Production method of environment-friendly high aromatic rubber plasticizer

Abstract

The invention belongs to the technical field of petrochemical industry, and particularly relates to a production method of an environment-friendly high-aromatic rubber plasticizer, which is characterized in that solvent extract oil is used as raw material oil, the method is carried out in a counter-current extraction tower, a double-solvent three-tower extraction process is adopted, and double solvents are a main solvent and an auxiliary solvent. According to the method, the solvent extract oil is used as a raw material and is extracted in the counter-current extraction tower, a double-solvent three-tower extraction process is adopted, double solvents are a main solvent and an auxiliary solvent, a considerable amount of less-ring environment-friendly aromatic hydrocarbon can be reserved, toxic polycyclic aromatic hydrocarbon can be removed to the maximum extent, and the rubber plasticizer meeting the requirements of European Union environmental protection instructions can be produced.

Description

Technical Field

[0001] The present invention belongs to the technical field of petrochemical industry, and particularly relates to a production method of an environment-friendly high-aromatic rubber plasticizer. Background Art

[0002] The oils used in the rubber synthesis or rubber processing are collectively called 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, the aromatic type oil has the characteristics of high density, high viscosity, good affinity and excellent processing performance, and has excellent properties such as good compatibility with rubber and good wet skid resistance for tires. 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 have toxicity such as carcinogenicity and damage to the reproductive system, so 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] After rubber is filled with oil, its processing performance and service performance are improved. At the same time, the output of rubber is increased and the cost is reduced. 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.

[0004] At present, there are mainly two types of domestic environment-friendly rubber plasticizers: aromatic-based mineral oil and naphthenic-based mineral oil. Among them, aromatic-based mineral oil is mainly applied to the oil filling of tires and related products and rubber.

[0005] In terms of the domestic market, with the continuous increase in the production of automobiles, the production of tires 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, replacing aromatic oil as an environment-friendly rubber filling oil for use in oil-filled rubber and tire production will surely attract great attention, and its demand will also increase.

[0006] 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. This method is difficult to produce products with high yield, high aromatic hydrocarbon content, and quality that can meet the requirements of the European Union. 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 obtained from the secondary extraction is 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 CA).

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

[0008] The purpose of the present invention is to provide a production method for environmentally friendly high-aromatic rubber plasticizers, which can, on the basis of the existing technology, retain a considerable amount of less-ring environmentally friendly aromatic hydrocarbons and, to the greatest extent, remove toxic polycyclic aromatic hydrocarbons, so as to produce rubber plasticizers that meet the requirements of the EU environmental protection directives.

[0009] The present invention is realized through the following technical solutions:

[0010] The production method of the environmentally friendly high-aromatic rubber plasticizer of the present invention is characterized in that the solvent extract oil is used as the raw material oil, and it is carried out in a countercurrent extraction column, adopting a double-solvent three-column extraction process. The double solvents are the main solvent and the auxiliary solvent.

[0011] The raw material oil and the main solvent are mixed and then enter Extraction Column I from the upper part of Extraction Column I. The auxiliary solvent enters Extraction Column I from the lower part of the extraction column. The raffinate at the top of Extraction Column I is used as the raw material of Extraction Column II and enters Extraction Column II from the lower part of Extraction Column II. The main solvent enters the said Extraction Column II through the upper solvent inlet of Extraction Column II. The raffinate at the top of Extraction Column II is used as the raw material of Extraction Column III and enters Extraction Column III from the lower part of Extraction Column III. The main solvent enters the said Extraction Column III through the upper solvent inlet of Extraction Column III. The raffinate at the top of the said Extraction Column III can be recycled as the auxiliary solvent. The extract obtained from the bottom of Extraction Column III is obtained. After recovering the main solvent, a high-aromatic environmentally friendly rubber plasticizer is obtained.

[0012] The extract obtained from the bottom of Extraction Column II and the extract obtained from the bottom of Extraction Column I are mixed to obtain a mixed liquid of the extracts of Extraction Column I and Extraction Column II. After recovering the main solvent, a secondary extract oil is obtained.

