High aromatic rubber plasticizer and preparation method thereof

Abstract

The invention provides a high aromatic rubber plasticizer and a preparation method thereof, and relates to the technical field of petrochemical engineering, and the preparation method comprises the following steps: carrying out a solvent deasphalting process on naphthenic base vacuum residue to obtain deasphalted oil, and carrying out a hydrofining process on the deasphalted oil to obtain the high aromatic rubber plasticizer. According to the method, n-heptane insoluble substances of the deasphalted oil can be controlled to be 500 mg / kg or below, better conditions are provided for subsequent hydrofining, and the obtained rubber plasticizer product is high in yield and additional value and has higher market competitiveness; meanwhile, the rubber plasticizer product meets the limited substance requirement of environment-friendly operating oil, the CA value of the product is 25% or above, the compatibility with rubber materials, carbon black and the like is more excellent in the tire preparation process, and the tire can be endowed 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 and a preparation method thereof. Background Art

[0002] At present, the production of environmental protection 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 main products, a large amount of by-products with low added value, high processing costs, and environmental pollution risks during the processing, resulting in low overall economic benefits. Therefore, developing a production process for high-C A value aromatic-based environmental protection rubber plasticizers has great practical significance.

[0003] 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 environmental protection rubber oil with a C A value of 10% - 18% is obtained, and at the same time, some low-value primary extract oil or secondary extract oil is produced, resulting in a low yield of the main product. A production method of a heavy environmental protection rubber oil disclosed in the prior art obtains an environmental protection rubber oil that meets the requirements of the EU REACH regulation through a two-stage propane solvent extraction process. The C A value of the environmental protection rubber oil obtained by this process is only 10% - 20%, and the product yield is low; a preparation method of an environmental protection rubber oil disclosed in the prior art performs one-stage propane deasphalting on naphthenic vacuum residue to obtain deasphalted oil, then performs two-stage propane deasphalting on the deasphalted oil, and the obtained heavy deasphalted oil is mixed with naphthenic oil to obtain an environmental protection rubber oil (rubber plasticizer). The C A value of the obtained product is low. In the prior art, there is also a method using 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 (such as hydrorefining, single-stage furfural refining, and two-stage furfural refining) are respectively used to obtain an environmental protection 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 propane deasphalting and two-stage furfural refining processes have long flow paths and produce more by-products, resulting in a low yield of the main product. In the prior art, there is also a method using naphthenic fraction oil as a raw material, and a C AThe environmental protection rubber plasticizer with a value of 19% to 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, it is also disclosed that a vacuum distillate oil is used as a raw material, and a pretreated oil is obtained by hydrotreating, and then an extract oil is obtained through a furfural refining process. After hydrogenation, a high-aromatic environmental protection rubber oil is obtained. The rubber oil obtained by this process has a relatively high aromatic content, but the process flow is long, more by-products are generated, and the yield of the main product is low.

[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-aromatic rubber plasticizer, which can control the n-heptane insoluble matter of the deasphalted oil below 500 mg / kg, provide better conditions for subsequent hydrofining, and the obtained rubber plasticizer product has a high yield and added value and high market competitiveness.

[0006] Another purpose of the present invention is to provide a high-aromatic rubber plasticizer that can meet the requirements of limited substances for environmental protection operating oils, and the C value of the product is above 25%. A value is above 25%.

[0007] In order to achieve the above purposes of the present invention, the following technical solutions are specifically adopted:

[0008] In the first aspect, a preparation method of a high-aromatic rubber plasticizer includes the following steps:

[0009] Perform a solvent deasphalting process on the naphthenic vacuum residue to obtain deasphalted oil, and subject the obtained deasphalted oil to a hydrofining process to obtain a high-aromatic rubber plasticizer.

[0010] Further, the solvent used in the solvent deasphalting process includes at least one of pentane, isopentane, and hexane.

[0011] Further, in the solvent deasphalting process, the top temperature of the extraction column is 130°C to 160°C, and the bottom temperature is 120°C to 150°C.

[0012] Further, the agent-oil ratio used in the solvent deasphalting process is 4:1 to 10:1.

[0013] Further, in the hydrofining process, the reaction temperature is 300°C to 400°C;

[0014] In the hydrofining process, the volume ratio of hydrogen to deasphalted oil is (600 - 1200):1.

