Production process of yellowing-resistant rubber plasticizer naphthenic mineral oil
Through the high-pressure hydrotreatment-isomerial dewaxing-hydrore purification combination process, the production process of rubber plasticizer cycloalkyl mineral oil is optimized, and the problems of environmental pollution and poor product quality in traditional processes are solved, and the product is achieved with high compatibility, excellent stability and good photothermal stability.
Patent Information
- Application Number
- CN202510158061.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-13
- Publication Date
- 2025-04-25
AI Technical Summary
The production process of traditional rubber plasticizer cycloalkyl mineral oil has problems such as environmental pollution, poor product quality and poor yellowing resistance.
The high-pressure hydrotreatment-isomerial dewaxing-hydrogenation purification combination process is adopted, and the carbon chain structure of the refined oil is optimized and controlled through four hydrogenation devices of different pressures, so that the cycloalkane content of the product is greater than 50%, and the ultraviolet light stability and thermal stability are both above +28.
It has achieved good compatibility with rubber, excellent stability performance, clean and friendly production environment, and its overall quality is better than the requirements of HG/T 5085-2016 standard, and has good photothermal stability and yellowing resistance.
Smart Images
Figure SMS_1 
Figure SMS_2
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of rubber and plastic plasticizing applications, and in particular to a production process of cycloalkyl mineral oil, a yellowing-resistant rubber plasticizer. Background Art
[0002] Rubber plasticizer cycloalkane mineral oil is a fractionation product of petroleum. Its main components are compounds such as alkanes, cycloalkanes and very small amounts of aromatic hydrocarbons. It plays an important role as an auxiliary agent in the rubber industry, which can increase the plasticity, flexibility, tensile properties of rubber and make it easier to process.
[0003] An ideal rubber plasticizer requires good compatibility with rubber and good processing performance; strong antioxidant stability, excellent low-temperature fluidity, and high-temperature safety performance; low content of impurities such as acid, alkali, sulfur, nitrogen, and ash, little pollution to the environment, and no threat to human health. Therefore, rubber plasticizers must be deeply refined products from petroleum distillates.
[0004] The yellowing-resistant naphthenic mineral oil of rubber plasticizer requires more stringent technical indicators than ordinary rubber plasticizer naphthenic mineral oil, which is reflected in the good light and heat stability on the basis of ensuring a high CN value. The traditional processing technology adopts acid-base refining-kaolin refining. This process will produce a large amount of waste acid and alkali, waste kaolin, and cause serious environmental pollution. The product yield is low, the color is dark, and the quality is poor. Alternatively, a combined process of hydrogenation refining-secondary solvent refining-kaolin supplementary refining is adopted. This process is long, the processing cost is high, there is also waste kaolin pollution, the product color is light yellow, and the use of rubber plasticizers will cause the yellowing resistance of rubber to deteriorate.
[0005] According to the development trend of clean and environmentally friendly products, this invention adopts a combined process of high-pressure hydrogenation treatment - isomerization dewaxing - hydrogenation refining, which has the advantages of good compatibility between the product and rubber, excellent stability, and a clean and friendly production environment. Summary of the invention
[0006] The purpose of the present invention is to provide a production process of yellowing-resistant rubber plasticizer naphthenic mineral oil in view of the traditional production process. The product is refined by four-stage hydrogenation devices with different pressures, and the carbon chain structure of the refined oil is optimized and controlled according to the requirements of naphthenic characteristics, so that the naphthenic content of the product is greater than 50%, and the ultraviolet light stability and thermal stability are both above +28.