[0013] The secondary solvent is mixed with the extract withdrawn from the bottom of part of Extraction Tower II and then enters Extraction Tower I from the lower part of Extraction Tower I, or part of the extract withdrawn from the bottom of Extraction Tower II enters Extraction Tower I after being mixed with the feedstock oil and the primary solvent at the primary solvent inlet of Extraction Tower I.

[0014] The solvent-extracted oil described satisfies an open flash point of not less than 200 °C, a kinematic viscosity at 100 °C of not less than 13.0 mm 2 / s, a freezing point of not higher than 20 °C, and a CA value of not less than 30%.

[0015] The primary solvent is furfural, and the secondary solvent is a naphthenic or intermediate base oil with an open flash point of not less than 200 °C, a kinematic viscosity at 100 °C of not less than 13.0 mm 2 / s, a freezing point of not higher than 10 °C, and a C A value of not more than 5%.

[0016] The secondary solvent is mixed with the extract withdrawn from the bottom of part of Extraction Tower II and then enters Extraction Tower I from the lower part of Extraction Tower I. The mass ratio of the part of the extract withdrawn from the bottom of Extraction Tower II to the feedstock oil is 0.1:1 - 0.5:1.

[0017] Part of the extract withdrawn from the bottom of Extraction Tower II enters Extraction Tower I after being mixed with the feedstock oil and the primary solvent at the primary solvent inlet of Extraction Tower I. The mass ratio of the part of the extract withdrawn from the bottom of Extraction Tower II to the feedstock oil is 0.1:1 - 0.5:1.

[0018] The top temperature of Extraction Tower I is 45 °C - 80 °C, the bottom temperature is 40 °C - 50 °C, and the mass ratio of the primary solvent to the feedstock oil is 0.5:1 - 2.0:1; the mass ratio of the secondary solvent to the feedstock oil is 0.1:1 - 2.0:1.

[0019] The top temperature of Extraction Tower II is 55 °C - 90 °C, the bottom temperature is 40 °C - 60 °C, and the mass ratio of the primary solvent to the feedstock oil is 0.6:1 - 2.0:1.

[0020] The top temperature of Extraction Tower III is 80 °C - 110 °C, the bottom temperature is 50 °C - 70 °C, and the mass ratio of the primary solvent to the feedstock oil is 2.0:1 - 8.0:1.

[0021] Advantages of the present invention:

[0022] The production method of the environmentally friendly high-aromatic rubber plasticizer of the present invention uses solvent-extracted oil as the raw material, is carried out in a countercurrent extraction tower, and adopts a double-solvent three-tower extraction process. The double solvents are the primary solvent and the secondary solvent, which can not only retain a considerable amount of less-ring environmentally friendly aromatics but also greatly remove toxic polycyclic aromatics, and produce a rubber plasticizer that meets the requirements of EU environmental protection directives. Description of the drawings

[0023] Figure 1 This is the process flow diagram of the present invention.

[0024] The labels therein are respectively represented as follows: 1, raw material oil; 2, main solvent; 3, auxiliary solvent; 4, raffinate at the top of Extraction Tower I; 5, extract at the bottom of Extraction Tower I; 6, raffinate at the top of Extraction Tower II; 7, extract at the bottom of Extraction Tower II; 8, solvent inlet at the upper part of Extraction Tower II; 9, raffinate at the top of Extraction Tower III; 10, solvent inlet at the upper part of Extraction Tower III; 11, extract of Extraction Tower III; 12, mixed liquid of extracts from Extraction Tower I and Extraction Tower II; 13, Extraction Tower I; 14, Extraction Tower II; 15, Extraction Tower III. Specific Embodiments

[0025] The specific embodiments of the present invention will be further described below with reference to the accompanying drawings.

[0026] As Figure 1 shown, the production method of the environmentally friendly high-aromatic rubber plasticizer of the present invention is characterized in that solvent-extracted oil is used as the raw material oil, and it is carried out in a countercurrent extraction tower, adopting a double-solvent three-tower extraction process. The double solvents are the main solvent 2 and the auxiliary solvent 3.

