CN110982553B - Method for preparing coal-based environment-friendly rubber oil by adopting medium-low temperature coal tar hydrogenated tail oil fraction - Google Patents

Abstract

A method for preparing coal-based environment-friendly rubber oil by adopting medium-low temperature coal tar hydrogenation tail oil fraction comprises the steps of carrying out primary solvent refining on the medium-low temperature coal tar hydrogenation tail oil fraction to obtain primary raffinate oil; under the condition of the presence of a hydrodewaxing and hydrofinishing catalyst, the primary raffinate oil is subjected to a one-stage series hydrodewaxing-hydrofinishing combined process treatment, then is subjected to fractionation to obtain distillate oil with the temperature of more than 320 ℃, and finally is subjected to secondary solvent refining and solvent separation to obtain the coal-based environment-friendly rubber oil. The hydrodewaxing catalyst of the invention selectively cracks the high pour point normal paraffin and the similar normal paraffin in the reactant, supplements the olefin produced in the saturation cracking process of the refined catalyst by hydrogenation, simultaneously carries out partial hydrogenation saturation on the heavy aromatic hydrocarbon component in the raw material, and can convert the heavy aromatic hydrocarbon component into an effective naphthenic base component while reducing the pour point of an oil product, so that the viscosity of the product is reduced slightly, and a higher product yield can be obtained.

Description

A method for preparing coal-based environmental protection rubber oil by adopting medium and low temperature coal tar hydrogenation tail oil fractions

technical field

The invention belongs to the field of coal tar processing, in particular to a method for preparing a coal-based environment-friendly rubber oil by adopting medium and low temperature coal tar hydrogenation tail oil fractions.

Background technique

my country is rich in medium and low temperature coal tar resources, but the utilization rate is low. The products obtained from the hydrogenation of medium and low temperature coal tar can be used as vehicle fuels or chemical raw materials. Among them, the mid-low temperature coal tar hydrogenation tail oil fraction has low paraffin content, high naphthenic and aromatic content, and can be used to process and prepare naphthenic oil chemical products.

Rubber oil is a softening oil used in the process of rubber synthesis or when rubber is processed into products. Tire rubber oil is the most important application field of rubber oil and has good compatibility with rubber. The improvement of environmental protection requirements has also become increasingly strict on the quality of tire rubber oil. The European Union has completely banned the use of tire rubber oil with excessive polycyclic aromatic hydrocarbon content since 2010, which requires environmentally friendly tire rubber oil to be rich in a certain amount of aromatic hydrocarbons. , and make sure that the limited content of fused-ring aromatic hydrocarbons does not exceed the standard. The existing high-quality production raw materials for environmentally friendly rubber oil, such as naphthenic oil, are insufficient, and most of the rubber oils prepared from other types of raw materials have low compatibility with rubber; the coal tar hydrogenation tail oil fraction is rich in naphthenic and aromatic hydrocarbons, and the raw materials are easy to Therefore, it has great advantages to obtain environmentally friendly tire rubber oil after processing.

Patent CN201610946593.X invents a method for preparing environment-friendly naphthenic rubber oil from naphthenic vacuum wax oil. First, the naphthenic vacuum wax oil is subjected to hydrotreating and pre-refining, and then the obtained pre-refining and hydrogenation is carried out. The wax oil is degassed to obtain a degassed hydrogenated wax oil, and then the degassed and hydrogenated wax oil is subjected to solvent refining, and the obtained raffinate is removed from the solvent to obtain an environmentally friendly naphthenic rubber oil. The method has the characteristics of high yield and high utilization rate of raw materials, but has the problem of insufficient naphthenic oil resources.

The patent CN201110240555.X adopts a two-stage refining process of ternary compound solvent refining and high-pressure hydrorefining to process the aromatic extract oil of vacuum distillate oil, and then prepares environmentally friendly rubber oil. The raffinate obtained by the ternary compound solvent refining process retains a lot of mono- and bi-cyclic aromatic hydrocarbons, and removes the condensed aromatic hydrocarbons. The obtained tire rubber oil product has _a CA content of more than 16%, a PCA content of less than 3%, and 8 kinds of The content of PAHs is less than 10mg/kg, and the yield of environmentally friendly rubber oil is over 74%. The disadvantage is that the method adopts a high-pressure hydrogenation process, and the cost of equipment investment is high and the cost is relatively high.

Patent CN201710750822.5 uses reduced four-line oil as raw material, and prepares environmentally friendly rubber oil through a solvent refining-hydrorefining-hydrogenerating-upgrading-secondary solvent refining process, and the _CA content of the environmentally friendly rubber oil obtained by the modified process is as high as 25%. However, due to the adoption of a long process flow, the yield of the obtained environmentally friendly rubber oil product is low.

