阅读说明：本技术 一种高芳烃高黏度环保橡胶增塑剂的制备方法 (Preparation method of high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer ) 是由 马丙水 郭春梅 刘锐 高志斌 徐林勋 尹国栋 王耀伟 栾波 于 2021-08-06 设计创作，主要内容包括：本发明提供了一种高芳烃高黏度环保橡胶增塑剂的制备方法,包括以下步骤：a)将环烷基减压渣油依次进行加氢精制和临氢降凝,得到加氢液体产物；b)将步骤a)得到的加氢液体产物进行减压蒸馏,收集沸点≥360℃的馏分；再进行糠醛萃取,下层得到高芳烃高黏度环保橡胶增塑剂。该制备方法采用不同于传统的两段糠醛萃取工艺的组合工艺,实现整体较好的相互作用,能够解决传统的两段糠醛萃取工艺收率不高、稠环芳烃含量与芳碳含量之间的矛盾的技术问题。实验结果表明,该制备方法产品收率高,制备的高芳烃高黏度环保橡胶增塑剂的收率>65wt％,且产品的100℃运动黏度>57mm～(2)/s,CA含量>35wt％,PCA＜3wt％,PAHs含量＜10mg/kg,BaP含量＜1mg/kg,属于高芳烃高黏度环保橡胶增塑剂产品。(The invention provides a preparation method of a high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer, which comprises the following steps: a) sequentially carrying out hydrofining and hydrodewaxing on the naphthenic base vacuum residue to obtain a hydrogenated liquid product; b) carrying out reduced pressure distillation on the hydrogenation liquid product obtained in the step a), and collecting fractions with the boiling point being more than or equal to 360 ℃; and performing furfural extraction, and obtaining the high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer on the lower layer. The preparation method adopts a combined process different from the traditional two-stage furfural extraction process, realizes better overall interaction, and can solve the technical problems of low yield and contradiction between the content of polycyclic aromatic hydrocarbon and the content of aromatic carbon in the traditional two-stage furfural extraction process. The experimental result shows that the preparation method has high product yield, and the yield of the prepared high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer is high>65 wt% and of the productKinematic viscosity at 100 DEG C>57mm 2 S, CA content>35 wt%, PCA less than 3 wt%, PAHs content less than 10mg/kg, BaP content less than 1mg/kg, and belongs to high aromatic hydrocarbon high viscosity environment-friendly rubber plasticizer products.)

1. A preparation method of a high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer comprises the following steps:

a) sequentially carrying out hydrofining and hydrodewaxing on the naphthenic base vacuum residue to obtain a hydrogenated liquid product;

b) carrying out reduced pressure distillation on the hydrogenation liquid product obtained in the step a), and collecting fractions with the boiling point being more than or equal to 360 ℃; and performing furfural extraction, and obtaining the high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer on the lower layer.

2. The preparation method according to claim 1, wherein the distillation range of the naphthenic vacuum residue in the step a) is 420-580 ℃, the aromatic hydrocarbon content is 30-35 wt%, the polycyclic aromatic compound content is 10-15 wt%, the pour point is 10-35 ℃, and the viscosity at 100 ℃ is 25mm²/s～35mm²/s。

3. The production method according to claim 1, wherein the hydrofinishing in step a) is carried out in a reaction zone packed with a hydrofinishing catalyst; the hydrofining catalyst is selected from one or more of MLDW-4 catalyst, ICR-240 catalyst and HR1058 catalyst.

4. The preparation method according to claim 3, wherein the reaction temperature of the hydrofining is 300-350 ℃, the reaction pressure is 8-14 MPa, and the volume ratio of hydrogen to oil is (500-1500): 1, the liquid hourly space velocity is 0.5h^-1～1.0h^-1。

5. The process of claim 1 wherein the hydrodewaxing in step a) is conducted in a reaction zone packed with a hydrodewaxing catalyst; the hydrodewaxing catalyst is selected from one or more of FDW-3 catalyst, RDW-1 catalyst and TK-930 catalyst.