[0007] A production process of cycloalkyl mineral oil as a yellowing-resistant rubber plasticizer, characterized in that it comprises the following steps: S1, subjecting the crude oil to hydrodeacidification treatment, performing hydrodeacidification reaction at a hydrogen pressure of 6.0-7.0 MPa and a reaction temperature of 320-390° C. to obtain 1# refined oil; S2, subjecting the 1# refined oil obtained in S1 to high-pressure hydrogenation treatment, and performing deep hydrogenation reaction at a hydrogen pressure of 14.0-19.0 MPa and a reaction temperature of 290-350° C. to obtain 2# refined oil; S3, the 2# refined oil obtained in S2 enters the medium-pressure hydroisomerization treatment, performs the hydroisomerization reaction at a hydrogen pressure of 9.0-12.0 MPa and a reaction temperature of 300-350° C., and then enters the post-refining reactor, performs the hydrorefining of the isomerization reaction product at 250-290° C., and obtains 3# refined oil; S4, the refined oil obtained in S3 is fed into a high-pressure hydrotreating device, and subjected to deep hydrogenation reaction at a hydrogen pressure of 14.0-19.0 MPa and a reaction temperature of 200-300° C. to obtain 4# refined oil; S5. Add the 4# refined oil obtained in S4 to a stripping tower, use steam stripping to remove light components, and then use a vacuum dryer to remove moisture to obtain a yellowing-resistant rubber plasticizer cycloalkyl mineral oil.
[0008] Preferably, the UV stability of the yellowing-resistant rubber plasticizer cycloalkyl mineral oil is above +28 and the thermal stability is above +28.
[0009] Preferably, RS-2000 catalyst is used in S1 for desulfurization, denitrogenation and deacidification.
[0010] Preferably, RL-2+RJW-3 catalyst is used in S2 for aromatic saturation and trace impurity removal.
[0011] Preferably, S3 uses RIW-30+RLF-20 catalyst for isomerization decondensation and deep refining.
[0012] Preferably, RLF-20 catalyst is used in S4 for olefin saturation and aromatic saturation.
[0013] Preferably, the high pressure hydrogenation treatment in S2 is carried out by respectively loading RL-2 catalyst and RJW-3 catalyst in a series-connected hydrogenation reactor and a refining reactor to carry out hydrogenation and refining, so as to ensure that the CN value of the 2# refined oil is above 50.
[0014] Preferably, high pressure hydrogenation refining is performed in S4 to make the 4# refined oil meet the standard requirements of food grade white oil.
[0015] The advantages of the present invention are as follows: the overall quality of the yellowing-resistant rubber plasticizer naphthenic mineral oil is better than the standard requirements of HG / T 5085-2016 "Rubber Plasticizer Naphthenic Mineral Oil", and its ultraviolet light stability is +30, and its thermal stability is +30. The CN value of the product is greater than 50%, and it has good naphthenic characteristics. At the same time, the aromatic content of the product is extremely low, and the easy carbide test is passed. The production process and product performance are clean and friendly to human health. DETAILED DESCRIPTION
[0016] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments.
[0017] In the description of the embodiments of the present invention, it is also necessary to explain that, unless otherwise clearly specified and limited, the terms "setting" and "connection" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.
[0018] <Example 1> S1. The crude oil is subjected to a hydrodeacidification treatment. The hydrodeacidification reaction is carried out at a hydrogen pressure of 6.3 MPa and a reaction temperature of 335°C to obtain 1# refined oil; S2, subjecting the 1# refined oil obtained in S1 to high-pressure hydrogenation treatment, and performing deep hydrogenation reaction at a hydrogen pressure of 18.0 MPa and a reaction temperature of 340°C to obtain 2# refined oil; S3. The 2# refined oil obtained in S2 is added to the medium-pressure hydroisomerization treatment, and the hydroisomerization reaction is carried out at a hydrogen pressure of 10.5 MPa and a reaction temperature of 342°C. Then it enters the post-refining reactor at a reaction temperature of 284°C, and the isomerization reaction product is hydrorefined to obtain 3# refined oil.
[0019] S4. The refined oil obtained in S3 is fed into a high-pressure hydrogenation refining device for deep hydrogenation reaction at a hydrogen pressure of 18.0 MPa and a reaction temperature of 210° C. to obtain 4# refined oil.
[0020] S5, adding the refined oil obtained in S4 to a stripping tower, using steam stripping to remove light components, and then removing water through a vacuum dryer to obtain a yellowing-resistant rubber plasticizer naphthenic mineral oil. The yellowing-resistant rubber plasticizer naphthenic mineral oil has an ultraviolet light stability of more than +28 and a thermal stability of more than +28.
