Method for producing aryl environment-friendly rubber plasticizer

Abstract

The invention belongs to the technical field of petrochemical engineering, and particularly relates to a method for producing an aromatic environment-friendly rubber plasticizer, which is characterized in that a two-tower extraction process is adopted, one part of raw oil is mixed with a solvent and then enters from the upper part of an extraction tower I, and the other part enters from the lower part of the extraction tower I; raffinate at the top of the extraction tower I serves as a raw material of an extraction tower II and enters the extraction tower II from a raw material inlet, a solvent furfural enters the extraction tower II from a solvent inlet in the upper portion of the extraction tower II, raffinate is obtained at the top of the extraction tower II, and after the solvent is recycled, the aryl environment-friendly rubber plasticizer is obtained; and recovering the solvent to obtain secondary extract oil. According to the invention, a double-tower extraction mode is adopted, and the lubricating oil distillate oil or solvent extract oil is taken as a raw material, so that the content of polycyclic aromatic hydrocarbon in the raw material oil can be greatly reduced, and the content of environment-friendly low-cyclic aromatic hydrocarbon is reserved, so that the produced environment-friendly rubber plasticizer product is higher in yield and higher in CA value, and meets the requirements of tire oil.

Description

Technical Field

[0001] The present invention belongs to the technical field of petrochemical industry, and particularly relates to a method for producing an aromatic-based environment-friendly 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 extraction oil (DAE) refined by lubricating oil solvent, which contains a large amount of polycyclic aromatic hydrocarbon compounds. Polycyclic aromatic hydrocarbons are toxic such as carcinogenic and damaging the reproductive system. The European Union issued Directive 2005 / 69 / EC on December 9, 2005, requiring that since January 1, 2010, for all tires and rubber products entering the EU market, the total amount of 8 harmful polycyclic aromatic hydrocarbons listed in the rubber plasticizer 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, China's 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 environmentally friendly rubber plasticizers for tires: aromatic-based mineral oil and naphthenic-based mineral oil. Among them, aromatic-based mineral oil is mainly used in tire treads and related products as well as oil filling of synthetic 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 companies in China, the increase in the export volume of radial tires of domestic large enterprises and the trend of developing environmentally friendly green products, environmentally friendly rubber plasticizers, as the main raw materials 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 content, and meeting the EU environmental protection requirements by simply using the 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 subjected to secondary extraction, and the extract 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 content of environmentally friendly oil (i.e., low aromatic carbon rate C A low).

[0006] It is difficult to produce environmentally friendly rubber plasticizer products with a C A value of more than 25% using the existing solvent refining technology. Therefore, there is an urgent expectation to develop a production method for high-aromatic environmentally friendly rubber plasticizers. Summary of the Invention

[0007] The purpose of the present invention is to provide a method for producing aromatic-based environmentally friendly rubber plasticizers. By adopting a two-column extraction method, using lubricating oil fraction oil or solvent extract oil as raw materials, the content of polycyclic aromatic hydrocarbons in the raw material oil is greatly reduced, and the content of environmentally friendly less-ring aromatic hydrocarbons is retained.

[0008] The present invention is realized by the following technical solutions:

[0009] The method for producing aromatic-based environmentally friendly rubber plasticizers of the present invention is characterized in that lubricating oil fraction oil or solvent extract oil is used as the raw material oil, furfural is used as the solvent, and it is carried out in a countercurrent extraction column, adopting a two-column extraction process,

[0010] A part of the raw material oil is mixed with the solvent and enters Extraction Column I from the upper part of Extraction Column I, and another part enters Extraction Column I from the lower part of Extraction Column I. The raffinate at the top of Extraction Column I enters Extraction Column II from the lower raw material inlet of Extraction Column II as the raw material of Extraction Column II. The solvent furfural enters Extraction Column II from the upper solvent inlet of Extraction Column II. The raffinate is obtained at the top of Extraction Column II, and the aromatic-based environmentally friendly rubber plasticizer is obtained after recovering the solvent. The raffinates at the bottoms of Extraction Column I and Extraction Column II are mixed, and the secondary extract is obtained after recovering the solvent.

[0011] The lubricating oil fraction oil or 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 13.0%, and a freezing point of not higher than 20 °C.

[0012] The mass ratio of the part of the feedstock oil mixed with the solvent to all of the feedstock oil is from 0.1:1 to 0.9:1.