6. The preparation method according to claim 5, wherein the reaction temperature of the hydrodewaxing is 340-380 ℃, the reaction pressure is 8-14 MPa, and the volume ratio of hydrogen to oil is (500-1500): 1, the liquid hourly space velocity is 2.0h^-1～2.5h^-1。

7. The method according to claim 1, wherein the vacuum degree of the reduced pressure distillation in the step b) is 100mmHg to 500 mmHg.

8. The preparation method according to claim 1, wherein the top temperature of the furfural extraction in the step b) is 100-150 ℃, the bottom temperature is 80-110 ℃, and the ratio of the solvent to the oil is (1.0-4.0): 1.

9. the production method according to any one of claims 1 to 8, further comprising, before the hydrofinishing in the step a):

pre-sulfurizing the catalyst for hydrorefining and hydrodewaxing; the vulcanized oil used for the pre-vulcanization treatment is sulfur-containing diesel oil; the sulfur source in the sulfur-containing diesel oil is carbon disulfide and/or dimethyl disulfide; the content of the sulfur source in the sulfur-containing diesel oil is 2 to 5 weight percent.

10. The preparation method according to claim 9, wherein the hydrogen partial pressure of the pre-vulcanization treatment is 5MPa to 15MPa, and the space velocity is 0.1h^-1～2h^-1The volume ratio of hydrogen to oil is (500-1500): 1, the temperature is 200-380 ℃, and the time is 10-48 h.

Technical Field

The invention relates to the technical field of petrochemical industry, in particular to a preparation method of a high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer.

Background

With the rapid development of the tire industry, the amount of synthetic rubber used is rapidly increasing, and the development of rubber plasticizers is also rapid. The global environmental problems are increasingly prominent, various environmental regulations are in turn coming out, and rubber plasticizers also face new requirements for environmental protection. The 2005/69/EC directive issued by the European parliament and the European Union in 9.12.2005 puts a clear limit on the content of PAHs in tires and rubber: the mass of BaP in each 1kg of rubber plasticizer is less than 1mg, and the total mass of 8 PAHs in each 1kg of rubber plasticizer is less than 10 mg. 2005/69/EC were replaced by the EU REACH regulation which has been carried out 1/2010 and which specifies that the 8 PAHs [ respectively benzo (a) pyrene (BaP), benzo (e) pyrene, benzo (a) anthracene, chrysene, benzo (b) fluoranthene, benzo (j) fluoranthene, benzo (k) fluoranthene, dibenzo (a, h) anthracene ] content in the oil does not exceed 10mg/kg, with BaP not exceeding 1mg/kg, otherwise the rubber plasticizer could not be put on the market and used for the production of tires or tire components.

GB/T33322-2016 rubber plasticizer aromatic base mineral oil formulates the technical index requirement of A2530 brand according to aromatic carbon content and viscosity grade, but at present, no supplier meeting the technical index requirement of A2530 is provided at home, and only one Germany H & R company produces the high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer similar to A2530 on the market. CN201310169306.5, CN201310169705.1, CN201310198501.0, CN201310199979.5 and CN201310291645.0 all adopt a furfural refining process or an improved furfural refining process and other processes to prepare environment-friendly rubber plasticizers, but the yield of target products is not more than 65 wt%, and the content of CA is not more than 35 wt%, so that the contradictions between the low yield of the traditional two-stage furfural extraction process and the content of polycyclic aromatic hydrocarbon (PCA) and aromatic Carbon (CA) are not well solved.

Disclosure of Invention

In view of the above, the invention aims to provide a preparation method of a high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer, which is simple to operate, high in safety and high in product yield; the kinematic viscosity at 100 ℃ of the high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer prepared further>57mm²S, CA content>35 wt%, PCA < 3 wt%, PAHs content < 10mg/kg, BaP content < 1 mg/kg.

The invention provides a preparation method of a high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer, which comprises the following steps:

a) sequentially carrying out hydrofining and hydrodewaxing on the naphthenic base vacuum residue to obtain a hydrogenated liquid product;

b) carrying out reduced pressure distillation on the hydrogenation liquid product obtained in the step a), and collecting fractions with the boiling point being more than or equal to 360 ℃; and performing furfural extraction, and obtaining the high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer on the lower layer.

