A method for hydrogenating crude oil

Abstract

The present invention discloses a method for hydrogenating a feedstock oil. The method comprises: mixing the feedstock oil with a hydrogenation agent, then contacting the feedstock oil with a hydrogenation catalyst to perform a hydrogenation reaction, separating the deactivated hydrogenation agent after the reaction, regenerating the agent, and then continuing to use the hydrogenation agent as a hydrogenation agent; wherein the hydrogenation agent is an alkane having at least two phenyl groups, wherein the alkane contains at least two carbon atoms and at least one carbon atom has a -CH2- structure. In the present invention, the feedstock oil is hydrogenated in the presence of the hydrogenation agent, and the hydrogenation agent not only has good hydrogenation performance but can also be effectively recycled through regeneration.

Description

Technical Field

[0001] The present invention relates to a feedstock oil hydrogenation method, in particular to a feedstock oil hydrogenation method using a hydrogen donor. Background Art

[0002] During the residual oil hydrogenation process, due to the heavy oil molecules, the catalytic system forms a gas-liquid-solid three-phase state. Therefore, it is difficult for hydrogen molecules to directly and fully contact the hydrogenation active phase. They must first be dissolved in the oil, but this has limited solubility and poor hydrogenation effect. The use of liquid-phase hydrogen donors can increase the content of activatable hydrogen in heavy processing raw materials, thereby improving the processing effect of the oil products. The actual hydrogen supply effect of hydrogen donors used in the prior art is also not ideal, and there are currently few reports on the hydrogen supply principles of hydrogen donors.

[0003] CN105567319A discloses a method for treating heavy oil. The method comprises mixing a hydrogen donor with deoiled asphalt and coal, and performing a hydrogenation treatment in the presence of a hydrogenation catalyst to obtain a hydrotreated product, wherein the hydrogen donor is a hydrocarbon containing a hydrogen-to-carbon atomic ratio of 1.1-1.6. This method is simple in process, but the hydrogen donor lacks specificity and selectivity, and the hydrogen supply effect of the hydrogen donor will continue to decrease after repeated use.

[0004] CN103555363A discloses a method for hydrogenating and delaying coking high-acid feedstock. This method adds a hydrogen donor as a mixed feedstock to a conventional high-acid coking feedstock to carry out a hydrogenation delayed coking reaction. The hydrogen donor used is a partially saturated aromatic hydrocarbon-rich oil product obtained from the effluent of a catalytic cracking distillate hydrogenation reaction or its separation process, with a distillation range of 200°C to 500°C and a partially saturated aromatic hydrocarbon content of 20% to 100%. This method has a simple process, but the hydrogen donor has low hydrogen supply efficiency, high hydrogen consumption, and cannot be effectively recovered.

[0005] CN106883873A discloses a method for reforming and reducing the viscosity of low-quality heavy oil. This method uses straight-run distillate as a hydrogen donor, which is mixed with low-quality residual oil for processing. While this method has a wide range of hydrogen donors, the hydrogen supply effect of straight-run distillate is poor, similar to that of blending, making it difficult to effectively and deeply process the oil.

[0006] Currently, the hydrogen donors used in residual oil processing are primarily petroleum fractions, lacking clear design concepts and ideas, let alone the selection and structural optimization of hydrogen donors. The actual effect of hydrogen donors is similar to blending, resulting in low efficiency. Summary of the Invention

[0007] In view of the shortcomings of the prior art, the present invention provides a crude oil hydrogenation method. In the present invention, the crude oil is hydrogenated in the presence of a hydrogen donor, which not only has good hydrogen supply performance but can also be effectively recycled through regeneration treatment.

[0008] The present invention provides a method for hydrogenating a crude oil, comprising: mixing the crude oil with a hydrogen donor, then contacting the crude oil with a hydrogenation catalyst to carry out a hydrogenation reaction, and after the reaction is completed, separating the deactivated hydrogen donor, regenerating the hydrogen donor, and then continuing to use the hydrogen donor;

[0009] The hydrogen donor is an alkane having at least two phenyl groups, wherein the alkane contains at least two carbon atoms and at least one carbon atom is a -CH2- structure.

[0010] Furthermore, the boiling point of the hydrogen donor is 200°C-350°C.

