Production method of rubber plasticizer aryl mineral oil

Abstract

The invention relates to the technical field of petrochemical engineering, in particular to a production method of aryl mineral oil as a rubber plasticizer. The method comprises the following steps: taking lubricating oil solvent extract oil and lubricating oil distillate oil as raw material oil, taking furfural as a solvent, carrying out extraction in a counter-current extraction tower, and adopting a two-tower extraction process to obtain the aryl environment-friendly rubber plasticizer. According to the invention, the content of polycyclic aromatic hydrocarbons in the raw material oil can be greatly reduced, the content of environment-friendly low-cyclic aromatic hydrocarbons is reserved, the yield of the produced environment-friendly rubber plasticizer product is higher, and the CA value of the product is higher.

Description

Technical Field:

[0001] The present invention relates to the technical field of petrochemical industry, and particularly relates to a production method of aromatic-based mineral oil as a rubber plasticizer. Background Art:

[0002] The oils used in the process of rubber synthesis or rubber processing are collectively referred to as rubber oils, also known as rubber plasticizers. Rubber plasticizers are one of the important raw materials for rubber processing, and are divided into aromatic type, naphthenic type and paraffinic type. Among them, aromatic type oils have the characteristics of high density, high viscosity, good affinity and excellent processing performance, and have excellent properties such as good compatibility with rubber and the ability to endow tires with good wet skid resistance. This type of oil is represented by the extracted oil (DAE) refined by lubricating oil solvent. It contains a large amount of polycyclic aromatic hydrocarbon compounds, and polycyclic aromatic hydrocarbons have toxicities such as carcinogenicity and damage to the reproductive system. Therefore, they are limited in use in some developed countries. The European Union issued Directive 2005 / 69 / EC on December 9, 2005, requiring that since January 1, 2010, in all tires and rubber products entering the EU market, the total amount of 8 harmful polycyclic aromatic hydrocarbons listed in the filling oil used shall not exceed 10 mg per kilogram, and the content of benzo[a]pyrene (BaP) shall not exceed 1 mg per kilogram.

[0003] In recent years, the domestic tire industry has developed rapidly. As a major tire manufacturing country in the world, tire oil has become the largest application field of rubber oil, and more than one-third of domestic tires are exported overseas. At present, there are mainly two types of domestic environmental protection rubber plasticizers: aromatic-based mineral oil and naphthenic-based mineral oil. Among them, aromatic-based mineral oil is mainly used in tires and related products and as the filling oil for rubber.

[0004] In terms of the domestic market, with the continuous increase in automobile production, the tire production has also been showing a relatively fast upward trend. With the increase in investment by international well-known tire enterprises in China, the increase in the export volume of radial tires of domestic large enterprises, and the trend of developing environmentally friendly green products, environmental protection rubber plasticizers, as environmental protection rubber filling oils used in oil-filled rubber and tire production, will inevitably attract great attention, and their demand will also increase.

[0005] In the production of environmentally friendly rubber plasticizers, some production methods have been proposed at home and abroad. For example, CN200910050832.3 proposes to use solvents such as furfural and phenol to extract and remove polycyclic aromatic hydrocarbons in the raw material oil, and then recover the solvent to obtain environmentally friendly aromatic oil. The problem with this method is that it is difficult to produce products with high yield, high aromatic hydrocarbon content and quality meeting EU requirements by simply using traditional solvent extraction process. CN200910088932.5 proposes another refining method, that is, the third-stage reduced crude oil and furfural are in countercurrent contact in the extraction column as described above, and the refined oil is obtained after recovering the solvent. Then the refined oil is extracted again, and the extract oil obtained from the secondary extraction is the environmentally friendly rubber oil. This technology still has problems such as low yield of environmentally friendly oil and low aromatic hydrocarbon content of environmentally friendly oil (i.e., low aromatic carbon rate C A low).

[0006] The invention patent CN103382399B, a production method of a high-performance environmentally friendly rubber oil, the raw materials of the present invention are a compound of two petroleum products, one is the extract oil of lubricating oil solvent refining, and the other is the lubricating oil fraction oil with higher aromatic hydrocarbon and naphthene hydrocarbon content. Using this compound raw material as the raw material for producing environmentally friendly rubber oil and adopting the conventional lubricating oil refining process, it is possible to trial-produce C A value between 15.0 - 25%, aromatic hydrocarbon content between 40.0 - 55%, benzo[a]pyrene less than 1 μg / g, total content of 8 specific polycyclic aromatic hydrocarbons less than 10 μg / g, and the yield is 20 - 30 percentage points higher than that of the environmentally friendly rubber oil obtained with pure lubricating oil solvent extract oil as the raw material.