Preferably, the distillation range of the naphthenic vacuum residue in the step a) is 420-580 ℃, the aromatic hydrocarbon content is 30-35 wt%, the polycyclic aromatic compound content is 10-15 wt%, the pour point is 10-35 ℃, and the viscosity at 100 ℃ is 25mm²/s～35mm²/s。

Preferably, the hydrofinishing in step a) is carried out in a reaction zone packed with a hydrofinishing catalyst; the hydrofining catalyst is selected from one or more of MLDW-4 catalyst, ICR-240 catalyst and HR1058 catalyst.

Preferably, the reaction temperature of the hydrofining is 300-350 ℃, the reaction pressure is 8-14 MPa, and the volume ratio of hydrogen to oil is (500-1500): 1, the liquid hourly space velocity is 0.5h^-1～1.0h^-1。

Preferably, the hydrodewaxing in step a) is carried out in a reaction zone packed with a hydrodewaxing catalyst; the hydrodewaxing catalyst is selected from one or more of FDW-3 catalyst, RDW-1 catalyst and TK-930 catalyst.

Preferably, the reaction temperature of the hydrodewaxing is 340-380 ℃, the reaction pressure is 8-14 MPa, and the volume ratio of hydrogen to oil is (500-1500): 1, the liquid hourly space velocity is 2.0h^-1～2.5h^-1。

Preferably, the vacuum degree of the reduced pressure distillation in the step b) is 100mmHg to 500 mmHg.

Preferably, in the step b), the top temperature of the furfural extraction is 100-150 ℃, the bottom temperature of the furfural extraction is 80-110 ℃, and the agent-oil ratio is (1.0-4.0): 1.

preferably, before the hydrorefining in step a), the method further comprises:

pre-sulfurizing the catalyst for hydrorefining and hydrodewaxing; the vulcanized oil used for the pre-vulcanization treatment is sulfur-containing diesel oil; the sulfur source in the sulfur-containing diesel oil is carbon disulfide and/or dimethyl disulfide; the content of the sulfur source in the sulfur-containing diesel oil is 2 to 5 weight percent.

Preferably, the hydrogen partial pressure of the pre-vulcanization treatment is 5MPa to 15MPa, and the space velocity is 0.1h^-1～2h^-1The volume ratio of hydrogen to oil is (500-1500): 1, the temperature is 200-380 ℃, and the time is 10-48 h.

The invention provides a preparation method of a high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer, which comprises the following steps: a) sequentially carrying out hydrofining and hydrodewaxing on the naphthenic base vacuum residue to obtain a hydrogenated liquid product; b) carrying out reduced pressure distillation on the hydrogenation liquid product obtained in the step a), and collecting fractions with the boiling point being more than or equal to 360 ℃; and performing furfural extraction, and obtaining the high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer on the lower layer. Compared with the prior art, the preparation method provided by the invention adopts a combined process different from the traditional two-stage furfural extraction process, realizes better integral interaction, and can solve the problems of low yield, polycyclic aromatic hydrocarbon (PCA) content and aromatic hydrocarbon (FAR) content of the traditional two-stage furfural extraction processThe technical problem of the contradiction between the Carbon (CA) contents. The experimental result shows that the preparation method provided by the invention has high product yield, and the prepared high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer has high yield>65 wt%; and the kinematic viscosity at 100 ℃ of the prepared high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer>57mm²S, CA content>35 wt%, PCA less than 3 wt%, PAHs content less than 10mg/kg, BaP content less than 1mg/kg, and belongs to high aromatic hydrocarbon high viscosity environment-friendly rubber plasticizer products.

Meanwhile, the preparation method provided by the invention is simple to operate, high in safety and wide in application prospect.

Drawings

FIG. 1 is a flow chart of a pseudo three-stage process in example 1 of the present invention.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a preparation method of a high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer, which comprises the following steps:

a) sequentially carrying out hydrofining and hydrodewaxing on the naphthenic base vacuum residue to obtain a hydrogenated liquid product;

b) carrying out reduced pressure distillation on the hydrogenation liquid product obtained in the step a), and collecting fractions with the boiling point being more than or equal to 360 ℃; and performing furfural extraction, and obtaining the high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer on the lower layer.