SUMMARY OF THE INVENTION

Aiming at the characteristics of insufficient naphthenic oil raw material resources and long production process flow in the production of environmentally friendly rubber oil, the present invention provides a method for preparing coal-based environmentally friendly rubber oil by using medium and low temperature coal tar hydrogenation tail oil fractions with simple process flow .

For achieving the above object, the present invention adopts the following technical scheme:

A method for preparing coal-based environment-friendly rubber oil by adopting medium and low temperature coal tar hydrogenation tail oil fractions, comprising the following steps:

(1) carrying out a solvent refining to the medium and low temperature coal tar hydrogenation tail oil fraction, and obtaining a raffinate oil and a raffinate oil after separating the solvent;

(2) in the presence of hydropour pour point depressurization and hydrotreating supplementary refining catalyst, the primary raffinate oil is subjected to a one-stage series hydropour pour point depressurization-hydrogenation supplementary refining combined process treatment to obtain a hydrogenated liquid product;

(3) fractionating the hydrogenated liquid product to obtain a distillate oil greater than 320°C;

(4) Perform secondary solvent refining on the distillate oil above 320° C. described in step (3), and separate the solvent to obtain a coal-based environmentally friendly rubber oil.

A further improvement of the present invention is that, in step (1), the medium and low temperature coal tar hydrogenation tail oil fraction is one or both of the middle and low temperature coal tar full fraction hydrogenation tail oil and the medium and low temperature coal tar fraction hydrogenation tail oil .

A further improvement of the present invention is that, in step (1), the primary solvent refining is multi-stage countercurrent refining, the number of stages is 2 to 5, and the solvent is one of furfural, phenol and N-methylpyrrolidone;

The mass ratio of the solvent of the primary solvent refining to the medium and low temperature coal tar hydrogenation tail oil fraction is (0.5～4):1;

The primary solvent refining temperature is 50°C to 120°C.

A further improvement of the present invention is that, in step (1), the mass ratio of the solvent of the primary solvent refining to the medium and low temperature coal tar hydrogenation tail oil fraction is (1～3):1; the primary solvent refining temperature is 70°C～ 90°C.

A further improvement of the present invention is that, in step (2), when the one-stage series-connected hydro-depression-hydrogenation supplementary refining combined process is processed, according to the flow direction, the primary raffinate passes through the hydro-depression reaction zone and hydrogenation. The supplementary refining reaction zone is filled with the hydrogenation decompression catalyst, and the hydrogenation supplementary refining reaction zone is filled with the hydrogenation supplementary refining catalyst. ): 1, the hydropour point depressurization catalyst and the hydrogenation supplementary refining catalyst are both sulfurized catalysts.

The further improvement of the present invention is that the volume ratio of the hydropour point depressurization catalyst to the hydrogenation supplementary refining catalyst is (2-4): 1; The catalyst is HTLF-1 catalyst or FV-5 catalyst.

A further improvement of the present invention lies in that, in step (2), in the one-stage series of combined hydropour point depressurization-hydrogenation supplementary refining process, the reaction temperature of the hydropour point depressurization process is 330°C to 380°C, and the hydrogenation supplementary refining process The reaction temperature of the process is 350°C to 380°C, and the reaction pressure of the hydropour condensation reaction zone and the hydrogenation supplementary refining reaction zone is 4MPa to 16MPa during the one-stage series-connected hydropour condensation-hydrogenation supplementary refining combined process treatment. , the volume ratio of hydrogen to oil is 300:1 ~ 1000:1, and the volumetric space velocity of liquid hour is 0.5h ^-1 ~ 3h ^-1 .

A further improvement of the present invention lies in that the reaction temperature of the hydropour condensation process is 350°C to 370°C;

The reaction temperature of the hydrogenation supplementary refining process is 350℃～370℃;

The reaction pressure of the hydropour condensation reaction zone and the hydrogenation supplementary refining reaction zone is 8MPa～10MPa;

The volume ratio of hydrogen oil is 500:1～800:1;

The liquid hourly volume space velocity is 1.0h ^-1 to 2.5h ^-1 .

A further improvement of the present invention is that, in step (3), the distillation range of the secondary solvent refining raw material is 320°C to 450°C; the temperature of the secondary solvent refining is 70°C to 90°C.

A further improvement of the present invention is that, in step (4), the secondary solvent refining is multi-stage countercurrent refining, and the solvent is any one of furfural, phenol and N-methylpyrrolidone; the temperature for secondary solvent refining is At 50℃～120℃, the mass ratio of solvent to distillate oil greater than 320℃ is (0.5～4):1; the mass ratio of solvent to distillate oil greater than 320℃ is (1～3):1.