[0007] Using the existing solvent refining technology, it is difficult to produce environmentally friendly rubber plasticizer products with a C A value above 25%. Therefore, there is an urgent expectation to develop a production method for high-aromatic-hydrocarbon environmentally friendly rubber plasticizers. Summary of the Invention:

[0008] The technical problem to be solved by the present invention is to provide a production method of aromatic-based mineral oil for rubber plasticizers, which can greatly reduce the content of polycyclic aromatic hydrocarbons in the raw material oil, retain the content of environmentally friendly less-ring aromatic hydrocarbons, and has a higher yield of the produced environmentally friendly rubber plasticizer products and a higher C A value.

[0009] The technical solution adopted by the present invention is: a production method of aromatic-based mineral oil for rubber plasticizers, which includes the following steps: using the extract oil of lubricating oil solvent and the lubricating oil fraction oil as the raw material oil, performing in a countercurrent extraction column, adopting a two-column extraction process, using furfural as the solvent, the extract oil of lubricating oil solvent in the raw material oil is mixed with the solvent furfural and enters the extraction column from the upper solvent inlet of the extraction column Ⅰ, and the other part of the lubricating oil fraction oil in the raw material oil enters the extraction column from the lower raw material inlet of the extraction column Ⅰ;

[0010] The raffinate at the top of Extraction Tower I enters Extraction Tower II as the raw material for Extraction Tower II from the raw material inlet at the lower part of Extraction Tower II. The solvent furfural enters Extraction Tower II from the solvent inlet at the upper part of Extraction Tower II. The raffinate is obtained at the top of Extraction Tower II, and after recovering the solvent, an aromatic-based environmental protection rubber plasticizer is obtained. The extract obtained at the bottoms of Extraction Tower I and Extraction Tower II is mixed and the solvent is recovered to obtain a secondary extract oil.

[0011] Further, the lubricating oil solvent extract oil satisfies an open flash point of not less than 200 °C, a kinematic viscosity at 100 °C of not less than 20.0 mm 2 / s, a C A value of not less than 35%, and a freezing point of not higher than 20 °C. If the freezing point is higher than 20 °C, solvent dewaxing treatment can be carried out.

[0012] Further, the lubricating oil fraction oil satisfies an open flash point of not less than 200 °C, a kinematic viscosity at 100 °C of not less than 20.0 mm 2 / s, a C A value of not less than 20%, and a freezing point of not higher than 20 °C. If the freezing point is higher than 20 °C, solvent dewaxing treatment can be carried out.

[0013] Further, the mass ratio of the lubricating oil fraction oil to the lubricating oil solvent extract oil in the raw material oil is 0.25 - 1:1.

[0014] Further, the top temperature of Extraction Tower I is 50 °C - 65 °C, the bottom temperature is 40 °C - 45 °C, and the mass ratio of the solvent entering Extraction Tower I to the raw material oil is 0.5 - 1:1.

[0015] Further, the top temperature of Extraction Tower II is 60 °C - 80 °C, the bottom temperature is 40 °C - 50 °C, and the mass ratio of the solvent entering Extraction Tower II to the raw material oil is 0.5 - 1:1.

[0016] The beneficial effects of the present invention are as follows: The present invention can greatly reduce the content of polycyclic aromatic hydrocarbons in the raw material oil, retain the content of environmentally friendly less-ring aromatic hydrocarbons, and the yield of the produced environmental protection rubber plasticizer product is higher and the C A value is higher. Description of the Drawings:

[0017] The following further describes the present invention in detail with reference to the drawings and specific embodiments.

[0018] Figure 1 is the process flow chart of the present invention.

[0019] The labels therein are respectively represented as follows: 1. Extraction Tower I; 2. Extraction Tower II; 3. Solvent for Extraction Tower I; 4. Lubricating Oil Solvent Extracted Oil; 5. Lubricating Oil Fraction Oil; 6. Raffinate of Extraction Tower I; 7. Extract of Extraction Tower I; 8. Solvent for Extraction Tower II; 9. Raffinate of Extraction Tower II; 10. Extract of Extraction Tower II. Detailed implementation method:

[0020] As Figure 1 shown, a production method of aromatic-based mineral oil for rubber plasticizer, the method includes the following steps: Using the two parts of lubricating oil solvent extracted oil 4 and lubricating oil fraction oil 5 as raw material oils, adopting a two-tower extraction process, carried out in a countercurrent extraction tower. The lubricating oil solvent extracted oil 4 in the raw material oil is mixed with the solvent 3 for Extraction Tower I and enters the extraction tower from the upper solvent inlet of Extraction Tower I. Another part of the lubricating oil fraction oil 5 in the raw material oil enters the extraction tower from the lower raw material inlet of Extraction Tower I; The raffinate 6 of Extraction Tower I enters the extraction tower from the lower raw material inlet of Extraction Tower II as the raw material of Extraction Tower II. The solvent 8 for Extraction Tower II enters the extraction tower from the upper solvent inlet of Extraction Tower II. The raffinate 9 of Extraction Tower II is recovered of the solvent to obtain the aromatic-based environmental protection rubber plasticizer. The extracts obtained at the bottoms of Extraction Tower I and Extraction Tower II are mixed and the solvent is recovered to obtain the secondary extracted oil.

[0021] Example 1

[0022] Using the furfural extracted oil of paraffin-based reduced fourth-line fraction dewaxed oil and naphthenic-based reduced third-line hydrotreated deacidified oil as raw material oils, with a mass ratio of 1:0.25, and the properties are shown in Table 1. Carried out in a countercurrent extraction tower, adopting a two-tower extraction process, using furfural as the solvent. The operating conditions of Extraction Tower I are: the top temperature of the tower is 50 °C, the bottom temperature of the tower is 40 °C, and the mass ratio of the furfural solvent entering Extraction Tower I to the total raw material oil is 0.5:1. The furfural extracted oil in the raw material is mixed with the solvent and enters the extraction tower from the solvent inlet of Extraction Tower I; The naphthenic-based reduced third-line hydrotreated deacidified oil enters the extraction tower from the lower raw material inlet of Extraction Tower I. The raffinate at the top of Extraction Tower I enters the extraction tower from the lower raw material inlet of Extraction Tower II as the raw material of Extraction Tower II. The solvent furfural enters the extraction tower from the upper solvent inlet of Extraction Tower II. The operating conditions of Extraction Tower II are: the top temperature of the tower is 60 °C, the bottom temperature of the tower is 40 °C, and the mass ratio of the furfural solvent entering Extraction Tower II to the total raw material oil is 0.8:1.0. After the refined liquid at the top of Extraction Tower II is recovered of the solvent, the environmental protection rubber plasticizer is obtained, and the properties are shown in Table 1. The extracts at the bottoms of Extraction Tower I and Extraction Tower II are mixed and the solvent is recovered to obtain the secondary extracted oil.

[0023] Comparative Example 1

[0024] The same feedstock oil, extraction process conditions and extraction column as in Example 1 are adopted, that is, the top temperature of Extraction Column I is 50°C, the bottom temperature is 40°C, the mass ratio of the solvent furfural entering Extraction Column I to the total feedstock oil is 0.5:1.0. The solvent enters the extraction column from the upper part of Extraction Column I. The total feedstock oil, namely the mixed oil of furfural extract oil and naphthenic minus three-line hydrodesulfurized oil, enters the extraction column from the lower raw material inlet of Extraction Column I. The raffinate of Extraction Column I enters Extraction Column II as the raw material from the lower raw material inlet. The solvent furfural enters Extraction Column II from the upper solvent inlet of Extraction Column II. The operating conditions of Extraction Column II are: the top temperature is 60°C, the bottom temperature is 40°C, and the mass ratio of the solvent furfural entering Extraction Column II to the total feedstock oil is 0.8:1.0. The refined liquid at the top of Extraction Column II is recovered of the solvent to obtain an environment-friendly rubber plasticizer, and its properties are shown in Table 1. The liquid withdrawn from the bottom of Extraction Column I and Extraction Column II is mixed and recovered of the solvent to obtain a secondary extract oil.

[0025] Example 2

[0026] Using the furfural extract oil of paraffin-based minus four-line dewaxed oil and naphthenic minus three-line hydrodesulfurized oil as the feedstock oil, with a mass ratio of 1.0:1, and its properties are shown in Table 2. It is carried out in a countercurrent extraction column, adopting a two-column extraction process, using furfural as the solvent. The operating conditions of Extraction Column I are: the top temperature is 65°C, the bottom temperature is 45°C, and the mass ratio of the solvent furfural entering Extraction Column I to the total feedstock oil is 1.0:1. The furfural extract oil in the raw material is mixed with the solvent and enters Extraction Column I from the upper solvent inlet of Extraction Column I; the naphthenic minus three-line hydrodesulfurized oil enters Extraction Column I from the lower raw material inlet of Extraction Column I. The raffinate at the top of Extraction Column I enters Extraction Column II as the raw material from the lower raw material inlet of the extraction column. The solvent furfural enters Extraction Column II from the upper solvent inlet of Extraction Column II. The operating conditions of Extraction Column II are: the top temperature is 80°C, the bottom temperature is 50°C, and the mass ratio of the solvent furfural entering Extraction Column II to the total feedstock oil is 0.5:1. The refined liquid at the top of Extraction Column II is recovered of the solvent to obtain an environment-friendly rubber plasticizer, and its properties are shown in Table 2. The liquid withdrawn from the bottom of Extraction Column I and Extraction Column II is mixed and recovered of the solvent to obtain a secondary extract oil.