[0027] The raw material oil 1 is mixed with the main solvent 2 and then enters Extraction Tower I 13 from the upper part of Extraction Tower I 13. The auxiliary solvent 3 enters Extraction Tower I 13 from the lower part of the Extraction Tower I 13. The raffinate 4 at the top of Extraction Tower I is used as the raw material of Extraction Tower II 14 and enters Extraction Tower II 14 from the lower part of Extraction Tower II 14. The main solvent 2 enters the said Extraction Tower II 14 through the solvent inlet 8 at the upper part of Extraction Tower II. The raffinate 6 at the top of Extraction Tower II is used as the raw material of Extraction Tower III 15 and enters Extraction Tower III 15 from the lower part of Extraction Tower III 15. The main solvent 2 enters the said Extraction Tower III 15 through the solvent inlet 10 at the upper part of Extraction Tower III. The raffinate 9 at the top of Extraction Tower III obtained from the said Extraction Tower III can be recycled as the auxiliary solvent. The extract 11 of Extraction Tower III is obtained at the bottom of the said Extraction Tower III 15. After recovering the main solvent, a high-aromatic environmentally friendly rubber plasticizer is obtained.

[0028] The extract 7 at the bottom of Extraction Tower II is mixed with the extract 5 at the bottom of Extraction Tower I to obtain the mixed liquid 12 of extracts from Extraction Tower I and Extraction Tower II. After recovering the main solvent, secondary extracted oil is obtained.

[0029] The auxiliary solvent 3 is mixed with a part of the extract 7 at the bottom of Extraction Tower II and then enters Extraction Tower I 13 from the lower part of Extraction Tower I 13, or a part of the extract 7 at the bottom of the said Extraction Tower II enters the said Extraction Tower I 13 after being mixed with the raw material oil 1 and the main solvent 2 at the main solvent inlet of the Extraction Tower I 13.

[0030] The solvent-extracted oil described above satisfies the requirements that the open flash point is not less than 200°C, the kinematic viscosity at 100°C is not less than 13.0 mm 2 / s, the freezing point is not higher than 20°C, and the CA value is not less than 30%. If the freezing point is higher than 20°C, solvent dewaxing treatment can be carried out.

[0031] The main solvent 2 described above is furfural, and the auxiliary solvent 3 is a naphthenic or intermediate base base oil with an open flash point not less than 200°C, a kinematic viscosity at 100°C not less than 13.0 mm 2 / s, a freezing point not higher than 10°C, and a C A value not greater than 5%.

[0032] The auxiliary solvent 3 described above is mixed with a part of the extract 7 at the bottom of the extraction tower II and then enters the extraction tower I 13 from the lower part of the extraction tower I 13. The mass ratio of the part of the extract 7 at the bottom of the extraction tower II to the feedstock oil 1 is 0.1:1 - 0.5:1.

[0033] A part of the extract 7 at the bottom of the extraction tower II described above enters the extraction tower I 13 after being mixed with the feedstock oil 1 and the main solvent 2 at the main solvent inlet of the extraction tower I 13. The mass ratio of the part of the extract 7 at the bottom of the extraction tower II to the feedstock oil 1 is 0.1:1 - 0.5:1.

[0034] The top temperature of the extraction tower I 13 described above is 45°C - 80°C, the bottom temperature is 40°C - 50°C, the mass ratio of the main solvent 2 to the feedstock oil 1 is 0.5:1 - 2.0:1; the mass ratio of the auxiliary solvent 3 to the feedstock oil 1 is 0.1:1 - 2.0:1.

[0035] The top temperature of the extraction tower II 14 described above is 55°C - 90°C, the bottom temperature is 40°C - 60°C, and the mass ratio of the main solvent 2 to the feedstock oil 1 is 0.6:1 - 2.0:1.

[0036] The top temperature of the extraction tower III 15 for recovering the auxiliary solvent is 80°C - 110°C, the bottom temperature is 50°C - 70°C, and the mass ratio of the main solvent 2 to the feedstock oil 1 is 2.0:1 - 8.0:1.