[0013] The furfural extraction conditions are as follows: the top temperature of Extraction Tower I is 45°C to 90°C, the bottom temperature of Extraction Tower I is 40°C to 50°C, and the mass ratio of the solvent to the feedstock oil is 0.3:1 to 1.0:1; the top temperature of Extraction Tower II is 60°C to 90°C, the bottom temperature of Extraction Tower II is 40°C to 60°C, and the mass ratio of the solvent to the feedstock oil is 0.5:1 to 1.0:1.

[0014] Advantages of the present invention:

[0015] The method for producing an aromatic-based environmentally friendly rubber plasticizer of the present invention adopts a two-tower extraction method, using a lubricating oil fraction oil or a solvent-extracted oil as the raw material, which can greatly reduce the polycyclic aromatic hydrocarbon content in the raw material oil and retain the environmentally friendly less-ring aromatic hydrocarbon content, thereby making the yield of the produced environmentally friendly rubber plasticizer product higher and the C A value higher, meeting the requirements of tire oil. Description of the Drawings

[0016] Figure 1 is a process flow chart of the present invention.

[0017] The reference numerals therein are respectively represented as: 1, feedstock oil of Extraction Tower I; 2, solvent of Extraction Tower I; 3, raffinate at the top of Extraction Tower I; 4, extract at the bottom of Extraction Tower I; 5, raffinate at the top of Extraction Tower II; 6, extract at the bottom of Extraction Tower II; 7, solvent of Extraction Tower II; 8, Extraction Tower I; 9, Extraction Tower II. Detailed Embodiments

[0018] The following further illustrates the detailed embodiments of the present invention with reference to the drawings.

[0019] As Figure 1 shown, the method for producing an aromatic-based environmentally friendly rubber plasticizer of the present invention is characterized in that a lubricating oil fraction oil or a solvent-extracted oil is used as the raw material oil, furfural is used as the solvent, and it is carried out in a countercurrent extraction tower, adopting a two-tower extraction process,

[0020] A part of the raw material oil 1 is mixed with the solvent 2 and then enters Extraction Tower I 8 from the upper part of Extraction Tower I 8, and another part enters Extraction Tower I 8 from the lower part of Extraction Tower I 8. The raffinate 3 at the top of Extraction Tower I enters Extraction Tower II 9 from the lower raw material inlet of Extraction Tower II 9 as the raw material of Extraction Tower II 9. The furfural solvent 7 of Extraction Tower II enters Extraction Tower II 9 from the upper solvent inlet of Extraction Tower II 9. The raffinate 5 is obtained at the top of Extraction Tower II 9, and after recovering the solvent, an aromatic-based environmentally friendly rubber plasticizer is obtained. The extract 4 at the bottom of Extraction Tower I and the extract 6 at the bottom of Extraction Tower II are mixed, and after recovering the solvent, a secondary extracted oil is obtained.

[0021] The lubricating oil fraction or solvent-extracted oil described above satisfies the conditions 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, the C A value is not less than 13.0%, and the freezing point is not higher than 20 °C. If the freezing point is higher than 20 °C, dewaxing treatment is required.

[0022] The mass ratio of the part where the raw material oil 1 is mixed with the solvent 2 to all the raw material oil is 0.1:1 to 0.9:1.

[0023] The furfural extraction conditions are as follows: the top temperature of the extraction tower I 8 is 45 °C to 90 °C, the bottom temperature of the extraction tower I 8 is 40 °C to 50 °C, and the mass ratio of the solvent 2 to the raw material oil 1 is 0.3:1 to 1.0:1; the top temperature of the extraction tower II 9 is 60 °C to 90 °C, the bottom temperature of the extraction tower II 9 is 40 °C to 60 °C, and the mass ratio of the solvent 7 to the raw material oil (both refer to the initial raw material) is 0.5:1 to 1.0:1.