[0015] Further, in the hydrofining process, the volume space velocity is 0.2h -1 ~1.0h-1 , the hydrogen partial pressure is greater than 10 MPa.

[0016] Further, the catalyst loading method in the hydrofining process includes staged loading;

[0017] The catalyst includes a hydrodesulfurization catalyst, a hydrodemetallization catalyst, and a hydrofining catalyst.

[0018] Further, the volume ratio of the hydrodesulfurization catalyst to the total catalyst is 10% - 30%;

[0019] Preferably, the volume ratio of the hydrodemetallization catalyst to the total catalyst is 10% - 30%;

[0020] Preferably, the volume ratio of the hydrofining catalyst to the total catalyst is 40% - 80%.

[0021] In a second aspect, a high-aromatic rubber plasticizer prepared by the preparation method described in any one of the above.

[0022] Further, the C A value of the high-aromatic rubber plasticizer is above 25%;

[0023] Preferably, the kinematic viscosity of the high-aromatic rubber plasticizer at 100 °C ≥ 50 mm 2 / s, the flash point ≥ 240 °C, and the PCA content ≤ 3%;

[0024] Preferably, the benzo[a]pyrene content of the high-aromatic rubber plasticizer is less than 1 mg / kg, and the PAHs content is less than 10 mg / kg.

[0025] Compared with the prior art, the present invention has at least the following beneficial effects:

[0026] The preparation method of the high-aromatic rubber plasticizer provided by the present invention uses naphthenic vacuum residue as the raw material, and the deasphalted oil yield is above 60%. After hydrofining, the yield of the obtained high-aromatic rubber plasticizer product is not less than 55% of the vacuum residue, converting low-value asphalt products into high-value rubber plasticizers, with high market competitiveness.

[0027] The high-aromatic rubber plasticizer provided by the present invention meets the requirements of the limited substances for environmentally friendly processing oils in the "Technical Specification for Green Design Product Evaluation - Automotive Tires", i.e., the BaP content ≤ 1 mg / kg and the PAHs content ≤ 10 mg / kg; at the same time, the C A value of the high-aromatic rubber plasticizer is above 25%, and it has better compatibility with rubber compounds, carbon black, etc. during the tire preparation process, and can endow the tire with more excellent use performance. Specific Embodiments

[0028] The technical solution 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 belong to the scope of protection 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, including the following steps:

[0030] Perform a solvent deasphalting process on the naphthenic vacuum residue to obtain deasphalted oil, and take the deasphalted oil for a hydrofining process to obtain a high-aromatic rubber plasticizer.

[0031] The raw material used in the present invention is naphthenic vacuum residue, and the deasphalted oil yield is above 60%. After hydrofining, the yield of the obtained high-aromatic rubber plasticizer product is not less than 55% of the vacuum residue, converting the low-value asphalt product into a high-value rubber plasticizer with relatively high market competitiveness.

[0032] In the present invention, the solvent used in the solvent deasphalting process includes but is not limited to at least one or a mixture of pentane, isopentane, and hexane, and pentane can be further preferably used.

[0033] Adopting a high-separation pentane solvent deasphalting process can control the n-heptane insoluble matter in the deasphalted oil below 500 mg / kg, providing better conditions for subsequent hydrofining.

[0034] In a preferred embodiment, the top temperature of the extraction column in the solvent deasphalting process can be 130°C to 160°C, and its typical but non-limiting temperatures are, for example, 130°C, 140°C, 150°C, 160°C; the bottom temperature can be 120°C to 150°C, and its typical but non-limiting temperatures are, for example, 120°C, 130°C, 140°C, 150°C.

[0035] At the same time, the solvent / oil ratio used in the solvent deasphalting process can be 4:1 to 10:1.

[0036] In a preferred embodiment, the reaction temperature in the hydrofining process can be 300°C to 400°C, and its typical but non-limiting reaction temperatures are, for example, 300°C, 320°C, 340°C, 360°C, 380°C, 400°C; the volume ratio of hydrogen to deasphalted oil in the hydrofining process can be (600 - 1200):1, and its typical but non-limiting volume ratios are, for example, 600:1, 700:1, 800:1, 900:1, 1000:1, 1100:1, 1200:1.

[0037] In the present invention, the space velocity by volume in the hydrofining process may be 0.2 h -1 ~1.0 h -1 , and its typical but non-limiting space velocity by volume is, for example, 0.2 h -1 , 0.3 h -1 , 0.4 h -1 , 0.5 h -1 , 0.6 h -1 , 0.7 h -1 , 0.8 h -1 , 0.9 h -1 , 1.0 h -1 , and the hydrogen partial pressure may be greater than 10 MPa.