[0011] Furthermore, the hydrogen donor is at least one of diphenylethane and its homologues, 1,1,2-triphenylethane and its homologues, preferably diphenylethane and / or 1,1,2-triphenylethane (structural formula is as follows).

[0012]

[0013] Furthermore, the raw oil is one or more of atmospheric residue oil, vacuum residue oil, heavy secondary processing oil, etc.

[0014] Furthermore, the initial boiling point of the feedstock oil is greater than 300°C, preferably 350-400°C, and the residual carbon is not less than 8wt%, preferably not less than 10wt%.

[0015] Furthermore, the hydrogenation catalyst can be a conventional hydrogenation catalyst, such as a residue hydrotreating catalyst (hydrogenation protectant, hydrodemetallization catalyst, hydrodesulfurization catalyst, hydrodenitrogenation and / or carbon removal catalyst, etc.), and can be graded and loaded in a conventional manner. The active metal in the hydrogenation catalyst includes a Group VIB and / or Group VIII metal. The hydrogenation catalyst is in a sulfurized state when used.

[0016] Furthermore, the conditions for the hydrogenation reaction are as follows: the mass ratio of the hydrogen donor to the feedstock oil is 1:2-1:30, preferably 1:5-1:25, the reaction temperature is 200-400°C, preferably 250-370°C, the hydrogen pressure is 5.0-25.0 MPa, preferably 8.0-20.0 MPa, the hydrogen-oil volume ratio is 500:1-1500:1, preferably 600:1-1000:1, and the feedstock oil liquid volume space velocity is 0.1-1.0h -1 , preferably 0.2-0.5h -1 .

[0017] Furthermore, the deactivated hydrogen donor can be separated by the following methods:

[0018] The material after the reaction of the raw oil and the hydrogen donor is separated by a distillation tower. The separation conditions are: the number of theoretical plates of the distillation tower is 3-9, preferably 4-7, the bottom temperature of the distillation tower is 240°C-320°C, preferably 260-310°C, the top temperature is 70-140°C, preferably 80-135°C, the top pressure is 0.02-0.2 MPa, preferably 0.04-0.15 MPa, the top reflux ratio is 0.2-3.0, preferably 0.5-2.0, the bottom product includes product oil, and the top product includes deactivated hydrogen donor.

[0019] Furthermore, a selective hydrogenation catalyst is used to regenerate the deactivated hydrogen donor.

[0020] Furthermore, the regeneration treatment conditions are as follows: reaction temperature is 220-380°C, preferably 260-340°C, reaction pressure is 1.0-5.0 MPa, preferably 2.0-4.0 MPa, space velocity is 2.0-6.0 h -1 , preferably 3.0-5.0h -1 .

[0021] Furthermore, the selective hydrogenation catalyst includes a carrier, an active metal, a promoter and a stabilizer, the active metal is molybdenum, the promoter is tetraphenylporphyrin cobalt, and the stabilizer is tetraphenylporphyrin copper.

[0022] Furthermore, based on the weight of the selective hydrogenation catalyst, the content of the carrier is 50%-90%, preferably 55%-80%, the content of molybdenum calculated as MoO3 is 8%-18%, preferably 10%-16%, the content of the auxiliary agent calculated as tetraphenylporphyrin cobalt is 2%-20%, preferably 5%-15%, and the content of the stabilizer calculated as tetraphenylporphyrin copper is 2%-20%, preferably 5%-15%.

[0023] Furthermore, in the selective hydrogenation catalyst, the carrier is alumina. The properties of the carrier are as follows: a specific surface area of ​​250-450m 2 / g, preferably 280-380m 2 / g, pore volume of 0.5-1.0cm 3 / g, preferably 0.6-1.0cm 3 / g.

[0024] Furthermore, the preparation method of the selective hydrogenation catalyst comprises the following steps:

[0025] (1) preparing a molybdenum-containing catalyst intermediate;

[0026] (2) Cobalt tetraphenylporphyrin, copper tetraphenylporphyrin and an organic solvent are mixed to prepare an organic impregnation solution, the molybdenum-containing catalyst intermediate obtained in step (1) is impregnated with the organic impregnation solution, and the mixture is dried to obtain a selective hydrogenation catalyst.