[0021] RS-2000 catalyst is used in S1 for desulfurization, denitrogenation and deacidification.
[0022] RL-2+RJW-3 catalysts are used in S2 for aromatic saturation and trace impurity removal. The high-pressure hydrogenation treatment in S2 uses a series of hydrogenation reactors and refining reactors to load RL-2 catalysts and RJW-3 catalysts for hydrogenation and refining, respectively, to ensure that the CN value of 2# refined oil is above 50.
[0023] S3 uses RIW-30+RLF-20 catalysts, RIW-30 catalyst is used for isomerization decondensation and deep refining, and RLF-20 catalyst is used for hydrofining.
[0024] RLF-20 catalyst is used in S4 for olefin saturation and aromatic saturation. High pressure hydrofining in S4 makes 4# refined oil meet the standard requirements of food grade white oil.
[0025] <Example 2> S1. The crude oil is subjected to a hydrodeacidification treatment. The reactor is subjected to a hydrogen pressure of 6.3 MPa and a reaction temperature of 336°C to perform a hydrodeacidification reaction to obtain 1# refined oil; S2, the 1# refined oil obtained in S1 is subjected to high-pressure hydrogenation treatment, and the reactor is subjected to deep hydrogenation reaction at a hydrogen pressure of 18.5 MPa and a reaction temperature of 335°C to obtain 2# refined oil; S3. The 2# refined oil obtained in S2 is added to the medium-pressure hydroisomerization treatment, and the reactor carries out the hydroisomerization reaction at a hydrogen pressure of 10.5 MPa and a reaction temperature of 334°C. Then it enters the post-refining reactor, and the isomerization reaction product is hydrorefined at 288°C to obtain 3# refined oil.
[0026] S4. The refined oil obtained in S3 is fed into a high-pressure hydrogenation refining device for deep hydrogenation reaction at a hydrogen pressure of 18.0 MPa and a reaction temperature of 220° C. to obtain 4# refined oil.
[0027] S5, adding the refined oil obtained in S4 to a stripping tower, using steam stripping to remove light components, and then removing water through a vacuum dryer to obtain a yellowing-resistant rubber plasticizer naphthenic mineral oil. The yellowing-resistant rubber plasticizer naphthenic mineral oil has an ultraviolet light stability of more than +28 and a thermal stability of more than +28.
[0028] RS-2000 catalyst is used in S1 for desulfurization, denitrogenation and deacidification.
[0029] RL-2+RJW-3 catalysts are used in S2 for aromatic saturation and trace impurity removal. The high-pressure hydrogenation treatment in S2 uses a series of hydrogenation reactors and refining reactors to load RL-2 catalysts and RJW-3 catalysts for hydrogenation and refining, respectively, to ensure that the CN value of 2# refined oil is above 50.
[0030] S3 uses RIW-30+RLF-20 catalysts, RIW-30 catalyst is used for isomerization decondensation and deep refining, and RLF-20 catalyst is used for hydrofining.
[0031] RLF-20 catalyst is used in S4 for olefin saturation and aromatic saturation. High pressure hydrofining in S4 makes 4# refined oil meet the standard requirements of food grade white oil.
[0032] <Experimental test data> The product in Example 1 was commissioned to Hubei Product Quality Supervision and Inspection Institute for testing. The overall quality was better than the standard requirements of HG / T 5085-2016 "Rubber Plasticizer Cycloalkyl Mineral Oil", and met the production and use requirements of high-grade SBS styrene thermoplastic elastomers and adhesives. The test results are shown in Table 1.
[0033] Table 1 Rubber plasticizer naphthenic mineral oil test report
[0034] The product in Example 2 was commissioned to Hangzhou Xike Testing Technology Co., Ltd. for testing. The overall quality was better than the standard requirements of HG / T5085-2016 "Rubber Plasticizer Cycloalkane Mineral Oil", among which 16 polycyclic aromatic hydrocarbons (PAHs) were not detected. The test results are shown in Table 2.