[0024] Examples

[0025] Example 1

[0026] Using the furfural extract of the dewaxed oil of the fourth reduced line of a certain crude oil as the raw material oil, the properties are shown in Table 1 in the appendix. The refining conditions are as follows: the top temperature of the extraction tower I 8 is 50 °C, the bottom temperature of the extraction tower I 8 is 40 °C, the mass ratio of the solvent furfural 2 to the raw material oil 1 is 0.5:1.0, the mass ratio of the raw material mixed with the solvent to the raw material oil is 0.8:1. The raffinate 3 at the top of the extraction tower I enters the extraction tower II 9 from the lower part as the raw material of the extraction tower II 9, and the solvent furfural 7 enters the extraction tower II 9 from the upper part of the extraction tower II 9. The operating conditions of the extraction tower II 9 are: the top temperature is 60 °C, the bottom temperature is 40 °C, and the mass ratio of the solvent furfural 7 to the raw material oil is 0.8:1. The refined liquid of the extraction tower II 9 is recycled to obtain an environmental protection rubber plasticizer, and the properties are shown in Table 1. The extract 4 at the bottom of the extraction tower I and the extract 6 at the bottom of the extraction tower II are mixed and recycled to obtain a secondary extracted oil.

[0027] Comparative Example 1

[0028] Using the same feedstock oil, extraction process conditions, and extraction column as in Example 1, i.e., the top temperature of Extraction Column Ⅰ8 is 50°C, the bottom temperature is 40°C, the mass ratio of solvent furfural 2 to feedstock oil 1 is 0.5:1.0. The solvent enters Extraction Column Ⅰ8 from the upper part, and the feedstock oil 1 enters Extraction Column Ⅰ8 from the lower part. The raffinate 3 of Extraction Column Ⅰ enters Extraction Column Ⅱ9 as the feedstock from the lower part. Solvent furfural 7 enters Extraction Column Ⅱ9 from the upper part. The operating conditions of Extraction Column Ⅱ9 are: the top temperature is 60°C, the bottom temperature is 40°C, and the mass ratio of solvent furfural 7 to the feedstock oil is 0.8:1. After the refined liquid of Extraction Column Ⅱ9 recovers the solvent, an environmentally friendly rubber plasticizer is obtained, and its properties are shown in Table 2. The bottom draw 4 of Extraction Column Ⅰ and the bottom draw 6 of Extraction Column Ⅱ are mixed and the solvent is recovered to obtain a secondary extracted oil. The properties of the environmentally friendly rubber plasticizer are shown in Table 1.

[0029] Example 2

[0030] Using the naphthenic minus three hydrotreated and deacidified oil as the feedstock oil, the properties are shown in Appendix 2. The refining conditions are: the top temperature of Extraction Column Ⅰ8 is 80°C, the bottom temperature is 50°C, the mass ratio of solvent furfural 2 to feedstock oil 1 is 0.3:1, and the mass ratio of the feedstock in the part mixed with the solvent to the feedstock oil is 0.9:1. The raffinate 3 of Extraction Column Ⅰ enters Extraction Column Ⅱ9 as the feedstock from the lower part. Solvent furfural 7 enters Extraction Column Ⅱ9 from the upper part. The operating conditions of Extraction Column Ⅱ9 are: the top temperature is 90°C, the bottom temperature is 60°C, and the mass ratio of solvent furfural 7 to the feedstock oil is 0.5:1. After the refined liquid of Extraction Column Ⅱ9 recovers the solvent, an environmentally friendly rubber plasticizer is obtained, and its properties are shown in Table 2. The bottom draw 4 of Extraction Column Ⅰ and the bottom draw 6 of Extraction Column Ⅱ are mixed and the solvent is recovered to obtain an extracted oil.

[0031] Comparative Example 2

[0032] Using the same feedstock oil, extraction process conditions, and extraction column as in Example 2, the refining conditions are: the top temperature of Extraction Column Ⅰ8 is 80°C, the bottom temperature is 50°C, the mass ratio of solvent furfural 2 to feedstock oil 1 is 0.3:1. The solvent enters Extraction Column Ⅰ8 from the upper part, and the feedstock oil 1 enters Extraction Column Ⅰ8 from the lower part. The raffinate 3 of Extraction Column Ⅰ enters Extraction Column Ⅱ9 as the feedstock from the lower part. Solvent furfural 7 enters Extraction Column Ⅱ9 from the upper part. The operating conditions of Extraction Column Ⅱ9 are: the top temperature is 90°C, the bottom temperature is 60°C, and the mass ratio of solvent furfural 7 to the total feedstock oil is 0.5:1. After the refined liquid of Extraction Column Ⅱ9 recovers the solvent, an environmentally friendly rubber plasticizer is obtained, and its properties are shown in Table 2. The bottom draw 4 of Extraction Column Ⅰ and the bottom draw 6 of Extraction Column Ⅱ are mixed and the solvent is recovered to obtain an extracted oil.