[0027] Furthermore, in step (1), the molybdenum-containing catalyst intermediate can be prepared by conventional preparation methods in the art, such as: preparing an impregnation solution containing a soluble molybdenum salt, then impregnating the catalyst support with the impregnation solution, drying, and calcining to obtain the molybdenum-containing catalyst intermediate.

[0028] Furthermore, in the preparation process of the molybdenum-containing catalyst intermediate, the soluble molybdenum salt is one or more of ammonium heptamolybdate tetrahydrate, ammonium tetramolybdate, and ammonium monomolybdate.

[0029] Furthermore, during the preparation of the molybdenum-containing catalyst intermediate, the impregnation is performed using a conventional impregnation method, such as equal volume impregnation. The drying conditions are as follows: a drying temperature of 80-180°C, preferably 100-160°C, and a drying time of 2.0-8.0 hours, preferably 3.0-6.0 hours. The calcination conditions are as follows: a calcination temperature of 350-600°C, preferably 400-550°C, and a calcination time of 3.0-7.0 hours.

[0030] Furthermore, in step (2), the organic solvent is one or more of toluene, xylene, tetralin, aniline, and biphenyl.

[0031] Furthermore, in step (2), the tetraphenylporphyrin cobalt and tetraphenylporphyrin copper can be mixed with organic solvents to prepare a cobalt-containing organic impregnation solution and a copper-containing organic impregnation solution, respectively, or can be mixed with organic solvents at the same time to prepare an organic impregnation solution containing cobalt and copper.

[0032] Furthermore, in step (2), the mass concentration of tetraphenylporphyrin cobalt and / or tetraphenylporphyrin copper in the organic impregnation solution is 50-300 g / L, preferably 100-200 g / L.

[0033] Furthermore, in step (2), the impregnation is a conventional impregnation method in the art, such as equal volume impregnation.

[0034] Furthermore, in step (2), the drying condition is drying under vacuum conditions, wherein the vacuum degree is 1-200 Pa, preferably 5-100 Pa, the drying temperature is 60-160° C., preferably 100-140° C., and the drying time is 1.0-8.0 hours, preferably 2.0-6.0 hours.

[0035] Furthermore, the selective hydrogenation catalyst needs to be sulfurized before use.

[0036] Furthermore, the sulfidation treatment generally adopts wet sulfidation. The sulfidation liquid used in the sulfidation treatment includes a sulfur-containing compound and an organic solvent, wherein the sulfur-containing compound is at least one of dimethyl disulfide, carbon disulfide, diethyl sulfide, ethyl mercaptan, n-butyl mercaptan, di-tert-phenyl polysulfide, and dimethyl sulfoxide. The organic solvent is at least one of cyclohexane, n-heptane, aviation kerosene, and diesel. The mass fraction of the sulfur-containing compound in the sulfidation liquid is 0.5%-3%, preferably 1%-3%, and the flow rate of the sulfidation liquid is 0.5-4.0 mL·h -1 ·g -1 Oxidized catalyst, preferably 1.0-4.0 mL·h -1 ·g -1 Oxidized catalyst.

[0037] Furthermore, the pressure of the vulcanization treatment is 1.0-4.0 MPa, preferably 1.5-3.0 MPa. The vulcanization treatment is preferably divided into two temperature stages, the first stage temperature is 210°C-250°C, the vulcanization time is 2.0-10.0 hours, and the second stage temperature is 300-370°C, the vulcanization time is 3.0-8.0 hours.

[0038] Compared with the prior art, the present invention has the following advantages:

[0039] The feedstock oil hydrogenation method of the present invention achieves high utilization of the hydrogen donor, facilitating hydrodesulfurization of the feedstock oil and carbon removal by the denitrifier. Furthermore, the product of the hydrogen donor reaction is easily separated from the feedstock oil system, and the separated deactivated hydrogen donor can be recycled after regeneration.

[0040] The selective hydrogenation catalyst of the present invention has good hydrogenation saturation ability and selectivity for olefins, which can ensure the hydrogenation saturation of olefins while preventing the hydrogenation saturation of aromatic hydrocarbons. The selective hydrogenation catalyst of the present invention also has good hydrodesulfurization activity.