The invention firstly carries out hydrofining and hydrodewaxing on naphthenic base vacuum residue oil in sequence to obtain a hydrogenated liquid product.

In the invention, the naphthenic vacuum residue is a raw material for preparing the high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer; the distillation range of the naphthenic vacuum residue is preferably 420-580 ℃, more preferably 460-560 ℃, and the content of aromatic hydrocarbon (CA) is preferably 30-35 wt%, more preferablyIs selected from 31 wt% to 32 wt%, the content of polycyclic aromatic compound (PCA) is preferably 10 wt% to 15 wt%, more preferably 13 wt% to 14 wt%, the pour point is preferably 10 to 35 deg.C, more preferably 20 to 30 deg.C, and the viscosity at 100 deg.C is preferably 25mm²/s～35mm²S, more preferably 30mm²/s～32mm²/s。

In the present invention, the hydrorefining is preferably carried out in a reaction zone in which a hydrorefining catalyst is packed, specifically, in a reaction zone in which a hydrorefining catalyst is packed in a fixed bed reactor (i.e., a hydrorefining reaction zone). In the present invention, the hydrofinishing catalyst is preferably selected from one or more of MLDW-4 catalyst, ICR-240 catalyst and HR1058 catalyst; wherein the MLDW-4 catalyst is provided by Exxon Mobil, the ICR-240 catalyst is provided by Chevron Chinese energy company, and the HR1058 catalyst is provided by Akwson (Beijing) trade company, Inc.

In the present invention, the hydrodewaxing is preferably carried out in a reaction zone packed with a hydrodewaxing catalyst, more specifically, in a reaction zone packed with a hydrodewaxing catalyst (i.e., a hydrodewaxing reaction zone) in a fixed-bed reactor. In the present invention, the hydrodewaxing catalyst is preferably selected from one or more of FDW-3 catalyst, RDW-1 catalyst and TK-930 catalyst; wherein the FDW-3 catalyst is provided by China petrochemical industry institute of Dalian (smoothie) petrochemical, the RDW-1 catalyst is provided by petrochemical science institute, and the TK-930 catalyst is provided by Topussol catalyst GmbH.

In the preferred embodiment of the invention, the hydrofining catalyst and the hydrodewaxing catalyst are sequentially filled in the two-stage hydrogenation fixed bed reactor along the flow direction of the naphthenic base vacuum residue raw material; the mass ratio of the hydrofining catalyst to the hydrodewaxing catalyst is preferably (1-5): 1, more preferably 1: 1.

in the present invention, before the hydrorefining, it is preferable to further include:

pre-sulfurizing the catalyst for hydrorefining and hydrodewaxing; namely, the catalyst filled in the two-stage hydrogenation fixed bed reactor is presulfurized. In the invention, the presulfurization treatment refers to reacting the catalyst in the presence of hydrogen and vulcanized oil for a period of time, so as to improve the activity of the catalyst.

In the invention, the vulcanized oil used for the pre-vulcanization treatment is preferably sulfur-containing diesel oil and consists of a sulfur source and diesel oil; the sulfur source in the sulfur-containing diesel oil is preferably carbon disulfide (CS)₂) And/or dimethyldisulfide (DMDS), more preferably dimethyldisulfide; the content of the sulfur source in the sulfur-containing diesel oil is preferably 2 wt% to 5 wt%, and more preferably 3 wt%.

In the present invention, the hydrogen partial pressure in the prevulcanization treatment is preferably 5MPa to 15MPa, more preferably 10MPa, and the space velocity is preferably 0.1h^-1～2h^-1More preferably 2h^-1The volume ratio of hydrogen to oil is preferably (500-1500): 1, more preferably 500: 1, the temperature is preferably 200 to 380 ℃, more preferably 340 to 360 ℃, and the time is preferably 10 to 48 hours, more preferably 24 hours.

