Rubber plasticizer and preparation method thereof

Abstract

The invention provides a 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 solvent deasphalting on naphthenic base vacuum residue to obtain deasphalted oil, carrying out reduced pressure distillation on the deasphalted oil to obtain a fraction less than or equal to 520 DEG C and a fraction more than or equal to 520 DEG C, and carrying out hydrotreating, isodewaxing and finishing on the fraction of which the temperature is less than or equal to 520 DEG C to obtain a rubber plasticizer-naphthenic mineral oil product, and / or the fraction greater than or equal to 520 DEG C is used as a rubber plasticizer-aryl mineral oil product. According to the invention, an asphalt product with low additional value can be converted into a rubber plasticizer with high additional value, so that higher market competitiveness is exerted; according to the invention, a rubber plasticizer-aryl mineral oil product and a rubber plasticizer-naphthenic mineral oil product can be produced at the same time, and the characteristics of the naphthenic oil in the middle sea are fully exerted.

Description

Technical Field

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

[0002] At present, the production of environmentally friendly rubber plasticizers mainly has two processes, 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 the processing process, resulting in relatively low overall economic benefits. Therefore, developing a production process for environmentally friendly rubber plasticizers with low cost and high C A value has great practical significance.

[0003] For the production of high-aromatic rubber plasticizers, in the prior art, naphthenic cut 3 heavy fraction oil is used as the 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 C A value of the environmentally friendly rubber oil obtained by this process is only 10% - 20%, and the product yield is 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). The C A value of the obtained product is on the low side. In the prior art, there is also a method using inferior naphthenic heavy wax oil as the 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 used respectively 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%), while the propane deasphalting and two-stage furfural refining processes have a long process flow 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 the raw material, and a C is produced by a hydrotreating and two-stage solvent extraction process AThe environmentally friendly 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. The prior art also discloses that using vacuum distillate oil as raw material, through hydrotreating to obtain pretreated oil, and then through furfural refining process to obtain extract oil, and after hydrogenation, a high-aromatic environmentally friendly 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 objectives of the present invention is to provide a preparation method of a rubber plasticizer, which can simultaneously produce a rubber plasticizer - aromatic base mineral oil product and a rubber plasticizer - naphthenic base mineral oil product, giving full play to the characteristics of CNOOC naphthenic base oil.

[0006] Another objective of the present invention is to provide a rubber plasticizer. The rubber plasticizer - aromatic base mineral oil product has more prominent environmental protection performance, and at the same time has better compatibility with rubber compounds, carbon black, etc. The rubber plasticizer - naphthenic base mineral oil product can meet the HG / T 5781-2021 rubber plasticizer high-viscosity mineral oil standard.

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

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

[0009] Subjecting naphthenic base vacuum residue to solvent deasphalting to obtain deasphalted oil, taking the deasphalted oil for vacuum distillation to obtain a fraction of ≤520°C and a fraction of ≥520°C, taking the fraction of ≤520°C for hydrotreating, isodewaxing, and supplementary refining to obtain a rubber plasticizer - naphthenic base mineral oil product; and / or, taking the fraction of ≥520°C as a rubber plasticizer - aromatic base mineral oil product.

[0010] Further, the naphthenic base vacuum residue includes Suizhong 36-1 vacuum residue, Qinhuangdao 32-6 vacuum residue, and Jinzhou 9-3 vacuum residue;

[0011] The solvent used in the solvent deasphalting includes at least one of pentane, isopentane, and hexane, preferably pentane.

[0012] Further, the top temperature of the extraction tower in the solvent deasphalting is 130°C to 160°C, and the bottom temperature is 120°C to 150°C.

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

[0014] Furthermore, the yield of the deasphalted oil is above 80%.

[0015] In a second aspect, a rubber plasticizer prepared by the preparation method according to any one of the above.

[0016] Furthermore, the C value of the rubber plasticizer - naphthenic base mineral oil product N ≥ 45%.

[0017] Furthermore, the kinematic viscosity at 100 °C of the rubber plasticizer - naphthenic base mineral oil product is above 18 mm 2 / s.