[0041] The selective hydrogenation catalyst of the present invention uses cobalt tetraphenylporphyrin as a cobalt source, which increases the distance between cobalt atoms. When cobalt forms a Co-Mo-S active phase during the sulfurization process, the distance between Co atoms is increased. The size of the active center of the Co-Mo-S active phase is correspondingly reduced, further improving the selective adsorption performance of the active phase for olefins. In addition, copper tetraphenylporphyrin (Cu) acts as a hydrogenation stabilizer, and copper has a strong interaction with activated hydrogen, which can suppress the activity of hydrogen. Simultaneously, since cobalt tetraphenylporphyrin and copper tetraphenylporphyrin have similar physical and chemical properties, the transformations in the catalyst surface loading and sulfurization process are also relatively similar, making it easier for copper to be distributed around the cobalt. Since Cu easily forms a strong Cu-S bond with S during the hydrogenation process, the adsorbed S atoms can prevent Co from adsorbing aromatic hydrocarbons, further improving the catalyst's hydrogenation selectivity for olefins. DETAILED DESCRIPTION

[0042] The present invention will be further described below with reference to the examples, but it should be understood that the scope of the present invention is not limited by the examples. In the present invention, unless otherwise explicitly stated, percentages and percentage contents are all based on mass.

[0043] The method used for hydrogenation of crude oil in each embodiment and comparative example is a fixed bed combination method, and the hydrogenation catalyst used is a graded catalyst. The following catalysts are loaded in sequence according to the direction of material flow: a hydrogenation protective agent (FZC-100B), a hydrodemetallization catalyst (FZC-204A), a hydrodesulfurization catalyst (FZC-33B), and a hydrodecarbonization catalyst (FZC-41B). In the order of loading, the filling volume ratio of the above catalysts is 1:1:2:4, and the total catalyst loading amount is 160.0 mL.

[0044] Example 1

[0045] Diphenylethane and residue oil F-0 (properties shown in Table 1) were fully mixed at a mass ratio of 1:20. The resulting mixed raw material was recorded as F-1 and subjected to hydrogenation reaction at a reaction temperature of 360°C, a reaction pressure of 14.0 MPa, and a liquid hourly volume space velocity of 0.5 h -1 , the volume ratio of hydrogen to oil is 1000:1.

[0046] The product of the reaction time of 500-1000 h was collected and recorded as P-1.

[0047] P-1 was passed into a distillation column having five trays, a bottom temperature of 300°C, a top temperature of 130°C, a top pressure of 0.2 MPa, and a reflux ratio of 1.0. The resulting top product was U-1, and the resulting bottom product was B-1.

[0048] Example 2

[0049] 1,1,2-Triphenylethane and residual oil F-0 (properties shown in Table 1) were thoroughly mixed in a mass ratio of 1:10. The resulting mixed raw material was recorded as F-2 and subjected to hydrogenation reaction under the same conditions as in Example 1. The product was collected after 500-1000 hours of reaction and recorded as P-2.

[0050] P-2 was introduced into a distillation tower. The operating conditions of the distillation tower were the same as those in Example 1. The top product obtained was U-2, and the bottom product obtained was B-2.

[0051] Example 3

[0052] Diphenylethane and 1,1,2-triphenylethane were thoroughly mixed with residual oil F-0 (properties shown in Table 1) in a mass ratio of 1:1:10. The resulting mixed raw material was recorded as F-3 and subjected to hydrogenation reaction under the same conditions as in Example 1. The product was collected after 500-1000 hours of reaction and recorded as P-3.

[0053] P-3 was introduced into a distillation tower. The operating conditions of the distillation tower were the same as those in Example 1. The top product obtained was U-3, and the bottom product obtained was B-3.

[0054] Comparative Example 1

[0055] The residue F-0 was subjected to hydrogenation reaction (conditions were the same as those in Example 1), and the product was collected after 500-1000 hours. The obtained product was recorded as DB-1.

[0056] Comparative Example 2

[0057] Tetralin and residue F-0 were fully mixed in a mass ratio of 1:5. The resulting mixed raw material was recorded as DF-2. DF-2 was used for hydrogenation reaction (conditions were the same as in Example 1). The product of the reaction was collected for 500-1000 hours and recorded as DP-2.