In the present invention, before the hydrorefining, it is preferable to further include:

preheating naphthenic base vacuum residue; the temperature of the preheating is preferably 80 ℃ to 120 ℃, more preferably 100 ℃.

In the present invention, the reaction temperature of the hydrofining is preferably 300 to 350 ℃, more preferably 310 to 340 ℃, the reaction pressure is preferably 8 to 14MPa, more preferably 8 to 12MPa, and the hydrogen-oil volume ratio is preferably (500 to 1500): 1, more preferably (800 to 1200): 1, the liquid hourly volume space velocity is preferably 0.5h^-1～1.0h^-1More preferably 0.6h^-1～0.9h^-1(ii) a Further, the hydrorefined product oil is obtained.

In the invention, the reaction temperature of the hydrodewaxing is preferably 340-380 ℃, more preferably 340-360 ℃, the reaction pressure is preferably 8-14 MPa, more preferably 8-12 MPa, and the volume ratio of hydrogen to oil is preferably (500-1500): 1, more preferably (800 to 1200): 1, the liquid hourly volume space velocity is preferably 2.0h^-1～2.5h^-1More preferably 2.0h^-1～2.3h^-1(ii) a Further obtaining the hydrodewaxing produced oil, namely the hydrogenation liquid product.

After the hydrogenation liquid product is obtained, the obtained hydrogenation liquid product is subjected to reduced pressure distillation, and fractions with the boiling point of more than or equal to 360 ℃ are collected; and performing furfural extraction, and obtaining the high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer on the lower layer.

In the present invention, the degree of vacuum of the reduced pressure distillation is preferably 100mmHg to 500mmHg, more preferably 150mmHg to 250 mmHg; collecting the fraction with the boiling point of more than or equal to 360 ℃, namely collecting the fraction with the boiling point of more than or equal to 360 ℃ under normal pressure.

Aiming at furfural extraction, the invention simulates the extraction effect of an extraction tower of an industrial device and carries out the research of a pseudo three-section extraction test; this process corresponds to a static operation of the extraction column in three theoretical equilibrium stages, and although it differs from a dynamic extraction column, the results are closer to those of an actual extraction column than in a single-stage extraction.

In the invention, the top temperature of the furfural extraction (i.e. the furfural extraction by the pseudo three-stage process) is preferably 100-150 ℃, more preferably 110-130 ℃, the bottom temperature of the furfural extraction is preferably 80-110 ℃, more preferably 90-100 ℃, and the ratio of the solvent to the oil is preferably (1.0-4.0): 1, more preferably (2.0 to 3.0): 1.

according to the preparation method provided by the invention, a specific reaction catalyst is utilized in the hydrofining reaction section, and operation parameters such as reaction temperature, reaction pressure, reaction space velocity, hydrogen-oil ratio and the like are optimized, so that the degrees of the hydrogenation depth, the cracking depth, the desulfurization, the denitrification, the deoxidation and the demetallization rate of the raw oil are well controlled, the desulfurization, the denitrification and the deoxidation rates of the hydrofining reaction section are improved, the cracking degree is deepened, but the saturation depth of aromatic hydrocarbon is reduced, the yield of low-boiling fraction and gas in the generated oil is reduced, and the conversion rate of the raw material is increased; by utilizing a specific reaction catalyst in the hydrodewaxing reaction section and optimizing the operating parameters such as reaction temperature, reaction pressure, reaction space velocity, hydrogen-oil ratio and the like, the conversion rate of isodewaxing and catalytic dewaxing is improved, the service life of the isodewaxing and catalytic dewaxing catalyst is prolonged, the hydrogenation saturation effect of unsaturated hydrocarbon is improved, and the prepared hydrogenation liquid product has better low-temperature performance; and then, performing furfural extraction on the hydrogenated liquid product after vacuum distillation, adjusting and controlling the contradiction between the content of the condensed ring aromatic hydrocarbon (PCA) and the content of aromatic Carbon (CA) by adjusting parameters such as an optimizing agent oil ratio, the temperatures of the tower top and the tower bottom, and the like, enriching the monocyclic and bicyclic aromatic hydrocarbons, and finally obtaining a high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer (high-viscosity-level product) on the lower layer. The preparation method provided by the invention is safe, simple to operate, easy to obtain raw materials, low in cost and easy to realize industrial mass production.