Compared with the prior art, the present invention has the beneficial effects as follows: the present invention uses low-cost medium and low temperature coal tar hydrogenation tail oil fractions as raw materials, and has resource advantages; The solvent refining combined process is used to prepare environmentally friendly rubber oil products. The hydrogen depointing reactor and the hydrogenation supplementary refining reactor are connected in series, and the hydrogen passes through one time, and no higher pressure is required (the hydrogen pressure is not higher than 10MPa), which reduces the equipment investment and the process. The process is simple and the benefit is high; the hydropour point depressant catalyst selectively cracks the high freezing point n-paraffins and n-paraffin-like hydrocarbons in the reactants, and supplements the olefins produced in the saturated cracking process of the refining catalyst through hydrogenation, and at the same time makes the heavy metals in the raw materials. Partial hydrogenation and saturation of high-quality aromatic components can reduce the pour point of oil, and at the same time, it can also partially convert heavy aromatic components into effective naphthenic components, so that the viscosity of the product decreases less, and higher oil can be obtained. Product yield. The invention not only expands the utilization range of coal tar, but also under the condition of ensuring product yield, the prepared rubber oil product meets the requirements of EU environmental protection standards, the pour point is lower than 6°C, and the low temperature physical properties of the rubber product can be improved.

Description of drawings

FIG. 1 is a flow chart of a method for preparing a coal-based environmentally friendly rubber oil provided by the present invention.

Detailed ways

The present invention will be described in detail below with reference to the accompanying drawings.

The specific embodiments provided by the present invention are only used to illustrate and explain the present invention, and are not used to limit the present invention.

The invention uses coal tar hydrogenated tail oil as raw material, and prepares the environmental protection rubber oil through the combined process of solvent refining-hydrogen pour point depressurization-hydrogenation supplementary refining-solvent refining.

Referring to Fig. 1, the preparation method of coal-based environmentally friendly rubber oil provided by the present invention comprises the following steps:

(1) a solvent refining is carried out to the medium and low temperature coal tar hydrogenation tail oil fraction, and a raffinate oil and a raffinate oil are obtained after separating the solvent;

(2) in the presence of hydropour pour point depressurization and hydrotreating supplementary refining catalyst, the primary raffinate oil is subjected to a one-stage series hydropour pour point depressurization-hydrogenation supplementary refining combined process treatment to obtain a hydrogenated liquid product;

(3) fractionating the hydrogenated liquid product to obtain >320° C. distillate oil as a raw material for secondary solvent refining;

(4) Perform secondary solvent refining on the >320° C. distillate oil described in step (3), and separate the solvent to obtain secondary raffinate oil, which is coal-based environmentally friendly rubber oil.

In the above preparation method, the medium and low temperature coal tar hydrogenation tail oil fraction includes medium and low temperature coal tar full fraction hydrogenation tail oil, medium and low temperature coal tar fraction hydrogenation tail oil, and the medium and low temperature coal tar hydrogenation tail oil fraction is added One or more of the tail oil obtained from hydrotreating, hydrorefining and hydrocracking processes.

In step (1), the primary solvent refining is multi-stage countercurrent refining, the number of stages is 2 to 5, and the solvent is one of furfural (ie 2-furancarboxaldehyde), phenol and N-methylpyrrolidone;

In step (1), the mass ratio of the solvent of the primary solvent refining to the coal tar hydrogenation tail oil fraction is (0.5～4):1, preferably (1～3):1;

In step (1), the primary solvent refining temperature may be 50°C to 120°C, preferably 70°C to 90°C.

In step (2), according to the logistics direction, the one-stage series-connected hydropour point depressurization-hydrogenation supplementary refining combined process includes a hydrogenation point depressurization reaction zone and a hydrogenation supplementary refining reaction zone, that is, according to the logistics direction, the primary raffinate oil is After passing through the hydropour condensation reaction zone and the hydrogenation supplementary refining reaction zone, according to the volume ratio of (1～5):1, preferably (2～4):1, the hydropour condensation catalyst and the hydrogenation supplementary refining catalyst are respectively loaded, The catalysts used are all sulfurized catalysts. Hydrogen pour point depressant catalyst is commercially available FDW-3 catalyst (Sinopec Changling Branch) or RDW-1 catalyst (Sinopec Fushun Branch), and the hydrogenation supplementary refining catalyst is commercially available HTLF -1 catalyst (Liaoning Haitai Technology Development Co., Ltd.) or FV-5 catalyst (Sinopec Fushun Petrochemical Research Institute).