[0058] DP-2 was introduced into a distillation tower. The operating conditions of the distillation tower were the same as those in Example 1. The top product obtained was DU-2, and the bottom product obtained was DB-2.

[0059] Table 1 Properties of Residue F-0

[0060] Project Name raw material Initial distillation point, ℃ 386 <![CDATA[Density (15 °C), kg / m 3 > 998 Sulfur content, μg / g 31852 Nitrogen content, μg / g 2785 Saturated fraction, wt% 43.4 Aromatic content, wt% 34.9 Gum, wt% 19.2 Asphaltene, wt% 2.5 Carbon residue, wt% 15.3

[0061] The properties of the bottom products B-1, B-2, B-3, DB-1 and DB-2 were analyzed and evaluated as shown in Table 2.

[0062] Table 2 Evaluation results of tower bottom products

[0063] product B-1 B-2 B-3 DB-1 DB-2 Sulfur content, μg / g 1125 753 563 3152 2106 Nitrogen content, μg / g 562 470 311 1128 852 Carbon residue, wt% 2.1 1.6 1.3 4.9 3.7

[0064] The top products U-1, U-2, U-3 and DU-2 were subjected to chromatographic analysis, and the results are shown in Table 3.

[0065] The calculation method of hydrogen donor utilization rate is:

[0066] Hydrogen donor utilization rate = (deactivated hydrogen donor) / (undeactivated hydrogen donor+deactivated hydrogen donor)×100%.

[0067] Table 3 Analysis of the composition of the top product

[0068] product U-1 U-2 U-3 DU-2 Diphenylethane, wt% 12.8 7.2 - - 1,1,2-Triphenylethane, wt% - 7.3 16.2 - Stilbene, wt% 85.3 40.3 - - Triphenylethylene, wt% - 39.8 80.6 - Tetralin, wt% - - 47.8 Naphthalene, wt% - - 46.3 Hydrogen donor utilization rate, % 86.9 84.6 83.2 50.8

[0069] Example 4

[0070] Preparation of selective hydrogenation catalyst:

[0071] Weigh 1000.0g of alumina dry rubber powder, add 30.0g of citric acid and 20.0g of sesbania powder, mix well, add 1000.0g of aqueous solution containing 3.0% nitric acid, roll for 30.0min, and squeeze into strips using a 1.8mm diameter clover plate. Dry at 120℃ for 4.0h and calcine at 550℃ for 4.0h. The calcined carrier is designated as S-0 (analysis shows that the carrier has a specific surface area of ​​350m 2 / g, pore volume is 0.9cm 3 / g).

[0072] Weigh 50.0 g of ammonium heptamolybdate tetrahydrate and 150.0 g of deionized water, stir thoroughly at 60° C. for 20 min, cool to room temperature, and then dilute to 200.0 mL with deionized water. The resulting solution is designated as Q-1.

[0073] Take 200g of carrier S-0, impregnate it with Q-1, dry it naturally for 24 hours, then dry it at 120℃ for 4 hours, and then calcine it at 450℃ for 5.0 hours. The obtained intermediate is recorded as MT-1.

[0074] Weigh 30.0 g of copper tetraphenylporphyrin and 30.0 g of cobalt tetraphenylporphyrin and dissolve them in 160.0 g of toluene to obtain the impregnation solution YQ-1. Use YQ-1 to impregnate MT-1, then vacuum dry at 100°C, 20 Pa, for 5 h. The resulting catalyst is designated CT-1.

[0075] Example 5

[0076] Preparation of selective hydrogenation catalyst:

[0077] Weigh 60.0 g of ammonium heptamolybdate tetrahydrate and 150.0 g of deionized water, stir thoroughly at 60° C. for 20 min, cool to room temperature, and then dilute to 200.0 mL with deionized water. The resulting solution is designated as Q-2.

[0078] Take 200g of carrier S-0 (same as Example 4), impregnate it with Q-2, dry it naturally for 24 hours, then dry it at 120℃ for 4 hours, and then calcine it at 450℃ for 5.0 hours. The obtained intermediate is recorded as MT-2.