[0037] A production method of an environmentally friendly high-aromatic rubber plasticizer according to the present invention is specifically implemented as follows Figure 1As shown in the figure: After the main solvent 2 is mixed with the feedstock oil 1, it enters the extraction tower I 13 from the upper part of the extraction tower I 13. The secondary solvent 3 is mixed with a part of the withdrawn liquid from the bottom of the extraction tower II 14 and then enters the extraction tower I 13 from the lower part of the extraction tower I 13, or a part of the withdrawn liquid from the bottom of the extraction tower II 14 enters the extraction tower I 13 after being mixed with the feedstock oil 1 and the main solvent 2 at the main solvent inlet of the extraction tower I 13; The mixed liquid 12 of the withdrawn liquids from the extraction tower I and the extraction tower II obtains the secondary extracted oil after recovering the main solvent; The raffinate 4 at the top of the extraction tower I is the feedstock for the extraction tower II 14 and enters the extraction tower II 14 from the lower part of the extraction tower II 14. The main solvent 2 enters the extraction tower II 14 from the upper part of the extraction tower II 14 through the upper solvent inlet 8 of the extraction tower II. The raffinate 6 at the top of the extraction tower II 14 is obtained as the feedstock for the extraction tower III 15 and enters the extraction tower III 15 from the lower part of the extraction tower III 15. The main solvent enters the extraction tower III 15 from the upper part of the extraction tower III 15 through the upper solvent inlet 10 of the extraction tower III. The raffinate 9 at the top is obtained, which can be recycled as the secondary solvent. The withdrawn liquid 11 at the bottom of the extraction tower III 15 obtains the high-aromatic environmental protection rubber plasticizer after recovering the main solvent.

[0038] Example 1

[0039] Using the furfural extracted oil of a certain crude oil vacuum gas oil as the feedstock oil, the properties are shown in Table 1. The feedstock oil 1 is mixed with the main solvent furfural 2 and then enters the extraction tower I 13 from the upper part of the extraction tower I 13. The secondary solvent 3 enters the extraction tower I 13 from the lower part of the extraction tower I 13. After the feedstock oil 1 is solvent-refined in the extraction tower I 13, the raffinate 4 at the top of the extraction tower I 13 is used as the feedstock for the extraction tower II 14 and enters the extraction tower II 14 from the feedstock oil inlet at the lower part of the extraction tower II 14. The main solvent furfural 2 enters the extraction tower II 14 from the upper part of the extraction tower II 14. The raffinate 6 at the top of the extraction tower II 14 is obtained as the feedstock for the extraction tower III 15 and enters the extraction tower III 15 from the lower part of the extraction tower III 15. The main solvent furfural 2 enters the extraction tower III 15 from the upper part of the extraction tower III 15. The raffinate 9 at the top is obtained, which can be recycled as the secondary solvent. The withdrawn liquid 11 flowing out from the bottom of the extraction tower III obtains the high-aromatic environmental protection rubber plasticizer after recovering the main solvent, and the properties are shown in Table 1.

[0040] The secondary solvent 3 is a naphthenic base oil with a C A value of 4.2%, and its properties are shown in Table 1.

[0041] The refining conditions are as follows: The top temperature of the extraction tower I 13 is 65 °C, the bottom temperature is 40 °C, the mass ratio of the main solvent 2 to the feedstock oil 1 is 2:1, and the mass ratio of the secondary solvent 3 to the feedstock oil 1 is 2.0:1;

[0042] The top temperature of extraction column II 14 is 80°C, and the bottom temperature is 50°C. The mass ratio of main solvent 2 to feedstock oil 1 is 2.0:1;

[0043] The top temperature of extraction column III 15 is 100°C, and the bottom temperature is 70°C. The mass ratio of main solvent 2 to feedstock oil 1 is 8.0:1.