[0027] Comparative Example 2

[0028] Using the same feedstock oil as in Example 2, adopting the production method of a high-performance environment-friendly rubber oil in CN103382399B, that is, conventional single-column extraction. The solvent furfural enters the extraction column from the upper part of the extraction column. The total feedstock oil, namely the mixed oil of furfural extract oil and naphthenic minus three-line hydrodesulfurized oil, enters the extraction column from the lower raw material inlet of the extraction column. The raffinate of the extraction column is recovered of the solvent to obtain an environment-friendly rubber plasticizer. The extraction conditions are: the top temperature is 65°C, the bottom temperature is 45°C, and the mass ratio of the solvent furfural to the feedstock oil is 1.2:1. Its properties are shown in Table 2. The liquid withdrawn from the bottom is mixed and recovered of the solvent to obtain a secondary extract oil.

[0029] Example 3

[0030] Using the hydrotreating and deacidifying oil of the third side stream of naphthenic base and the furfural extraction oil of the third side stream of naphthenic base as the feedstock, with a mass ratio of 0.5:1, and the properties are shown in Table 3. It is carried out in a countercurrent extraction tower, adopting a two-tower extraction process, using furfural as the solvent. The operating conditions of Extraction Tower I are: the top temperature is 55°C, the bottom temperature is 40°C, and the mass ratio of the solvent furfural entering Extraction Tower I to the total feedstock is 0.7:1. The furfural extraction oil in the feedstock is mixed with the solvent and enters Extraction Tower from the solvent inlet at the upper part of Extraction Tower I; the hydrotreating and deacidifying oil of the third side stream of naphthenic base enters Extraction Tower from the feedstock inlet at the lower part of Extraction Tower I. The raffinate at the top of Extraction Tower I enters Extraction Tower II as the feedstock from the feedstock inlet at the lower part of Extraction Tower II, and the solvent furfural enters Extraction Tower from the solvent inlet at the upper part of Extraction Tower II. The operating conditions of Extraction Tower II are: the top temperature is 70°C, the bottom temperature is 40°C, and the mass ratio of the solvent furfural entering Extraction Tower II to the total feedstock is 0.75:1. After the refined liquid at the top of Extraction Tower II recovers the solvent, an environment-friendly rubber plasticizer is obtained, and the properties are shown in Table 3. The extracts at the bottoms of Extraction Tower I and Extraction Tower II are mixed and the solvent is recovered to obtain a secondary extraction oil.

[0031] Comparative Example 3

[0032] Using the same feedstock, extraction process conditions and extraction tower as in Example 3, that is, the top temperature of Extraction Tower I is 55°C, the bottom temperature is 40°C, the mass ratio of the solvent furfural to the total feedstock is 0.7:1, the solvent enters Extraction Tower from the upper part of Extraction Tower I, the total feedstock, that is, the mixed oil of furfural extraction oil and hydrotreating and deacidifying oil of the third side stream of naphthenic base, enters Extraction Tower from the feedstock inlet at the lower part of Extraction Tower I. The raffinate of Extraction Tower I enters Extraction Tower II as the feedstock from the feedstock inlet at the lower part of Extraction Tower II, and the solvent furfural enters Extraction Tower from the solvent inlet at the upper part of Extraction Tower II. The operating conditions of Extraction Tower II are: the top temperature is 70°C, the bottom temperature is 40°C, and the mass ratio of the solvent furfural entering Extraction Tower II to the total feedstock is 0.75:1. After the refined liquid at the top of Extraction Tower II recovers the solvent, an environment-friendly rubber plasticizer is obtained, and the properties are shown in Table 3. The extracts at the bottoms of Extraction Tower I and Extraction Tower II are mixed and the solvent is recovered to obtain a secondary extraction oil.