In step (2), in the one-stage series-connected hydropour pour point depressurization-hydrogenation supplementary refining combined process, the reaction temperature of the hydropour pour point depressurization process is 330°C to 380°C, preferably 350°C to 370°C; The reaction temperature of the refining process is 350°C to 380°C, preferably 350°C to 370°C;

In step (2), the reaction pressure of the one-stage series-connected hydropour condensation-hydrogenation supplementary refining combined process reaction zone is 4 MPa to 16 MPa, preferably 8 MPa to 10 MPa; and the volume ratio of hydrogen to oil is 300:1 to 1000:1 , preferably 500:1 to 800:1; the liquid hourly volume space velocity is 0.5h ^-1 to 3h ^-1 , preferably 1.0h ^-1 to 2.5h ^-1 .

In step (3), the distillation range of the secondary solvent refining raw material (ie the distillate oil greater than 320°C) is 320°C to 450°C.

In step (4), the secondary solvent refining is multi-stage countercurrent refining, and the solvent is any one of furfural, phenol and N-methylpyrrolidone; the solvent refining temperature is 50°C to 120°C, preferably 70°C ~90°C; the mass ratio of solvent to raw material is (0.5-4):1, preferably (1-3):1.

The following are specific examples.

Example 1 Preparation of coal-based environmentally friendly rubber oil

Using low-temperature coal tar full-fraction hydrogenated tail oil as raw material (see Table 1 for the properties of raw materials), three-stage countercurrent refining is carried out, the solvent is furfural, the refining temperature is 90 ° C, the solvent to raw material mass ratio is 4:1, and the top of the refining tower is The obtained product is recovered from solvent to obtain primary raffinate oil, which is used as the raw material for subsequent hydrorefining; the product obtained at the bottom of the refining tower is recovered from solvent to obtain primary raffinate oil for other purposes.

Table 1 Raw material properties of low temperature coal tar full fraction hydrogenation tail oil

In the presence of a hydro pour point depressing catalyst (FDW-3 catalyst) and a hydroprocessing supplementary refining catalyst (HTLF-1 catalyst), the primary raffinate is subjected to a one-stage series series hydro pour point depressing-hydrogenation supplementary refining combined process treatment , to obtain a hydrotreated oil (ie, a hydrogenated liquid product).

The one-stage series-connected hydropour point depressurization-hydrogenation supplementary refining combined process includes a hydropoint point depressurization reaction zone and a hydrotreating supplementary refining reaction zone. Specifically, according to the flow direction of the material, the hydropour point depressant is respectively filled according to the volume ratio of 4:1. Catalysts and hydrogenation supplementary refining catalysts, all catalysts used are sulfurized catalysts.

Specifically, the reaction temperature of the hydro pour point depressurization process is 340°C; the reaction temperature of the hydrogenation supplementary refining process is 360°C; The pressure is 8MPa, the volume ratio of hydrogen to oil is 800:1, and the liquid hourly volume space velocity is 2.0h ^-1 .

The obtained hydrogenated liquid product is often distilled under reduced pressure to obtain a distillate oil at 320°C to 450°C, which is used as a raw material for secondary solvent refining.

The distillate oil at 320°C to 450°C is subjected to secondary solvent refining, the refining method is three-stage countercurrent, the solvent is furfural, the solvent refining temperature is 80°C, and the mass ratio of solvent to raw material is 3:1. The obtained secondary raffinate is desolventized to obtain secondary raffinate oil, which is coal-based environmental protection rubber oil.

The performance parameters of the environmentally friendly rubber oil prepared in this example are shown in Table 2.

Example 2 Preparation of coal-based environmentally friendly rubber oil

Using the same raw materials as in Example 1, carry out three-stage countercurrent solvent refining, the solvent is furfural, the refining temperature is 100 ° C, the solvent to raw material mass ratio is 4:1, and the product obtained at the top of the refining tower is recovered after the solvent is obtained. A raffinate The oil is used as the raw material for the subsequent hydrorefining; the product obtained at the bottom of the refining tower is recovered and the solvent is recovered to obtain a once-extracted oil for other purposes.

In the presence of a hydro-depression catalyst (RDW-1 catalyst) and a hydroprocessing supplementary refining catalyst (FV-5 catalyst), the primary raffinate oil is subjected to a series of combined hydro-depression-hydrogenation supplementary refining process treatment , to obtain a hydrotreated oil.

The one-stage series-connected hydropour point depressurization-hydrogenation supplementary refining combined process includes a hydropour point depressurization reaction zone and a hydrotreating supplementary refining reaction zone. Specifically, the hydropour point depressurization catalyst is respectively filled with a volume ratio of 3:1 according to the material flow direction. and hydrogenation supplementary refining catalysts, all catalysts used are sulfurized catalysts.

Specifically, the reaction temperature of the hydro pour point depressurization process is 350°C; the reaction temperature of the hydrogenation supplementary refining process is 370°C; The pressure is 10MPa, the volume ratio of hydrogen to oil is 800:1, and the volumetric space velocity of liquid hour is 2.5h ^-1 .