[0079] Weigh 40.0 g of copper tetraphenylporphyrin and 40.0 g of cobalt tetraphenylporphyrin and dissolve them in 160.0 g of toluene to obtain the impregnation solution YQ-2. Use YQ-2 to impregnate MT-2, then vacuum dry at 100°C, 20 Pa, for 5 h. The resulting catalyst is designated CT-2.

[0080] Comparative Example 3

[0081] Weigh 50.0 g of ammonium heptamolybdate tetrahydrate, 15.0 g of cobalt nitrate hexahydrate, and 150.0 g of deionized water, stir thoroughly at 60°C for 20 min, cool to room temperature, and then dilute to 200.0 mL with deionized water. The resulting solution is recorded as DQ-1.

[0082] 200 g of carrier S-0 (same as Example 4) was taken and impregnated with DQ-1, dried naturally for 24 hours, then dried at 120°C for 4 hours, and finally calcined at 450°C for 5.0 hours. The obtained catalyst was recorded as DCT-1.

[0083] Table 4 Catalyst compositions obtained in each embodiment

[0084] Catalyst No. <![CDATA[MoO3,wt%]]> Copper tetraphenylporphyrin, wt% Tetraphenylporphyrin cobalt, wt% Carrier, wt% CT-1 13.1 9.9 9.9 67.1 CT-2 14.2 12.1 12.2 61.5

[0085] Table 5 Comparative Example Catalyst Composition

[0086] Catalyst No. <![CDATA[MoO3,wt%]]> CuO, wt% CoO, wt% Carrier, wt% DCT-1 16.0 - 1.5 82.5

[0087] The catalysts obtained in Examples 4-5 and Comparative Example 3 were subjected to sulfurization treatment, respectively, as follows:

[0088] Prepare a 2 wt% cyclohexane solution of DMDS (dimethyl disulfide) with a flow rate of 2.0 mL·h -1 ·g -1 Oxidized catalyst.

[0089] The pressure during vulcanization is 2.0 MPa, and the vulcanization is divided into two temperature stages. The temperature of the first stage is 230° C. and the vulcanization time is 4.0 hours. The temperature of the second stage is 320° C. and the vulcanization time is 4.0 hours.

[0090] Examples 6-8

[0091] The reaction temperature was 320 ° C, the hydrogen pressure was 2.0 MPa, and the space velocity was 3.0 h -1 Under the conditions of , the top product obtained in Examples 1-3 was regenerated using CT-1 prepared in Example 4, and the properties of the obtained product are shown in Table 6.

[0092] Examples 9-11

[0093] The reaction temperature was 320 ° C, the hydrogen pressure was 2.0 MPa, and the space velocity was 3.0 h -1 Under the conditions of , the top product obtained in Example 1-3 was regenerated using CT-2 prepared in Example 5, and the properties of the obtained product are shown in Table 6.

[0094] Comparative Examples 4-6

[0095] The reaction temperature was 320 ° C, the hydrogen pressure was 2.0 MPa, and the space velocity was 3.0 h -1 Under the conditions of , the tower top products obtained in Examples 1-3 were regenerated using DCT-1 prepared in Comparative Example 3, and the properties of the obtained products are shown in Table 6.

[0096] Comparative Example 7

[0097] The reaction temperature was 320 ° C, the hydrogen pressure was 2.0 MPa, and the space velocity was 3.0 h -1 Under the conditions of , the top product obtained in Comparative Example 2 was regenerated using CT-1 prepared in Example 1, and the properties of the obtained product are shown in Table 6.

[0098] Among them, the effective regeneration rate of hydrogen donor = (hydrogen donor 产物 ) / (Hydrogen Donor 原料 +Deactivated hydrogen donor 原料 )×100%.

[0099] Table 6 Composition analysis of recycled products

[0100]

[0101] It can be seen from the reaction results that the hydrogen donor of the present invention has good hydrogen supply performance when used for the raw material hydrogenation reaction, and the properties of the product after the raw material oil hydrogenation are significantly improved. Moreover, after regeneration using the special catalyst provided by the present invention, the effective regeneration rate exceeds 90%, and the hydrogen donor can be recycled.

