 30%; Preferably, the BaP content of the high-aromatic oil for green tires is ≤1 mg / kg, and the PAHs content is ≤10 mg / kg; Preferably, the kinematic viscosity of the high-aromatic oil for green tires at 100 °C is ≥ 100 mm 2 / s, and the flash point is ≥ 240 °C.

10. The rubber plasticizer according to claim 9, characterized in that, The described C A The flash point of the rubber plasticizer with a C value ≥ 12% is ≥ 210°C, and the aniline point is ≤ 95°C; Preferably, the BaP content of the rubber plasticizer with a C A value ≥ 12% is ≤ 1 mg / kg, the PAHs content is ≤ 10 mg / kg, and the polycyclic aromatic hydrocarbon content is less than 3%.

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