[0038] In a preferred embodiment, the catalyst loading method in the hydrofining process includes but is not limited to graded loading; wherein, the catalyst includes but is not limited to a hydrodemeshing catalyst, a hydrodemetallization catalyst, and a hydrofining catalyst.

[0039] Adopting the method of graded loading of the catalyst can greatly improve the operation life of the catalyst and is beneficial to reducing the operation cost of the device.

[0040] In a preferred embodiment, the volume ratio of the hydrodemeshing catalyst to the total catalyst may be 10% - 30%, and its typical but non-limiting volume ratios are, for example, 10%, 20%, 30%.

[0041] In a preferred embodiment, the volume ratio of the hydrodemetallization catalyst to the total catalyst may be 10% - 30%, and its typical but non-limiting volume ratios are, for example, 10%, 20%, 30%.

[0042] In a preferred embodiment, the volume ratio of the hydrofining catalyst to the total catalyst may be 40% - 80%, and its typical but non-limiting volume ratios are, for example, 40%, 50%, 60%, 70%, 80%.

[0043] A typical preparation method of a high-aromatic rubber plasticizer includes the following steps:

[0044] (1) Subjecting naphthenic vacuum residue to a solvent deasphalting process to obtain deasphalted oil;

[0045] Among them, the penetration of the naphthenic vacuum residue is less than 30 (0.1 mm);

[0046] The solvent used in the solvent deasphalting process is one or a mixture of solvents such as pentane, isopentane, and hexane;

[0047] In the solvent deasphalting process, the top temperature of the extraction column is 130°C to 160°C, the bottom temperature is 120°C to 150°C, and the solvent-to-oil volume ratio is 4:1 to 10:1;

[0048] (2) Subject the deasphalted oil to high-pressure hydrofining to obtain a high-aromatic rubber plasticizer product with a C A value greater than 25%;

[0049] Among them, in the high-pressure hydrofining, a staged catalyst loading method is adopted;

[0050] In the hydrofining, the reaction temperature is 300°C to 400°C, the volume ratio of hydrogen to deasphalted oil is (600 - 1200):1, and the volume space velocity in the hydrofining is 0.2 h -1 ~1.0 h -1 , and the hydrogen partial pressure is greater than 10 MPa;

[0051] The catalyst adopts a staged loading method of hydrodesulfurization, hydrodemetallization, and hydrofining catalysts; the proportion of the hydrodesulfurization catalyst in the total catalyst volume is 10% - 30%, the proportion of the hydrodemetallization catalyst in the total catalyst volume is 10% - 30%, and the proportion of the hydrofining catalyst in the total catalyst volume is 40% - 80%.

[0052] According to the second aspect of the present invention, there is provided a high-aromatic rubber plasticizer prepared by the preparation method described in any one of the above.

[0053] In the present invention, the C A value of the high-aromatic rubber plasticizer is above 25%.

[0054] In a preferred embodiment, the kinematic viscosity of the high-aromatic rubber plasticizer at 100°C ≥ 50 mm 2 / s, the flash point ≥ 240°C, and the PCA content ≤ 3%.

[0055] In the present invention, analyzed by the GC-MS method, the benzo[a]pyrene content of the high-aromatic rubber plasticizer is less than 1 mg / kg, and the PAHs content is less than 10 mg / kg (the PAHs content 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).

[0056] In summary, the high-aromatic rubber plasticizer of the present invention meets the requirements of the limited substances for environmentally friendly processing oils in the "Technical Specification for Green Design Product Evaluation - Automotive Tires", that is, the BaP content ≤ 1 mg / kg and the PAHs content ≤ 10 mg / kg; at the same time, the C AThe value is above 25%, and it has better compatibility with rubber compounds, carbon black, etc. during the tire manufacturing process, and can endow the tire with more excellent performance.

[0057] 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.