[0044] Comparative Example 1

[0045] The same feedstock oil and extraction column as in Example 1 are used, and a two-stage extraction process is adopted. That is, the top temperature of extraction column I 13 is 65°C, and the bottom temperature is 40°C. The mass ratio of main solvent furfural 2 to feedstock oil 1 is 0.8:1. Main solvent 2 enters extraction column I 13 from the upper part, and feedstock oil 1 enters extraction column I 13 from the lower part. The raffinate 4 at the top of extraction column I is used as the feedstock of extraction column II 14 and enters extraction column II 14 from the lower part. Main solvent furfural 2 enters extraction column II 14 from the upper part. The operating conditions of extraction column II 14 are: the top temperature is 80°C, the bottom temperature is 50°C, and the mass ratio of main solvent furfural 2 to feedstock oil 1 is 1.0:1. After the refined liquid of extraction column II 14 recovers the solvent, an environment-friendly rubber plasticizer is obtained, and its properties are shown in Table 1. The mixed liquid 12 of the extract from extraction column I and extraction column II is recovered the solvent to obtain a secondary extracted oil. The properties of the environment-friendly rubber plasticizer are shown in Table 1.

[0046] Example 2

[0047] Using the furfural extract of a certain crude oil vacuum gas oil as the feedstock oil, and its properties are shown in Appendix 2. After the feedstock oil 1 and the main solvent furfural 2 are mixed, they enter extraction column I 13 from the upper part, and the auxiliary solvent 3 enters extraction column I 13 from the lower part. After the feedstock oil is solvent-refined in extraction column I 13, the raffinate 4 at the top of extraction column I is used as the feedstock of extraction column II 14 and enters extraction column II 14 from the feedstock oil inlet at the lower part. Solvent furfural 2 enters extraction column II 14 from the upper part. The raffinate 6 at the top of extraction column II is used as the feedstock of extraction column III 15 and enters extraction column III 15 from the lower part. Solvent furfural 2 enters extraction column III 15 from the upper part. The raffinate 9 at the top of extraction column III can be recycled as an auxiliary solvent, and the extract 11 flowing out from the bottom of extraction column III is recovered the main solvent to obtain a high-aromatic environment-friendly rubber plasticizer, and its properties are shown in Appendix 2.

[0048] The auxiliary solvent 3 is a naphthenic base oil with a C A value of 4.2%, and its properties are shown in Table 1.

[0049] The refining conditions are as follows: the top temperature of extraction tower I 13 is 45°C, the bottom temperature is 40°C, the mass ratio of main solvent 2 to feedstock oil 1 is 0.5:1, and the mass ratio of auxiliary solvent 3 to feedstock oil 1 is 0.1:1;

[0050] The top temperature of extraction tower II 14 is 55°C, the bottom temperature is 40°C, and the mass ratio of main solvent 2 to the feedstock oil 1 is 0.6:1;

[0051] The top temperature of extraction tower III 15 is 80°C, the bottom temperature is 50°C, and the mass ratio of main solvent 2 to the feedstock oil 1 is 2.0:1.

[0052] Comparative Example 2

[0053] The same feedstock oil and extraction tower as in Example 2 are used, and a two-stage extraction process is adopted. That is, the top temperature of extraction tower I 13 is 45°C, the bottom temperature is 40°C, the mass ratio of main solvent furfural 2 to feedstock oil 1 is 0.5:1. The main solvent 2 enters extraction tower I 13 from the upper part, and the feedstock oil 1 enters extraction tower I 13 from the lower part. The raffinate 4 at the top of extraction tower I is used as the feedstock of extraction tower II 14 and enters extraction tower II 14 from the lower part. The main solvent furfural 2 enters extraction tower II 14 from the upper part. The operating conditions of extraction tower II 14 are: the top temperature is 55°C, the bottom temperature is 40°C, and the mass ratio of main solvent furfural 2 to feedstock oil 1 is 0.6:1. After the refined liquid of extraction tower II 14 recovers the solvent, an environmentally friendly rubber plasticizer is obtained, and its properties are shown in Table 2. The mixed liquid 12 of the extract from extraction tower I and extraction tower II is recovered the solvent to obtain a secondary extracted oil.