The obtained hydrogenated liquid product is often distilled under reduced pressure to obtain a distillate oil at 320°C to 450°C, which is used as a raw material for secondary solvent refining.

The distillate oil at 320°C to 450°C is subjected to secondary solvent refining, the refining method is three-stage countercurrent, the solvent is furfural, the solvent refining temperature is 90°C, and the mass ratio of solvent to raw material is 3:1. The obtained secondary raffinate is desolventized to obtain secondary raffinate oil, which is coal-based environmental protection rubber oil.

The performance parameters of the environmentally friendly rubber oil prepared in this example are shown in Table 2.

Example 3

Using the same raw materials as in Example 1, carry out three-stage countercurrent solvent purification, the solvent is N-methylpyrrolidone, the purification temperature is 80 ° C, the solvent to raw material mass ratio is 2:1, the product obtained at the top of the purification tower is recovered after the solvent The primary raffinate oil is obtained as the raw material for subsequent hydrorefining; the solvent is recovered from the product obtained at the bottom of the refining tower to obtain primary raffinate oil for other purposes.

In the presence of a hydro-depression catalyst (RDW-1 catalyst) and a hydroprocessing supplementary refining catalyst (FV-5 catalyst), the primary raffinate oil is subjected to a series of combined hydro-depression-hydrogenation supplementary refining process treatment , to obtain a hydrotreated oil.

The one-stage series-connected hydropour point depressurization-hydrogenation supplementary refining combined process includes a hydropoint point depressurization reaction zone and a hydrotreating supplementary refining reaction zone. Specifically, the hydropour point depressurization catalyst is respectively filled with a volume ratio of 4:1 according to the material flow direction. and hydrogenation supplementary refining catalysts, all catalysts used are sulfurized catalysts.

Specifically, the reaction temperature of the hydro pour point depressurization process is 340°C; the reaction temperature of the hydrogenation supplementary refining process is 360°C; The pressure is 8MPa, the volume ratio of hydrogen to oil is 800:1, and the liquid hourly volume space velocity is 2.0h ^-1 .

The obtained hydrogenated liquid product is often distilled under reduced pressure to obtain a distillate oil at 320°C to 450°C, which is used as a raw material for secondary solvent refining.

The distillate oil at 320°C to 450°C is subjected to secondary solvent refining, the refining method is three-stage countercurrent, the solvent is N-methylpyrrolidone, the solvent refining temperature is 80°C, and the mass ratio of solvent to raw material is 2:1 . The obtained secondary raffinate is desolventized to obtain secondary raffinate oil, which is coal-based environmental protection rubber oil.

The performance parameters of the environmentally friendly rubber oil prepared in this example are shown in Table 2.

The performance parameters of the environment-friendly rubber oil prepared by the embodiment 1-3 of table 2

Example 4

(1) a solvent refining is carried out to the mid-low temperature coal tar full-fraction hydrogenated tail oil, and a raffinate oil and a raffinate oil are obtained after separating the solvent; The solvent is furfural;

The mass ratio of the solvent of the primary solvent refining to the coal tar hydrogenation tail oil fraction is 0.5:1;

The primary solvent refining temperature may be 50°C.

(2) in the presence of hydropour pour point depressurization and hydrotreating supplementary refining catalyst, the primary raffinate oil is subjected to a series of hydropour pour point depressurization-hydrogenation supplementary refining combined process treatment to obtain a hydrogenated liquid product; wherein, according to In the direction of logistics, the one-stage series of combined hydropour condensation-hydrogenation supplementary refining process includes a hydropour condensation reaction zone and a hydrogenation supplementary refining reaction zone. And the hydrogenation supplementary refining reaction zone, in accordance with the volume ratio of 1:1, were loaded with hydropour point depressurization catalyst (FDW-3 catalyst) and hydrogenation supplementary refining catalyst (HTLF-1 catalyst), respectively,

In the one-stage series-connected hydropour pour point depressurization-hydrogenation supplementary refining combined process, the reaction temperature of the hydropour pour point reduction process is 330°C; the reaction temperature of the hydrogenation supplementary refining process is 350°C;

The reaction pressure of the one-stage series-connected hydropour pour point-hydrogenation supplementary refining combined process reaction zone is 16MPa; the volume ratio of hydrogen to oil is 300:1; and the liquid hourly volume space velocity is 0.5h ^-1 .

(3) fractional distillation of the hydrogenated liquid product to obtain >320°C distillate oil, which is used as a raw material for secondary solvent refining; wherein, the distillation range of the secondary solvent refining raw material is 320°C to 450°C.