[0035] Table 2 Analysis of polycyclic aromatic hydrocarbons content in naphthenic mineral oil of rubber plasticizer
[0036] Note: ND = Not Detected (< Detection Limit) The product meets the requirements of HG / T 5085-2016 "Rubber Plasticizer Cycloalkyl Mineral Oil" standard, and can be further customized according to the needs of downstream application fields. Through flexible and precise control of reaction temperature and reaction pressure, the product's internal indicators such as aniline point, kinematic viscosity (100°C), carbon type distribution, polycyclic aromatic hydrocarbon content, easily carbonized products, heavy metal content and other indicators meet the customization requirements. The product has a stable production process and quality, low aromatic content, does not contain harmful substances such as condensed aromatic hydrocarbons, and has good light and thermal stability. The product quality reaches or exceeds the level of similar imported products.
[0037] The above implementation cases are only for illustrating the technical solutions and features of the present invention, and their purpose is to enable people familiar with the technology to implement them better. They cannot be used to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention are within the protection scope of the present invention, and those not described in detail are prior art.
Claims
1. A production process of cycloalkyl mineral oil as a yellowing-resistant rubber plasticizer, characterized in that: The following steps are involved: S1, subjecting the crude oil to hydrodeacidification treatment, performing hydrodeacidification reaction at a hydrogen pressure of 6.0-7.0 MPa and a reaction temperature of 320-390° C. to obtain 1# refined oil; S2, subjecting the 1# refined oil obtained in S1 to high-pressure hydrogenation treatment, and performing deep hydrogenation reaction at a hydrogen pressure of 14.0-19.0 MPa and a reaction temperature of 290-350° C. to obtain 2# refined oil; S3, the 2# refined oil obtained in S2 enters the medium-pressure hydroisomerization treatment, performs the hydroisomerization reaction at a hydrogen pressure of 9.0-12.0 MPa and a reaction temperature of 300-350° C., and then enters the post-refining reactor, performs the hydrorefining of the isomerization reaction product at 250-290° C., and obtains 3# refined oil; S4, the refined oil obtained in S3 is fed into a high-pressure hydrotreating device, and subjected to deep hydrogenation reaction at a hydrogen pressure of 14.0-19.0 MPa and a reaction temperature of 200-300° C. to obtain 4# refined oil; S5. Add the 4# refined oil obtained in S4 to a stripping tower, use steam stripping to remove light components, and then use a vacuum dryer to remove moisture to obtain a yellowing-resistant rubber plasticizer cycloalkyl mineral oil.
2. The production process of a yellowing-resistant rubber plasticizer naphthenic mineral oil according to claim 1, characterized in that: The ultraviolet light stability of the yellowing-resistant rubber plasticizer cycloalkyl mineral oil is above +28, and the thermal stability is above +28.
3. The production process of a yellowing-resistant rubber plasticizer naphthenic mineral oil according to claim 1, characterized in that: RS-2000 catalyst is used in S1 for desulfurization, denitrogenation and deacidification.
4. The production process of a yellowing-resistant rubber plasticizer naphthenic mineral oil according to claim 1, characterized in that: RL-2+RJW-3 catalyst is used in S2 for aromatic saturation and trace impurity removal.
5. The production process of a yellowing-resistant rubber plasticizer naphthenic mineral oil according to claim 1, characterized in that: S3 uses RIW-30+RLF-20 catalyst for isomerization decondensation and deep refining.
6. The production process of a yellowing-resistant rubber plasticizer naphthenic mineral oil according to claim 1, characterized in that: RLF-20 catalyst is used in S4 for olefin saturation and aromatic saturation.
7. The production process of a yellowing-resistant rubber plasticizer naphthenic mineral oil according to claim 1, characterized in that: The S2 medium- and high-pressure hydroprocessing uses a series-connected hydrogenation reactor and a refining reactor to be loaded with RL-2 catalyst and RJW-3 catalyst respectively for hydrogenation and refining, ensuring that the CN value of 2# refined oil is above 50.
8. The production process of a yellowing-resistant rubber plasticizer naphthenic mineral oil according to claim 1, characterized in that: S4 medium and high pressure hydrogenation refining makes 4# refined oil meet the standard requirements of food grade white oil.