[0054] Example 3

[0055] Using the naphthenic acid reduced third-line furfural extracted oil as the feedstock oil, and its properties are shown in Appendix 3. The feedstock oil 1 and the main solvent furfural 2 are mixed and enter extraction tower I 13 from the upper part. The auxiliary solvent 3 enters extraction tower I 13 from the middle part. After the feedstock oil 1 is solvent-refined in extraction tower I 13, the raffinate 4 at the top of extraction tower (1) is used as the feedstock of extraction tower II 14 and enters the feedstock inlet at the lower part of extraction tower II 14. The main solvent furfural 2 enters extraction tower II 14 from the upper part. The raffinate 6 at the top of extraction tower II is used as the feedstock of extraction tower III 15 and enters extraction tower III 15 from the lower part. The main solvent furfural 2 enters extraction tower III 15 from the upper part. The raffinate 9 at the top of extraction tower III can be recycled as an auxiliary solvent. The extract 11 at the bottom of extraction tower III is recovered the main solvent to obtain a high-aromatic environmentally friendly rubber plasticizer, and its properties are shown in Appendix 3.

[0056] The auxiliary solvent 3 is a kind of C AThe intermediate base base oil with a value of 3.2% has properties shown in Table 3.

[0057] The refining conditions are as follows: the top temperature of Extraction Tower I 13 is 60°C, the bottom temperature is 40°C, the mass ratio of the main solvent 2 to the raw material oil 1 is 1.5:1, and the mass ratio of the auxiliary solvent 3 to the raw material oil 1 is 1.0:1;

[0058] The top temperature of Extraction Tower II 14 is 70°C, the bottom temperature is 40°C, and the mass ratio of the main solvent 2 to the raw material oil 1 is 0.9:1;

[0059] The top temperature of Extraction Tower III 15 is 85°C, the bottom temperature is 55°C, and the mass ratio of the main solvent 2 to the raw material oil 1 is 3.5:1.

[0060] Comparative Example 3

[0061] The same raw material oil and extraction tower as in Example 3 are used, and a two-stage extraction process is adopted. That is, the top temperature of Extraction Tower I 13 is 60°C, the bottom temperature is 40°C, the mass ratio of the main solvent furfural 2 to the raw material oil 1 is 0.8:1. The main solvent 2 enters Extraction Tower I 13 from the upper part, and the raw material oil 1 enters Extraction Tower I 13 from the lower part. The raffinate 4 at the top of Extraction Tower I enters Extraction Tower II 14 as the raw material from the lower part. The main solvent furfural 2 enters Extraction Tower II 14 from the upper part. The operating conditions of Extraction Tower II 14 are: the top temperature is 70°C, the bottom temperature is 40°C, and the mass ratio of the main solvent furfural 2 to the raw material oil 1 is 1.2:1. After the refined liquid of Extraction Tower II 14 recovers the solvent, an environmentally friendly rubber plasticizer is obtained, and its properties are shown in Table 3. The mixed liquid 12 of the extract of Extraction Tower I and Extraction Tower II obtains a secondary extracted oil after recovering the solvent.

[0062] Example 4

[0063] Using the naphthenic decanted oil from the third line of the vacuum distillation unit as the feedstock, whose properties are shown in Table 4 of the appendix. After the feedstock 1 is mixed with the main solvent furfural 2, they enter Extraction Tower I 13 from the upper part of the tower. The auxiliary solvent 3 is mixed with a part of the extract from the bottom of Extraction Tower II 14 and enters Extraction Tower I 13 from the lower part of the tower. The mass ratio of the extract to the feedstock 1 is 0.1:1. After the feedstock 1 is refined by solvent in Extraction Tower I 13, the raffinate 4 at the top of Extraction Tower I enters Extraction Tower II 14 as the feedstock for Extraction Tower II 14 from the feedstock inlet at the lower part of Extraction Tower II 14. The main solvent furfural 2 enters Extraction Tower II 14 from the upper part of the tower. The raffinate 6 at the top of Extraction Tower II enters Extraction Tower III 15 as the feedstock for Extraction Tower III 15 from the lower part of Extraction Tower III 15. The main solvent furfural 2 enters Extraction Tower III 15 from the upper part of the tower. The raffinate 9 at the top of Extraction Tower III can be recycled as the auxiliary solvent. The extract 11 flowing out from the bottom of Extraction Tower III is recovered to obtain the high-aromatic environmental protection rubber plasticizer after recovering the main solvent, whose properties are shown in Table 4 of the appendix.