[0033] Example 3

[0034] Using the furfural-extracted oil of naphthenic cut 3 as the feedstock, whose properties are shown in Table 3 of the appendix. The refining conditions are as follows: the temperature at the top of Extraction Tower I 8 is 45 °C, the temperature at the bottom is 40 °C, the mass ratio of solvent furfural 2 to feedstock oil 1 is 0.7:1, the mass ratio of the feedstock mixed with the solvent to the feedstock oil is 0.5:1. The raffinate 3 of Extraction Tower I is used as the feedstock of Extraction Tower II 9 and enters Extraction Tower II 9 from the lower part. Solvent furfural 7 enters Extraction Tower II 9 from the upper part. The operating conditions of Extraction Tower II 9 are: the temperature at the top of the tower is 60 °C, the temperature at the bottom is 40 °C, the mass ratio of solvent furfural 7 to feedstock oil is 0.8:1.0. After the refined liquid of Extraction Tower II 9 recovers the solvent, an environment-friendly rubber plasticizer is obtained, whose properties are shown in Table 3. The bottom draw 4 of Extraction Tower I and the bottom draw 6 of Extraction Tower II are mixed and the solvent is recovered to obtain a secondary extracted oil.

[0035] Comparative Example 3

[0036] Using the same feedstock oil, extraction process conditions and extraction tower as in Example 3. The refining conditions are as follows: the temperature at the top of Extraction Tower I 8 is 45 °C, the temperature at the bottom is 40 °C, the mass ratio of solvent furfural 2 to feedstock oil 1 is 0.7:1. Solvent 2 enters Extraction Tower I 8 from the upper part, and feedstock oil 1 enters Extraction Tower I 8 from the lower part. The raffinate 3 of Extraction Tower I is used as the feedstock of Extraction Tower II 9 and enters Extraction Tower II 9 from the lower part. Solvent furfural 7 enters Extraction Tower II 9 from the upper part. The operating conditions of Extraction Tower II 9 are: the temperature at the top of the tower is 60 °C, the temperature at the bottom is 40 °C, the mass ratio of solvent furfural 7 to the total feedstock oil is 0.8:1. After the refined liquid of Extraction Tower II 9 recovers the solvent, an environment-friendly rubber plasticizer is obtained, whose properties are shown in Table 3. The bottom draw 4 of Extraction Tower I and the bottom draw 6 of Extraction Tower II are mixed and the solvent is recovered to obtain an extracted oil.

[0037] Example 4

[0038] Using naphthenic cut 4 as the feedstock, whose properties are shown in Table 4 of the appendix. The refining conditions are as follows: using naphthenic cut 4 fraction oil as the feedstock, whose properties are shown in Table 4 of the appendix. The refining conditions are: the temperature at the top of Extraction Tower I 8 is 80 °C, the bottom temperature is 50 °C, the mass ratio of solvent furfural 2 to feedstock oil 1 is 0.3:1, the mass ratio of the feedstock mixed with the solvent to the feedstock oil is 0.1:1. The raffinate 3 of Extraction Tower I is used as the feedstock of Extraction Tower II 9 and enters Extraction Tower II 9 from the lower part. Solvent furfural 7 enters Extraction Tower II 9 from the upper part. The operating conditions of Extraction Tower II 9 are: the temperature at the top of the tower is 90 °C, the temperature at the bottom is 60 °C, the mass ratio of solvent furfural 7 to the feedstock oil is 0.6:1. After the refined liquid of Extraction Tower II 9 recovers the solvent, an environment-friendly rubber plasticizer is obtained, whose properties are shown in Table 4. The bottom draw 4 of Extraction Tower I and the bottom draw 6 of Extraction Tower II are mixed and the solvent is recovered to obtain an extracted oil.