Claims

1. A method for hydrogenating a feedstock oil, comprising: The raw oil is mixed with the hydrogen donor, and then contacted with the hydrogenation catalyst to carry out the hydrogenation reaction. After the reaction is completed, the deactivated hydrogen donor is separated and regenerated, and then it is continued to be used as a hydrogen donor; Wherein, the hydrogen donor is an alkane having at least two phenyl groups, wherein the alkane contains at least two carbon atoms and at least one carbon atom is a -CH2- structure; The boiling point of the hydrogen donor is 200°C-350°C.

2. The method according to claim 1, characterized in that The hydrogen donor is at least one of diphenylethane and its homologues, 1,1,2-triphenylethane and its homologues.

3. The method according to claim 2, characterized in that The hydrogen donor is diphenylethane and / or 1,1,2-triphenylethane.

4. The method according to claim 1, characterized in that The raw oil is one or more of atmospheric residue oil, vacuum residue oil, and heavy secondary processed oil.

5. The method according to claim 1, characterized in that The conditions for the hydrogenation reaction are: the mass ratio of the hydrogen donor to the raw oil is 1:2-1:30, the reaction temperature is 200-400°C, the raw oil liquid volume space velocity is 0.1-1.0h -1 .

6. The method according to claim 5, characterized in that The conditions for the hydrogenation reaction are: the mass ratio of the hydrogen donor to the raw oil is 1:5-1:25, the reaction temperature is 250-370°C, the raw oil liquid volume space velocity is 0.2-0.5 h -1 .

7. The method according to claim 1, characterized in that The deactivated hydrogen donor is separated in the following manner: the material after the reaction of the raw oil and the hydrogen donor is separated by a distillation tower, and the separation conditions are: the number of theoretical plates of the distillation tower is 3-9, the bottom temperature of the distillation tower is 240ºC-320ºC, the top temperature is 70-140ºC, the top pressure is 0.02-0.2MPa, the top reflux ratio is 0.2-3.0, the bottom product obtained includes product oil, and the top product obtained includes deactivated hydrogen donor.

8. The method according to claim 1, characterized in that The deactivated hydrogen donor is regenerated using a selective hydrogenation catalyst.

9. The method according to claim 1 or 8, characterized in that The regeneration treatment conditions are as follows: reaction temperature is 220-380℃, reaction pressure is 1.0-5.0 MPa, and space velocity is 2.0-6.0 h -1 .

10. The method according to claim 9, characterized in that The regeneration treatment conditions are as follows: reaction temperature is 260-340℃, reaction pressure is 2.0-4.0 MPa, and space velocity is 3.0-5.0 h -1 .

11. The method according to claim 8, characterized in that The selective hydrogenation catalyst comprises a carrier, an active metal, a promoter and a stabilizer. The active metal is molybdenum, the promoter is tetraphenylporphyrin cobalt, and the stabilizer is tetraphenylporphyrin copper.

12. The method according to claim 11, characterized in that Based on the weight of the selective hydrogenation catalyst, the content of the carrier is 50%-90%, the content of molybdenum calculated as MoO3 is 8%-18%, the content of the auxiliary agent calculated as tetraphenylporphyrin cobalt is 2%-20%, and the content of the stabilizer calculated as tetraphenylporphyrin copper is 2%-20%. The sum of the contents of the components of the selective hydrogenation catalyst is 100%.

13. The method according to claim 12, characterized in that Based on the weight of the selective hydrogenation catalyst, the content of the carrier is 55%-80%, the content of molybdenum calculated as MoO3 is 10%-16%, the content of the auxiliary agent calculated as tetraphenylporphyrin cobalt is 5%-15%, and the content of the stabilizer calculated as tetraphenylporphyrin copper is 5%-15%.

14. The method according to claim 11, characterized in that The preparation method of the selective hydrogenation catalyst comprises the following steps: (1) Preparation of molybdenum-containing catalyst intermediates; (2) Cobalt tetraphenylporphyrin, copper tetraphenylporphyrin and an organic solvent are mixed to prepare an organic impregnation solution, the molybdenum-containing catalyst intermediate obtained in step (1) is impregnated with the organic impregnation solution, and the mixture is dried to obtain a selective hydrogenation catalyst.

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