[0018] Furthermore, the C value of the rubber plasticizer - aromatic base mineral oil product A ≥ 31%.

[0019] Furthermore, the BaP content of the rubber plasticizer - aromatic base mineral oil product is ≤ 1 mg / kg, and the PAHs content is ≤ 10 mg / kg.

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

[0021] The preparation method of the rubber plasticizer provided by the present invention uses naphthenic base vacuum residue as the raw material, and the yield of the deasphalted oil reaches above 80%. It can convert low - value asphalt products into high - value rubber plasticizers, demonstrating high market competitiveness; the present invention can simultaneously produce rubber plasticizer - aromatic base mineral oil products and rubber plasticizer - naphthenic base mineral oil products, giving full play to the characteristics of CNOOC naphthenic base oil.

[0022] For the rubber plasticizer provided by the present invention, the rubber plasticizer - aromatic base mineral oil product (BaP content ≤ 1 mg / kg, PAHs content ≤ 2 mg / kg) is far lower than the limited substance requirements for environmentally friendly processing oils in the "Technical Specification for Green Design Product Evaluation - Automotive Tires" (i.e., the requirements of BaP content ≤ 1 mg / kg and PAHs content ≤ 10 mg / kg), with more prominent environmental protection performance. At the same time, its C A value is greater than 31%, 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 service performance; the rubber plasticizer - naphthenic base mineral oil product can meet the HG / T 5781 - 2021 standard for high - viscosity mineral oil rubber plasticizers, its kinematic viscosity at 100 °C is above 18 mm 2 / s, and at the same time its C N value ≥ 45%. Specific Embodiments

[0023] The technical solution 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. 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.

[0024] According to the first aspect of the present invention, a preparation method of a rubber plasticizer is provided, including the following steps:

[0025] The naphthenic vacuum residue is subjected to solvent deasphalting to obtain deasphalted oil. The deasphalted oil is taken for vacuum distillation to obtain a fraction of ≤520 °C and a fraction of ≥520 °C. The fraction of ≤520 °C is taken for hydrotreatment, isodewaxing, and supplementary refining to obtain a rubber plasticizer - naphthenic base mineral oil product; and / or, the fraction of ≥520 °C is used as a rubber plasticizer - aromatic base mineral oil product.

[0026] In the present invention, using naphthenic vacuum residue as the raw material, the yield of deasphalted oil reaches more than 80%, which can convert low - value - added asphalt products into high - value - added rubber plasticizers, showing high market competitiveness; at the same time, both a rubber plasticizer - aromatic base mineral oil product and a rubber plasticizer - naphthenic base mineral oil product are produced, giving full play to the characteristics of CNOOC naphthenic oil.

[0027] In a preferred embodiment, the naphthenic vacuum residue includes Suizhong 36 - 1 vacuum residue, Qinhuangdao 32 - 6 vacuum residue, and Jinzhou 9 - 3 vacuum residue.

[0028] In the present invention, the solvent used in solvent deasphalting includes but is not limited to at least one or a mixture of pentane, isopentane, and hexane, and can be further preferably pentane, which is more conducive to further improving the effect of solvent deasphalting.

[0029] In a preferred embodiment, the top temperature of the extraction column in solvent deasphalting 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; meanwhile, the solvent - to - oil ratio used can be 4:1 to 10:1.

[0030] The process parameters of solvent deasphalting in the present invention cooperate synergistically, which is more conducive to further improving the effect of solvent deasphalting and can further increase the yield of deasphalted oil to more than 80%.