In the tire manufacturing process, the polycyclic aromatic compound (PCA) content of the rubber plasticizer is required to be less than 3%, and the higher the aromatic hydrocarbon (CA) content of the rubber plasticizer is, the better, in order to impart good compatibility of the rubber plasticizer with the rubber. Therefore, the invention starts from the raw material source, the product performance, the production feasibility, the economy and the requirements of environmental protection and energy conservation, the naphthenic base vacuum residue oil is used as the raw material, and the high-aromatic hydrocarbon high-viscosity environment-friendly rubber plasticizer product with excellent performance is prepared by a combined process means of proper hydrorefining, hydrodewaxing and furfural refining (not only different from the traditional two-stage furfural extraction process, but also different from the non-catalytic oxidation process), so that the value maximization of the heavy wax oil fraction is realized, the considerable economic benefit is created, the green change is raised in the tire industry, the trend that the environment-friendly rubber plasticizer continuously replaces the common aromatic oil is created, and the large-scale industrial production is realized.

The invention provides a preparation method of a high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer, which comprises the following steps: a) sequentially carrying out hydrofining and hydrodewaxing on the naphthenic base vacuum residue to obtain a hydrogenated liquid product; b) carrying out reduced pressure distillation on the hydrogenation liquid product obtained in the step a), and collecting fractions with the boiling point being more than or equal to 360 ℃; and performing furfural extraction, and obtaining the high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer on the lower layer. Compared with the prior art, the preparation method provided by the invention adopts a combined process different from the traditional two-stage furfural extraction process, realizes better overall interaction, and can solve the technical problems of low yield and contradiction between the content of polycyclic aromatic hydrocarbon (PCA) and the content of aromatic Carbon (CA) in the traditional two-stage furfural extraction process. The experimental result shows that the preparation method provided by the invention has high product yield, and the prepared high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer is obtainedRate of change>65 wt%; and the kinematic viscosity at 100 ℃ of the prepared high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer>57mm²S, CA content>35 wt%, PCA less than 3 wt%, PAHs content less than 10mg/kg, BaP content less than 1mg/kg, and belongs to high aromatic hydrocarbon high viscosity environment-friendly rubber plasticizer products.

Meanwhile, the preparation method provided by the invention is simple to operate, high in safety and wide in application prospect.

To further illustrate the present invention, the following examples are provided for illustration.

Example 1

Sequentially filling a hydrofining catalyst and a hydrodewaxing catalyst in a two-stage hydrogenation fixed bed reactor along the flow direction of the naphthenic vacuum residue raw material; wherein the hydrofining catalyst is HR1058 catalyst, the hydrodewaxing catalyst is RDW-1 catalyst, and the mass ratio of the hydrofining catalyst to the hydrodewaxing catalyst is 1: 1.

pre-vulcanizing the catalyst filled in the two-stage hydrogenation fixed bed reactor; the presulfurization process conditions are as follows: dimethyl disulfide (DMDS) accounting for 3 percent of the weight of the vulcanized oil and the balance of refined diesel oil (the oil index is shown in table 1) are used as the vulcanized oil, hydrogen is introduced at the hydrogen partial pressure of 10MPa, and the space velocity is 2.0h^-1Hydrogen-oil volume ratio 500: 1, heating the catalyst bed layer from 120 ℃ to 350 ℃ at a heating rate of 15 ℃/h, and reacting for 24h at constant temperature.