[0064] The auxiliary solvent 3 is an intermediate-base base oil with a C A value of 3.2%, and its properties are shown in Table 4.

[0065] The refining conditions are as follows: the top temperature of Extraction Tower I 13 is 60°C, the bottom temperature is 40°C, the mass ratio of the main solvent 2 to the feedstock 1 is 1.5:1, and the mass ratio of the auxiliary solvent 3 to the feedstock 1 is 1.0:1;

[0066] The top temperature of Extraction Tower II 14 is 70°C, the bottom temperature is 40°C, and the mass ratio of the main solvent 2 to the feedstock 1 is 1.5:1;

[0067] The top temperature of Extraction Tower III 15 is 95°C, the bottom temperature is 65°C, and the mass ratio of the main solvent 2 to the feedstock 1 is 4.0:1.

[0068] Example 5

[0069] Using the naphthenic decanted oil from the third side stream of the vacuum distillation unit of a refinery as the feedstock, the properties of which are shown in Table 5 in the appendix. The feedstock 1 is mixed with the main solvent furfural 2 and a part of the extract liquid from the bottom of the extraction tower II 14, and then enters the extraction tower I 13 from the upper part of the extraction tower I 13. The mass ratio of the extract liquid to the feedstock 1 is 0.5:1. The auxiliary solvent 3 enters the extraction tower I 13 from the lower part of the extraction tower I 13. After the feedstock 1 is refined by the solvent in the extraction tower I 13, the raffinate 4 at the top of the extraction tower I is used as the feedstock of the extraction tower II 14 and enters the extraction tower II 14 from the feedstock inlet at the lower part of the extraction tower II 14. The main solvent furfural 2 enters the extraction tower II 14 from the upper part of the extraction tower II 14. The raffinate 6 at the top of the extraction tower II is used as the feedstock of the extraction tower III 15 and enters the extraction tower III 15 from the lower part of the extraction tower III 15. The main solvent furfural enters the extraction tower III 15 from the upper part of the extraction tower III 15. The raffinate 9 at the top of the extraction tower III can be recycled as the auxiliary solvent. The extract liquid 11 at the bottom of the extraction tower III is recovered the main solvent to obtain a high-aromatic environmental protection rubber plasticizer, the properties of which are shown in Table 5 in the appendix.

[0070] The auxiliary solvent 3 is an intermediate-base base oil with a C A value of 3.2%, and its properties are shown in Table 5.

[0071] The refining conditions are as follows: the top temperature of the extraction tower I 13 is 50 °C, the bottom temperature is 40 °C, the mass ratio of the main solvent 2 to the feedstock 1 is 0.7:1, and the mass ratio of the auxiliary solvent 3 to the feedstock 1 is 0.5:1;

[0072] The top temperature of the extraction tower II 14 is 70 °C, the bottom temperature is 40 °C, and the mass ratio of the main solvent 2 to the feedstock 1 is 0.9:1;

[0073] The top temperature of the extraction tower III 15 is 85 °C, the bottom temperature is 55 °C, and the mass ratio of the main solvent 2 to the feedstock 1 is 4.0:1.

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] It can be seen from the product yields and properties of Tables 1-3, Examples 1-3 and Comparative Examples 1-3 in the appendix that using the lubricating oil solvent extract as the feedstock, environmental protection rubber filling oil products with 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. C AA high-aromatic environmental protection rubber plasticizer with a value of more than 20%.

[0080] The production method of the environmental protection high-aromatic rubber plasticizer of the present invention uses solvent-extracted oil as the raw material and is carried out in a countercurrent extraction tower. The double-solvent three-column extraction process is adopted. The double solvents are the main solvent and the auxiliary solvent, which can not only retain a considerable amount of less-ring environmental protection aromatics, but also greatly remove toxic polycyclic aromatic hydrocarbons, and produce a rubber plasticizer that meets the requirements of EU environmental protection directives.