[0031] A preparation method of a rubber plasticizer includes the following steps:

[0032] (1) Solvent deasphalting is carried out on naphthenic residue oil to obtain deasphalted oil and deoiled asphalt;

[0033] The solvent used in solvent deasphalting is one or several mixed solvents of pentane, isopentane and hexane, preferably pentane;

[0034] The top temperature of the solvent deasphalting extraction column is 130°C to 160°C, the bottom temperature is 120°C to 150°C, and the solvent-to-oil ratio is 4:1 to 10:1;

[0035] (2) The obtained deasphalted oil is subjected to deep vacuum distillation to obtain fractions with a boiling point ≤520°C and fractions with a boiling point ≥520°C;

[0036] Deep vacuum distillation controls the BaP content and PAHs content of the heavy components in the deasphalted oil, and moderately reduces the PCA content, so as to improve the C A value;

[0037] (3) The obtained fractions with a boiling point ≤520°C are subjected to hydrotreating, isodewaxing and finishing to obtain rubber plasticizer - naphthenic base mineral oil product;

[0038] (4) The obtained fractions with a boiling point ≥520°C are directly used as rubber plasticizer - aromatic base mineral oil product.

[0039] 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.

[0040] In the present invention, the rubber plasticizer - aromatic base mineral oil product (BaP content ≤1mg / kg, PAHs content ≤2mg / kg) is far lower than the limit substance requirements for environmentally friendly processing oils in the "Technical Specification for Green Design Product Evaluation - Automotive Tires" (i.e., the requirements of BaP content ≤1mg / kg and PAHs content ≤10mg / kg), and its environmental performance is more prominent. At the same time, its C A value is greater than 31%, and its compatibility with rubber compounds, carbon black, etc. is more excellent during tire preparation, which is beneficial to endowing the tire with more excellent use performance.

[0041] It should be noted that the C A value of the rubber plasticizer - aromatic base mineral oil product is ≥31%. Analyzed by GC-MS method, its BaP (benzo[a]pyrene) content <1mg / kg, PAHs content <2mg / kg. The PAHs content refers to 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.

[0042] In the present invention, the rubber plasticizer - naphthenic base mineral oil product can meet the standard of HG / T 5781-2021 Rubber Plasticizer High Viscosity Mineral Oil, and its kinematic viscosity at 100 °C is above 18 mm 2 / s, and at the same time its C N value ≥ 45%.

[0043] 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.

[0044] Example 1

[0045] A preparation method of a rubber plasticizer includes the following steps:

[0046] (1) Using Suizhong 36-1 vacuum residue as raw material, adopting the pentane deasphalting process to obtain light deasphalted oil A1 (deasphalted oil) and deasphalted pitch A2;

[0047] In the pentane deasphalting process, the top temperature of the extraction column is 145 °C, the bottom temperature is 135 °C, and the adopted solvent-to-oil ratio is 7:1;

[0048] (2) Subjecting the light deasphalted oil A1 to vacuum distillation to obtain a fraction B1 with a temperature ≤ 520 °C and a fraction B2 with a temperature ≥ 520 °C;

[0049] (3) Using a commercially available hydrotreating catalyst, isodewaxing catalyst, and noble metal post-refining catalyst for the fraction B1, and performing hydrotreating, isodewaxing, and supplementary refining, that is, producing a high-viscosity rubber plasticizer - naphthenic base mineral oil product B11 by a three-stage high-pressure hydrogenation process;

[0050] (4) Using the fraction B2 as a rubber plasticizer - aromatic base mineral oil product.

[0051] In this example, the properties of the raw materials and the obtained products are shown in Table 1.

[0052] Table 1 Properties of Raw Materials and Products

[0053]

[0054] Example 2

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

[0056] (1) Using Qinhuangdao 32-6 vacuum residue as raw material, adopting the pentane deasphalting process to obtain light deasphalted oil C1 (deasphalted oil) and deasphalted pitch C2;

[0057] In the pentane deasphalting process, the top temperature of the extraction column is 145 °C, the bottom temperature is 135 °C, and the adopted solvent-to-oil ratio is 7:1;

[0058] (2) Subject the light deoiled C1 to vacuum distillation to obtain a fraction D1 with a temperature ≤ 520 °C and a fraction D2 with a temperature ≥ 520 °C;

[0059] (3) Subject the fraction D1 to hydrotreating, isodewaxing, and supplementary refining using commercially available hydrotreating catalysts, isodewaxing catalysts, and noble metal post-refining catalysts, i.e., produce a high-viscosity rubber plasticizer - naphthenic base mineral oil product D11 through a three-stage high-pressure hydrogenation process;

[0060] (4) Use the fraction D2 as a rubber plasticizer - aromatic base mineral oil product.