[0058] Example 1

[0059] A preparation method of a high-aromatic rubber plasticizer, comprising the following steps:

[0060] (1) Using the vacuum residue produced by the refinery affiliated to CNOOC, Suizhong 36-1, as the raw material, a solvent deasphalting process is carried out to obtain deasphalted oil A1;

[0061] The solvent used in the solvent deasphalting process is pentane, the volume ratio of the solvent to the oil is 8:1, the top temperature of the extraction column is 155 °C, the bottom temperature is 145 °C, and the operating pressure is 4.0 MPa;

[0062] (2) Using deasphalted oil A1 as the raw material, a high-pressure hydrofining process is carried out. In the way of staged catalyst loading, the reaction is carried out under the conditions of a reaction pressure of 15 MPa, a reaction temperature of 340 °C, a volume space velocity of 0.4 h -1 and a hydrogen-oil volume ratio of 1000:1 to obtain hydrogenated product oil B1, which is the high-aromatic rubber plasticizer product. The specific properties are shown in Table 1.

[0063] Example 2

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

[0065] (1) Using the vacuum residue produced by the refinery affiliated to CNOOC, Suizhong 36-1, as the raw material, a solvent deasphalting process is carried out to obtain deasphalted oil A1;

[0066] The solvent used in the solvent deasphalting process is pentane, the volume ratio of the solvent to the oil is 8:1, the top temperature of the extraction column is 155 °C, the bottom temperature is 145 °C, and the operating pressure is 4.0 MPa;

[0067] (2) Using deasphalted oil A1 as the raw material, a high-pressure hydrofining process is carried out. In the way of staged catalyst loading, the reaction is carried out under the conditions of a reaction pressure of 15 MPa, a reaction temperature of 335 °C, a volume space velocity of 0.3 h -1 and a hydrogen-oil volume ratio of 1000:1 to obtain hydrogenated product oil B2, which is the high-aromatic rubber plasticizer product. The specific properties are shown in Table 1.

[0068] Table 1 Properties of high-aromatic rubber plasticizer

[0069]

[0070] In summary, the present invention converts low-value asphalt products into high-value rubber plasticizers, obtaining high-yield high-C A value aromatic-based rubber plasticizer products with excellent environmental performance and being non-toxic green products, and the overall economic benefit of the technology is relatively high; the C A value of the rubber plasticizer product of the present invention is above 25%, and its compatibility with rubber compounds, carbon black, etc. is more excellent during the tire preparation process, and it can endow the tire with more excellent service performance.

[0071] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than limiting 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 high-aromatic rubber plasticizer, characterized in that, It includes the following steps: Subject the naphthenic residue to a solvent deasphalting process to obtain deasphalted oil, and take the deasphalted oil for a hydrofining process to obtain a high-aromatic rubber plasticizer.

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

3. The preparation method according to claim 2, characterized in that, In the solvent deasphalting process, the top temperature of the extraction column is 130°C to 160°C, and the bottom temperature is 120°C to 150°C.

4. The preparation method according to claim 3, characterized in that, The solvent-to-oil ratio used in the solvent deasphalting process is 4:1 to 10:

1.

5. The preparation method according to any one of claims 1-4, characterized in that, In the hydrofining process, the reaction temperature is 300°C to 400°C; In the hydrofining process, the volume ratio of hydrogen to deasphalted oil is (600 - 1200):

1.

6. The preparation method according to claim 5, characterized in that, The space velocity in the hydrofining process is 0.2 h -1 ~1.0 h -1 , and the hydrogen partial pressure is greater than 10 MPa.

7. The preparation method according to claim 5, characterized in that, The catalyst loading method in the hydrofining process includes graded loading; The catalyst includes a hydrodesulfurization catalyst, a hydrodemetallization catalyst, and a hydrofining catalyst.

8. The preparation method according to claim 7, wherein The volume ratio of the hydrodesulfurization catalyst to the total catalyst is 10% to 30%; Preferably, the volume ratio of the hydrodemetallization catalyst to the total catalyst is 10% to 30%; Preferably, the volume ratio of the hydrofining catalyst to the total catalyst is 40% to 80%.

9. A high-aromatic rubber plasticizer prepared by the preparation method according to any one of claims 1-8.

10. The high-aromatic rubber plasticizer according to claim 9, characterized in that, The C of the high-aromatic rubber plasticizer A value is above 25%; Preferably, the kinematic viscosity of the high-aromatic rubber plasticizer at 100 °C is ≥ 50 mm 2 / s, the flash point is ≥ 240 °C, and the PCA content is ≤ 3%; Preferably, the content of benzo[a]pyrene in the high-aromatic rubber plasticizer is less than 1 mg / kg, and the content of PAHs is less than 10 mg / kg.

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