TABLE 1 oil index of refined Diesel oil in inventive example 1

Naphthenic vacuum residue with the distillation range of 460-560 ℃ (oil index shown in table 2) is used as raw material, and the naphthenic vacuum residue has CA of 31.2 wt%, PCA of 13.43 wt%, pour point of 25 ℃, and viscosity of 31.2mm at 100 DEG C²S; preheating to 100 ℃, and feeding the mixture into the two-stage hydrogenation fixed bed reactorSequentially carrying out hydrofining and hydrodewaxing; wherein the reaction pressure of hydrofining is 10MPa, the reaction temperature is 330 ℃, and the reaction space velocity is 0.7h^-1Hydrogen-oil volume ratio 1000: 1; the reaction pressure of the hydrodewaxing is 10MPa, the reaction temperature is 350 ℃, and the reaction space velocity is 2.1h^-1Hydrogen-oil volume ratio 1000: 1.

TABLE 2 oil index of naphthenic vacuum residue feedstock of inventive example 1

After the hydrogenation of the raw material in the two-stage hydrogenation fixed bed reactor is finished, feeding the obtained hydrogenation liquid product into a reduced pressure distillation tower for distillation, and controlling the vacuum degree during distillation to be 150 mmHg; collecting the fraction with the boiling point being more than or equal to 360 ℃ under normal pressure.

Performing furfural extraction: simulating the extraction effect of an extraction tower of an industrial device, and carrying out a false three-section extraction test, wherein a false three-section process flow chart is shown in a figure 1; in the furfural extraction by the pseudo three-stage process, the temperature at the top of the tower is 110 ℃, the temperature at the bottom of the tower is 90 ℃, the ratio of the solvent to the oil is 2.0: 1, obtaining the high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer at the lower layer, wherein the yield is 65%.

Examples 2 to 5

By adopting the preparation method provided in example 1 and according to the process conditions in table 3, the high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer is obtained respectively.

TABLE 3 Process conditions for examples 2 to 5

Index detection is respectively carried out on the high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer prepared in the embodiments 1-5, and the specific detection method is as follows:

the kinematic viscosity of the prepared high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer is detected according to the standard determination of GB/T265-1988 petroleum product kinematic viscosity determination method and dynamic viscosity calculation method.

And detecting the pour point of the prepared high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer according to the standard determination of GB/T3535-2006 petroleum product pour point determination method.

According to the standard determination of SH/T0725-2002 'calculation method for carbon type composition of petroleum-based insulating oil', the carbon type composition of the prepared high-aromatic high-viscosity environment-friendly rubber plasticizer is detected.

And (3) detecting the content of the polycyclic aromatic hydrocarbon (PCA) in the prepared high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer according to the standard determination of NB/SH/T0838-2010 (determination of content of polycyclic aromatic hydrocarbon (PCA) in unused lubricating oil base oil and asphaltene-free vacuum residue).

The polycyclic aromatic hydrocarbon content of the prepared rubber plasticizer is detected according to the standard measurement of SN/T1877.3-2007 method for measuring polycyclic aromatic hydrocarbon in mineral oil.

The results are shown in Table 4.

Table 4 index data of high aromatic hydrocarbon and high viscosity environment-friendly rubber plasticizer prepared in embodiments 1 to 5 of the present invention

Measurement items	Example 1	Example 2	Example 3	Example 4	Example 5
						Yield/wt%	65	65	67	66	68
Kinematic viscosity (100 ℃ C.)/(mm)2/s)	57.2	57.1	58.1	57.3	57.5
						Pour point/. degree.C	15	15	15	12	10
CA/wt％	36.1	35.1	36.2	35.6	35.7
						PCA/wt％	2.76	2.48	2.67	2.34	2.78
PAHs/(mg/kg)	8.21	7.84	6.53	6.89	8.43
						Benzo (a) pyrene/(mg/kg)	＜1	＜1	＜1	＜1	＜1

As can be seen from Table 4, the kinematic viscosity at 100 ℃ of the high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer prepared in the embodiments 1 to 5 of the present invention>57mm²S, CA content>35 wt%, PCA less than 3 wt%, PAHs content less than 10mg/kg, BaP content less than 1mg/kg, and belongs to high aromatic hydrocarbon high viscosity environment-friendly rubber plasticizer products.

Meanwhile, the preparation method provided by the invention is simple to operate, high in safety and high in product yield, and the yield of the prepared high-aromatic-hydrocarbon high-viscosity environment-friendly rubber plasticizer is more than 65 wt%.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.