[0061] In this example, the properties of the raw materials and the products obtained therefrom are shown in Table 2.

[0062] Table 2 Properties of Raw Materials and Their Products

[0063]

[0064] Comparative Example 1

[0065] The difference between this comparative example and Example 1 is that in step (1), the Suizhong 36-1 vacuum residue is replaced with the Lufeng 12-3 vacuum residue;

[0066] For the remaining steps and their process parameters, refer to Example 1.

[0067] Compared with Example 1, the defect of this comparative example is that the Lufeng 12-3 vacuum residue is a paraffin-based crude oil fraction, and the light deoiled product obtained by pentane deasphalting has a low aromatic hydrocarbon content and cannot produce a high-aromatic rubber plasticizer product that meets the index requirements.

[0068] Comparative Example 2

[0069] The difference between this comparative example and Example 1 is that in step (2), the fractions obtained by vacuum distillation are a fraction B1 with a temperature ≤ 480 °C and a fraction B2 with a temperature ≥ 480 °C;

[0070] For the remaining steps and their process parameters, refer to Example 1.

[0071] Compared with Example 1, the defect of this comparative example is that the fraction B2 contains a relatively high content of eight carcinogenic aromatic hydrocarbons, and the BaP content and PAHs content do not meet the index requirements.

[0072] From the above examples and comparative examples, it can be seen that the present invention uses a typical naphthenic oil of CNOOC as the raw material. After solvent deasphalting and vacuum distillation, the fraction with a temperature ≥ 520 °C in the light deoiled product can be used as high-C AValue rubber plasticizer - aromatic-based mineral oil product, with excellent environmental protection indicators and very low content of 8 kinds of aromatic hydrocarbons; the fraction with a distillation range of ≤520°C in light deoiled oil adopts a three-stage high-pressure hydrogenation process to obtain a rubber plasticizer - naphthenic-based mineral oil product with excellent performance, and its kinematic viscosity at 100°C is above 18 mm 2 / s, and it has a relatively high flash point, and can be used as a naphthenic rubber plasticizer product with ultra-low volatility.

[0073] 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 it; 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 rubber plasticizer, characterized in that, It includes the following steps: Subject the naphthenic vacuum residue to solvent deasphalting to obtain deasphalted oil. Take the deasphalted oil and perform vacuum distillation to obtain a fraction with a temperature ≤520°C and a fraction with a temperature ≥520°C. Take the fraction with a temperature ≤520°C and perform hydrotreating, isodewaxing, and supplementary refining to obtain a rubber plasticizer - naphthenic base mineral oil product; and / or, use the fraction with a temperature ≥520°C as a rubber plasticizer - aromatic base mineral oil product.

2. The preparation method according to claim 1, characterized in that, The naphthenic vacuum residue includes Suizhong 36-1 vacuum residue, Qinhuangdao 32-6 vacuum residue, and Jinzhou 9-3 vacuum residue; Preferably, the solvent used in the solvent deasphalting includes at least one of pentane, isopentane, and hexane, and preferably pentane.

3. The preparation method according to claim 2, wherein, In the solvent deasphalting, 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 is 4:1 to 10:

1.

5. The preparation method according to any one of claims 1-4, characterized in that, The yield of the deasphalted oil is above 80%.

6. A rubber plasticizer prepared by the preparation method according to any one of claims 1-5.

7. The rubber plasticizer according to claim 6, characterized in that, The C value of the rubber plasticizer - naphthenic mineral oil product N ≥ 45%.

8. The rubber plasticizer according to claim 7, characterized in that, The kinematic viscosity of the rubber plasticizer - naphthenic mineral oil product at 100 °C is above 18 mm 2 / s.

9. The rubber plasticizer according to claim 6, wherein The C of the rubber plasticizer - aromatic mineral oil product A value ≥ 31%.

10. The rubber plasticizer according to claim 9, characterized in that, The BaP content of the rubber plasticizer - aromatic base mineral oil product is ≤1 mg / kg, and the PAHs content is ≤2 mg / kg.

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