(4) Perform secondary solvent refining on the >320° C. distillate oil described in step (3), and separate the solvent to obtain secondary raffinate oil, which is coal-based environmentally friendly rubber oil. Wherein, the secondary solvent refining is multi-stage countercurrent refining, and the solvent is any one of furfural, phenol and N-methylpyrrolidone; the solvent refining temperature is 120°C; and the mass ratio of solvent to raw material is 0.5:1.

Example 5

(1) a solvent refining is carried out to the middle and low temperature coal tar fraction hydrogenation tail oil, and a extraction oil and a raffinate oil are obtained after the solvent is separated; is phenol;

The mass ratio of the solvent of the primary solvent refining to the coal tar hydrogenation tail oil fraction is 1:1;

The primary solvent refining temperature may be 120°C.

(2) in the presence of hydropour pour point depressurization and hydrotreating supplementary refining catalyst, the primary raffinate oil is subjected to a series of hydropour pour point depressurization-hydrogenation supplementary refining combined process treatment to obtain a hydrogenated liquid product; wherein, according to In the direction of logistics, the one-stage series of combined hydropour condensation-hydrogenation supplementary refining process includes a hydropour condensation reaction zone and a hydrogenation supplementary refining reaction zone. Hydrogenation and supplementary refining reaction zone, according to the volume ratio of 2:1, were loaded with hydropour point depressurization catalyst (FDW-3 catalyst) and hydrogenation supplementary refining catalyst (HTLF-1 catalyst), and the catalysts used were all sulfurized catalysts.

In the one-stage series-connected hydropour pour point depressurization-hydrogenation supplementary refining combined process, the reaction temperature of the hydropour pour point reduction process is 380°C, and the reaction temperature of the hydrogenation supplementary refining process is 380°C;

The reaction pressure of the one-stage series-connected hydro-depression-hydrogenation supplementary refining combined process reaction zone is 16MPa; the volume ratio of hydrogen to oil is 1000:1; and the liquid hourly volume space velocity is 3h ^-1 .

(3) fractional distillation of the hydrogenated liquid product to obtain >320°C distillate oil, which is used as a raw material for secondary solvent refining; wherein, the distillation range of the secondary solvent refining raw material is 320°C to 450°C.

(4) Perform secondary solvent refining on the >320° C. distillate oil described in step (3), and separate the solvent to obtain secondary raffinate oil, which is coal-based environmentally friendly rubber oil. Wherein, the secondary solvent refining is multi-stage countercurrent refining, and the solvent is any one of furfural, phenol and N-methylpyrrolidone; the solvent refining temperature is 50°C; and the mass ratio of solvent to raw material is 4:1.

Example 6

(1) a solvent refining is carried out to the mid-low temperature coal tar full-cut hydrogenation tail oil, and a extraction oil and a raffinate oil are obtained after separating the solvent; wherein, the primary solvent refining is a multi-stage countercurrent refining, and the number of stages is 4, The solvent is N-methylpyrrolidone;

The mass ratio of the solvent of the primary solvent refining to the coal tar hydrogenation tail oil fraction is 3:1;

The primary solvent refining temperature may be 70°C.

(2) in the presence of hydropour pour point depressurization and hydrotreating supplementary refining catalyst, the primary raffinate oil is subjected to a series of hydropour pour point depressurization-hydrogenation supplementary refining combined process treatment to obtain a hydrogenated liquid product; wherein, according to In terms of logistics direction, the one-stage series of combined hydropour condensation-hydrogenation supplementary refining process includes a hydropoint depressurization reaction zone and a hydrogenation supplementary refining reaction zone, that is, according to the flow direction, the primary raffinate oil passes through the hydropour condensation reaction zone Hydrogenation and supplementary refining reaction zone, according to the volume ratio of 5:1, were loaded with hydropour point depressurization catalyst (FDW-3 catalyst) and hydrogenation supplementary refining catalyst (HTLF-1 catalyst), and the catalysts used were all sulfurized catalysts.

In the one-stage series-connected hydropour pour point depressurization-hydrogenation supplementary refining combined process, the reaction temperature of the hydropour pour point reduction process is 370°C; the reaction temperature of the hydrogenation supplementary refining process is 360°C;

The reaction pressure of the one-stage series-connected hydropour pour point-hydrogenation supplementary refining combined process reaction zone is 9MPa; the volume ratio of hydrogen to oil is 500:1; and the liquid hourly volume space velocity is 1.0h ^-1 .

(3) fractional distillation of the hydrogenated liquid product to obtain >320°C distillate oil, which is used as a raw material for secondary solvent refining; wherein, the distillation range of the secondary solvent refining raw material is 320°C to 450°C.