Claims

1. A production method of an environmentally friendly high-aromatic rubber plasticizer, characterized in that, Using solvent-extracted oil as the raw material oil, it is carried out in a countercurrent extraction tower, adopting a double-solvent three-column extraction process. The double solvents are the main solvent and the auxiliary solvent. The raw material oil is mixed with the main solvent and enters Extraction Tower I from the upper part of Extraction Tower I. The auxiliary solvent enters Extraction Tower I from the lower part of the extraction tower. The raffinate at the top of Extraction Tower I is used as the raw material for Extraction Tower II and enters Extraction Tower II from the lower part of Extraction Tower II. The main solvent enters the said Extraction Tower II through the solvent inlet at the upper part of Extraction Tower II. The raffinate at the top of Extraction Tower II is used as the raw material for Extraction Tower III and enters Extraction Tower III from the lower part of Extraction Tower III. The main solvent enters the said Extraction Tower III through the solvent inlet at the upper part of Extraction Tower III. The raffinate at the top of Extraction Tower III can be recycled as the auxiliary solvent. The extract obtained at the bottom of Extraction Tower III is obtained after recovering the main solvent, and a high-aromatic environmental protection rubber plasticizer is obtained. The extract at the bottom of Extraction Tower II is mixed with the extract at the bottom of Extraction Tower I to obtain a mixed liquid of the extracts from Extraction Tower I and Extraction Tower II. After recovering the main solvent, secondary extracted oil is obtained.

2. The production method of the environmentally friendly high-aromatic rubber plasticizer according to claim 1, characterized in that The auxiliary solvent is mixed with a part of the extract at the bottom of Extraction Tower II and then enters Extraction Tower I from the lower part of Extraction Tower I, or a part of the extract at the bottom of Extraction Tower II enters the said Extraction Tower I after being mixed with the raw material oil and the main solvent at the main solvent inlet of Extraction Tower I.

3. The production method of the environment-friendly high-aromatic rubber plasticizer according to claim 1, characterized in that The 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 13.0 mm 2 / s, the freezing point is not higher than 20 °C, and the C A value is not less than 30%.

4. The production method of the environment-friendly high-aromatic rubber plasticizer according to claim 1, characterized in that The main solvent is furfural, and the secondary solvent is a naphthenic or intermediate base oil with an open flash point of not less than 200 °C, a kinematic viscosity at 100 °C of not less than 13.0 mm 2 / s, a freezing point of not higher than 10 °C, and a C A value of not more than 5%.

5. The production method of the environment-friendly high-aromatic rubber plasticizer according to claim 2, characterized in that The auxiliary solvent is mixed with a part of the extract at the bottom of Extraction Tower II and then enters Extraction Tower I from the lower part of Extraction Tower I. The mass ratio of the part of the extract at the bottom of Extraction Tower II to the raw material oil is 0.1:1 - 0.5:

1.

6. The production method of the environmentally friendly high-aromatic rubber plasticizer according to claim 2, characterized in that A part of the extract at the bottom of Extraction Tower II enters the said Extraction Tower I after being mixed with the raw material oil and the main solvent at the main solvent inlet of Extraction Tower I. The mass ratio of the part of the extract at the bottom of Extraction Tower II to the raw material oil is 0.1:1 - 0.5:

1.

7. The production method of the environmentally friendly high-aromatic rubber plasticizer according to claim 1, characterized in that The top temperature of Extraction Tower I is 45°C - 80°C, and the bottom temperature is 40°C - 50°C. The mass ratio of the main solvent to the raw material oil is 0.5:1 - 2.0:1; the mass ratio of the auxiliary solvent to the raw material oil is 0.1:1 - 2.0:

1.

8. The production method of the environmentally friendly high-aromatic rubber plasticizer according to claim 1, characterized in that The top temperature of Extraction Tower II is 55°C - 90°C, and the bottom temperature is 40°C - 60°C. The mass ratio of the main solvent to the raw material oil is 0.6:1 - 2.0:

1.

9. The production method of the environmentally friendly high-aromatic rubber plasticizer according to claim 1, characterized in that The top temperature of Extraction Tower III is 80°C - 110°C, and the bottom temperature is 50°C - 70°C. The mass ratio of the main solvent to the raw material oil is 2.0:1 - 8.0:1.

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