[0039] Comparative Example 4

[0040] The same feedstock oil, extraction process conditions and extraction column as in Example 4 were used. The refining conditions were as follows: the temperature at the top of Extraction Column I 8 was 80 °C, the temperature at the bottom was 50 °C, the mass ratio of solvent furfural 2 to feedstock oil 1 was 0.3:1. Solvent 2 entered Extraction Column I 8 from the upper part, and feedstock oil 1 entered Extraction Column I 8 from the lower part. The raffinate 3 of Extraction Column I was used as the feedstock of Extraction Column II 9 and entered Extraction Column II 9 from the lower part. Solvent furfural 7 entered Extraction Column II 9 from the upper part. The operating conditions of Extraction Column II 9 were: the temperature at the top was 90 °C, the temperature at the bottom was 60 °C, and the mass ratio of solvent furfural 7 to the total feedstock oil was 0.6:1. After the refined liquid of Extraction Column II 9 recovered the solvent, an environmentally friendly rubber plasticizer was obtained, and its properties are shown in Table 4. The liquid withdrawn from the bottom of Extraction Column I 4 and the liquid withdrawn from the bottom of Extraction Column II 6 were mixed and the solvent was recovered to obtain an extracted oil.

[0041] Table 1 Properties of Feedstock Oil and Environmentally Friendly Rubber Plasticizer in Example 1

[0042]

[0043] Table 2 Properties of Feedstock Oil and Environmentally Friendly Rubber Filling Oil in Example 2

[0044]

[0045] Table 3 Properties of Feedstock Oil and Environmentally Friendly Rubber Filling Oil in Example 3

[0046]

[0047] Table 4 Properties of Feedstock Oil and Environmentally Friendly Rubber Filling Oil in Example 4

[0048]

[0049] It can be seen from the product yields and properties of Examples 1 - 4 and Comparative Examples 1 - 4 in Tables 1 - 4 that the method of this invention adopts adding part of the feedstock oil into the solvent for two-stage extraction. Compared with the conventional two-stage extraction, the product yield and C value can be increased under the same conditions. A Therefore, using lubricating oil fraction oil or lubricating oil solvent extracted oil as the feedstock oil, an environmentally friendly rubber plasticizer product with BaP less than 1 mg / kg, PCA less than 3%, and total content of 8 harmful aromatic hydrocarbons less than 10 mg / kg can be produced by this method.

[0050] The method for producing an aromatic-based environmentally friendly rubber plasticizer of the present invention adopts a two-column extraction method, using lubricating oil fraction oil or solvent extracted oil as the feedstock, which can greatly reduce the polycyclic aromatic hydrocarbon content in the feedstock oil and retain the environmentally friendly less-ring aromatic hydrocarbon content, so that the yield of the produced environmentally friendly rubber plasticizer product is higher and the C AThe value is higher, meeting the requirements of tire oil.

Claims

1. A method for producing an aromatic-based environmentally friendly rubber plasticizer, characterized in that, Using lubricating oil fraction or solvent-extracted oil as the feedstock and furfural as the solvent, it is carried out in a countercurrent extraction tower, adopting a two-column extraction process. A part of the feedstock is mixed with the solvent and enters Extraction Tower I from the upper part of Extraction Tower I, and the other part enters Extraction Tower I from the lower part of Extraction Tower I. The raffinate at the top of Extraction Tower I enters Extraction Tower II from the lower feed inlet of Extraction Tower II as the feedstock of Extraction Tower II. The solvent furfural enters Extraction Tower II from the upper solvent inlet of Extraction Tower II. The raffinate is obtained at the top of Extraction Tower II, and an aromatic-based environmental rubber plasticizer is obtained after solvent recovery. The extracts at the bottoms of Extraction Tower I and Extraction Tower II are mixed, and a secondary extract oil is obtained after solvent recovery.

2. The method for producing an aromatic-based environmentally friendly rubber plasticizer according to claim 1, wherein The lubricating oil fraction or solvent-extracted oil described above has 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 13.0%, and a freezing point of not higher than 20 °C.

3. The method for producing an aromatic-based environmentally friendly rubber plasticizer according to claim 1, characterized in that The mass ratio of the part of the feedstock mixed with the solvent to the total feedstock is 0.1:1 to 0.9:

1.

4. The method for producing an aromatic-based environmentally friendly rubber plasticizer according to claim 1, characterized in that The furfural extraction conditions are as follows: the top temperature of Extraction Tower I is 45°C to 90°C, the bottom temperature of Extraction Tower I is 40°C to 50°C, and the mass ratio of the solvent to the feedstock is 0.3:1 to 1.0:1; the top temperature of Extraction Tower II is 60°C to 90°C, the bottom temperature of Extraction Tower II is 40°C to 60°C, and the mass ratio of the solvent to the feedstock is 0.5:1 to 1.0:1.

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