[0033] Table 1 Properties of the Feedstock and Environment-Friendly Rubber Plasticizer in Example 1

[0034]

[0035] Table 2 Properties of the Feedstock and Environment-Friendly Rubber Filling Oil in Example 2

[0036]

[0037] Table 3 Properties of the Feedstock and Environment-Friendly Rubber Filling Oil in Example 3

[0038]

[0039] It can be seen from the product yields and properties of Table 1, Table 3, Example 1, Example 3, Comparative Example 1, and Comparative Example 3 that in the present invention, the extract oil in the raw material oil is added to the single-stage extraction solvent, and the fraction oil in the raw material enters the extraction tower from the raw material inlet. The raffinate is subjected to two-stage extraction. Compared with the conventional two-stage extraction, under the same conditions, not only can more polycyclic aromatic hydrocarbons be removed, but also the product yield and C A value can be increased. It can be seen from the product yields and properties of Table 2, Example 2, and Comparative Example 2 that this method adopts adding the extract oil in the raw material oil to the solvent, and the fraction oil in the raw material enters the extraction tower from the raw material inlet for two-stage extraction. Compared with the conventional single-stage extraction, under the same conditions, not only can more polycyclic aromatic hydrocarbons be removed, but also the product yield and C A value can be increased. Therefore, using the lubricating oil solvent extraction oil and the lubricating oil fraction oil as the raw material oil, environmental protection rubber plasticizer products with benzo[a]pyrene (BaP) less than 1 mg / kg, PCA less than 3%, and the total content of 8 harmful aromatic hydrocarbons less than 10 mg / kg can be produced by this method.

[0040] It can be understood that the above specific description of the present invention is only for explaining the present invention and is not limited to the technical solutions described in the embodiments of the present invention. Those of ordinary skill in the art should understand that the present invention can still be modified or equivalently replaced to achieve the same technical effect; as long as the use requirements are met, they are all within the protection scope of the present invention.

Claims

1. A production method of an aromatic-based mineral oil as a rubber plasticizer, characterized in that: The method comprises the following steps: using two parts of lube oil solvent-extracted oil and lube oil fraction oil as raw material oils, conducting in a countercurrent extraction tower, adopting a two-tower extraction process, using furfural as the solvent, mixing the lube oil solvent-extracted oil in the raw material oils with the solvent furfural and entering the extraction tower Ⅰ from the upper solvent inlet of the extraction tower Ⅰ, and entering the other part of the lube oil fraction oil in the raw material oils into the extraction tower Ⅰ from the lower raw material inlet of the extraction tower Ⅰ; The raffinate at the top of the extraction tower Ⅰ enters the extraction tower Ⅱ as the raw material of the extraction tower Ⅱ from the lower raw material inlet of the extraction tower Ⅱ, the solvent furfural enters the extraction tower Ⅱ from the upper solvent inlet of the extraction tower Ⅱ, the raffinate is obtained at the top of the extraction tower Ⅱ, and an aromatic-based environmental rubber plasticizer is obtained after recovering the solvent. The extract obtained at the bottoms of the extraction tower Ⅰ and the extraction tower Ⅱ is mixed and the solvent is recovered to obtain a secondary extract.

2. The production method of the aromatic-based mineral oil as the rubber plasticizer according to claim 1, characterized in that: The lubricating oil solvent-extracted oil meets the requirements that the flash point (open cup) is not less than 200 °C, the kinematic viscosity at 100 °C is not less than 20.0 mm 2 / s, the C A value is not less than 35%, and the freezing point is not higher than 20 °C. If the freezing point is higher than 20 °C, solvent dewaxing treatment can be carried out.

3. The production method of the aromatic-based mineral oil as the rubber plasticizer according to claim 1, characterized in that: The lubricating oil fraction satisfies the requirements that the open flash point is not less than 200 °C, the kinematic viscosity at 100 °C is not less than 20.0 mm 2 / s, and the C A value is not less than 20%, and the freezing point is not higher than 20 °C. If the freezing point is higher than 20 °C, solvent dewaxing treatment can be carried out.

4. The production method of the aromatic-based mineral oil as the rubber plasticizer according to claim 1, wherein: The mass ratio of the lube oil fraction oil to the lube oil solvent-extracted oil in the raw material oils is 0.25 - 1:

1.

5. The production method of the aromatic-based mineral oil as the rubber plasticizer according to claim 1, characterized in that: The temperature at the top of the extraction tower Ⅰ is 50°C - 65°C, the temperature at the bottom is 40°C - 45°C, and the mass ratio of the solvent entering the extraction tower Ⅰ to the raw material oil is 0.5 - 1:

1.

6. The production method of the aromatic-based mineral oil as the rubber plasticizer according to claim 1, wherein: The temperature at the top of the extraction tower Ⅱ is 60°C - 80°C, the temperature at the bottom is 40°C - 50°C, and the mass ratio of the solvent entering the extraction tower Ⅱ to the raw material oil is 0.5 - 1:1.

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