(4) Perform secondary solvent refining on the >320° C. distillate oil described in step (3), and separate the solvent to obtain secondary raffinate oil, which is coal-based environmentally friendly rubber oil. Wherein, the secondary solvent refining is multi-stage countercurrent refining, and the solvent is any one of furfural, phenol and N-methylpyrrolidone; the solvent refining temperature is 70°C; and the mass ratio of solvent to raw material is 1:1.

Example 7

(1) a solvent refining is carried out to the mid-low temperature coal tar full-fraction hydrogenation tail oil, and a extraction oil and a raffinate oil are obtained after separating the solvent; wherein, the solvent refining is a multi-stage countercurrent refining, and the number of stages is 3, The solvent is N-methylpyrrolidone;

The mass ratio of the solvent of the primary solvent refining to the coal tar hydrogenation tail oil fraction is 2:1;

The primary solvent refining temperature may be 80°C.

(2) in the presence of hydropour pour point depressurization and hydrotreating supplementary refining catalyst, the primary raffinate oil is subjected to a series of hydropour pour point depressurization-hydrogenation supplementary refining combined process treatment to obtain a hydrogenated liquid product; wherein, according to In the direction of logistics, the one-stage series of combined hydropour condensation-hydrogenation supplementary refining process includes a hydropour condensation reaction zone and a hydrogenation supplementary refining reaction zone. Hydrogenation and supplementary refining reaction zone, according to the volume ratio of 3:1, were loaded with hydropour point depressurization catalyst (FDW-3 catalyst) and hydrogenation supplementary refining catalyst (HTLF-1 catalyst), and the catalysts used were all sulfurized catalysts.

In the one-stage series-connected hydropour point depressurization-hydrogenation supplementary refining combined process, the reaction temperature of the hydropour pour point depressurization process is 360°C; the reaction temperature of the hydrogenation supplementary refining process is 360°C;

The reaction pressure of the one-stage series-connected hydropour pour point-hydrogenation supplementary refining combined process reaction zone is 9MPa; the volume ratio of hydrogen to oil is 700:1; and the liquid hourly volume space velocity is 1.5h ^-1 .

(3) fractional distillation of the hydrogenated liquid product to obtain >320°C distillate oil, which is used as a raw material for secondary solvent refining; wherein, the distillation range of the secondary solvent refining raw material is 320°C to 450°C.

(4) Perform secondary solvent refining on the >320° C. distillate oil described in step (3), and separate the solvent to obtain secondary raffinate oil, which is coal-based environmentally friendly rubber oil. Wherein, the secondary solvent refining is multi-stage countercurrent refining, and the solvent is any one of furfural, phenol and N-methylpyrrolidone; the solvent refining temperature is 85°C; and the mass ratio of solvent to raw material is 1.5:1.

The present invention is not limited to the above-described embodiments, and changes or improvements within the scope of the object of the present invention and the intended effect are also included in the content of the present invention.

Claims (3)

1. a method for adopting low-temperature coal tar full-cut hydrogenation tail oil to prepare coal-based environmental protection rubber oil, is characterized in that, comprises the following steps: The low-temperature coal tar full-fraction hydrogenated tail oil is used as the raw material. In the low-temperature coal tar full-fraction hydrogenated tail oil, the mass content of aromatics is 46.1%, and the mass of PCA is 9.8%. The three-stage countercurrent refining is carried out, the solvent is furfural, and the refining temperature is 90 ° C, the mass ratio of solvent to raw material is 4:1, and the product obtained from the top of the refining tower is recovered from the solvent to obtain primary raffinate oil; In the presence of the FDW-3 catalyst and the HTLF-1 catalyst, the primary raffinate oil is subjected to a series of combined hydropump-hydrogenation and supplementary refining process treatment to obtain a hydrogenated liquid product; The one-stage series-connected hydropour point depressurization-hydrogenation supplementary refining combined process includes a hydropour point depressurization reaction zone and a hydrotreating supplementary refining reaction zone. According to the material flow, FDW-3 catalyst and HTLF-3 catalyst are respectively filled in a volume ratio of 4:1. 1 catalyst, all catalysts used are sulfurized catalysts; The reaction temperature of the hydropour condensation reaction zone is 340°C; the reaction temperature of the hydrogenation supplementary refining reaction zone is 360°C; the reaction pressure of the hydropoint depressurization-hydrogenation supplementary refining reaction zone Both are 8 MPa, the volume ratio of hydrogen to oil is 800:1, and the liquid hourly volume space velocity is 2.0 h ^-1 ; The obtained hydrogenated liquid product is often distilled under reduced pressure to obtain distillate oil at 320°C to 450°C, which is used as a raw material for secondary solvent refining; The distillate oil at 320°C to 450°C is subjected to secondary solvent refining, the refining method is three-stage countercurrent, the solvent is furfural, the solvent refining temperature is 80°C, and the mass ratio of the solvent to the raw material is 3:1. The secondary raffinate oil is obtained by removing the solvent from the primary raffinate, which is coal-based environmental protection rubber oil; the coal-based environmental protection rubber oil has a pour point of 4° _C and a carbon type distribution CA of 15%. 2. a method for preparing coal-based environmental protection rubber oil by adopting low-temperature coal tar full-cut hydrogenation tail oil, is characterized in that, comprises the following steps: Using low temperature coal tar full fraction hydrogenation tail oil as raw material, in the low temperature coal tar full fraction hydrogenation tail oil, the mass content of aromatics is 46.1%, and the mass of PCA is 9.8%. is 100 ° C, the mass ratio of solvent to raw material is 4:1, and the product obtained from the top of the refining tower is recovered to obtain primary raffinate oil after solvent recovery; In the presence of the RDW-1 catalyst and the FV-5 catalyst, the primary raffinate oil is subjected to a one-stage series hydropump depressurization-hydrogenation supplementary refining combined process treatment to obtain a hydrotreated oil; The one-stage series-connected hydropour point depressurization-hydrogenation supplementary refining combined process includes a hydropour point depressurization reaction zone and a hydrotreating supplementary refining reaction zone, and RDW-1 catalyst and FV-5 catalyst are respectively charged according to the volume ratio of 3:1 according to the material flow direction. Catalysts, all catalysts used are sulfided catalysts; The reaction temperature of the hydropour condensation reaction zone is 350°C; the reaction temperature of the hydrogenation supplementary refining reaction zone is 370°C; Both are 10 MPa, the volume ratio of hydrogen to oil is 800:1, and the volumetric space velocity of liquid hour is 2.5 h ^-1 ; The obtained hydrogenated liquid product is often distilled under reduced pressure to obtain distillate oil at 320°C to 450°C, which is used as a raw material for secondary solvent refining; The distillate oil at 320°C to 450°C is subjected to secondary solvent refining, the refining method is three-stage countercurrent, the solvent is furfural, the solvent refining temperature is 90°C, and the mass ratio of the solvent to the raw material is 3:1. The secondary raffinate oil is obtained by removing the solvent from the primary raffinate, which is coal-based environmentally friendly rubber oil; the coal-based environmentally friendly rubber oil has a pour point of 3° _C and a carbon distribution CA of 14%. 3. a method for preparing coal-based environmental protection rubber oil by adopting low-temperature coal tar full-cut hydrogenation tail oil, is characterized in that, comprises the following steps: Using low temperature coal tar full fraction hydrogenation tail oil as raw material, in the low temperature coal tar full fraction hydrogenation tail oil, the mass content of aromatics is 46.1%, the mass of PCA is 9.8%, and the three-stage countercurrent solvent refining is carried out, and the solvent is N-methyl Pyrrolidone, the refining temperature is 80 °C, the mass ratio of solvent to raw material is 2:1, and the product obtained from the top of the refining tower is recovered from the solvent to obtain a raffinate oil; In the presence of the RDW-1 catalyst and the FV-5 catalyst, the primary raffinate oil is subjected to a one-stage series hydropump depressurization-hydrogenation supplementary refining combined process treatment to obtain a hydrotreated oil; The one-stage series-connected hydropour point depressurization-hydrogenation supplementary refining combined process includes a hydropour point depressurization reaction zone and a hydrotreating supplementary refining reaction zone, and the RDW-1 catalyst and the FV-5 catalyst are respectively charged according to the volume ratio of 4:1 according to the material flow direction. Catalysts, all catalysts used are sulfided catalysts; The reaction temperature of the hydropour condensation reaction zone is 340°C; the reaction temperature of the hydrogenation supplementary refining reaction zone is 360°C; the reaction pressure of the hydropoint depressurization-hydrogenation supplementary refining reaction zone Both are 8 MPa, the volume ratio of hydrogen to oil is 800:1, and the liquid hourly volume space velocity is 2.0 h ^-1 ; The obtained hydrogenated liquid product is often distilled under reduced pressure to obtain distillate oil at 320°C to 450°C, which is used as a raw material for secondary solvent refining; The distillate oil at 320°C to 450°C is subjected to secondary solvent refining, the refining method is three-stage countercurrent, the solvent is N-methylpyrrolidone, the solvent refining temperature is 80°C, and the mass ratio of the solvent to the raw material is 2:1 , the obtained secondary raffinate is obtained by removing the solvent to obtain secondary raffinate oil, which is coal-based environmental protection rubber oil; the pour point of the coal-based environmental protection rubber oil is 0 ° _C , and the carbon type distribution CA is 12% .

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