Treatment method of waste hydrogenation catalyst, hydrogenation catalyst obtained by treatment and application of hydrogenation catalyst
阅读说明：本技术 废加氢催化剂的处理方法和处理得到的加氢催化剂及其应用 (Treatment method of waste hydrogenation catalyst, hydrogenation catalyst obtained by treatment and application of hydrogenation catalyst ) 是由 王振 杨清河 胡大为 孙淑玲 邵志才 于 2019-04-18 设计创作，主要内容包括：本发明涉及废加氢催化剂处理领域,公开了废加氢催化剂的处理方法和处理得到的加氢催化剂及其应用,该方法包括：1)在含氧气氛下,将废加氢催化剂进行烧炭和扩孔处理,所述烧炭和扩孔处理包括可选的阶段(1)和阶段(2),所述阶段(1)的条件包括：温度为200-500℃,时间为1-10小时,所述阶段(2)的条件包括：温度为500-850℃,时间为1-10小时；2)采用含有有机化合物的溶液浸渍步骤1)得到的固体产物,然后进行干燥,所述有机化合物选自C1-C20的有机醇、有机酸、有机胺和有机铵盐中的至少一种。本发明提供的废加氢催化剂的处理方法得到的加氢催化剂用于重油和/或渣油加氢处理过程中,具有较好的脱硫和脱残炭性能。(The invention relates to the field of waste hydrogenation catalyst treatment, and discloses a treatment method of a waste hydrogenation catalyst, a hydrogenation catalyst obtained by treatment and application thereof, wherein the method comprises the following steps: 1) under oxygen-containing atmosphere, carrying out charcoal burning and hole expanding treatment on the waste hydrogenation catalyst, wherein the charcoal burning and hole expanding treatment comprises optional stages (1) and (2), and the conditions of the stage (1) comprise: the temperature is 200-500 ℃ and the time is 1-10 hours, and the conditions of the stage (2) comprise: the temperature is 500-850 ℃, and the time is 1-10 hours; 2) impregnating the solid product obtained in the step 1) with a solution containing an organic compound selected from at least one of organic alcohols, organic acids, organic amines and organic ammonium salts of C1-C20, and then drying. The hydrogenation catalyst obtained by the method for treating the waste hydrogenation catalyst provided by the invention is used in the heavy oil and/or residual oil hydrotreating process, and has better desulfurization and carbon residue removal performances.)
1. A process for treating a spent hydroprocessing catalyst, the process comprising:
1) under oxygen-containing atmosphere, carrying out charcoal burning and hole expanding treatment on the waste hydrogenation catalyst, wherein the charcoal burning and hole expanding treatment comprises optional stages (1) and (2), and the conditions of the stage (1) comprise: the temperature is 200-500 ℃ and the time is 1-10 hours, and the conditions of the stage (2) comprise: the temperature is 500-850 ℃, and the time is 1-10 hours;
2) impregnating the solid product obtained in the step 1) with a solution containing an organic compound selected from at least one of organic alcohols, organic acids, organic amines and organic ammonium salts of C1-C20, and then drying.
2. The treatment method according to claim 1, wherein the organic compound is at least one of glycerol, citric acid, ethylenediaminetetraacetic acid, monoethanolamine, diethylenetriamine, hydroxyethylethylenediamine, nitrilotriacetic acid, and diethylenetriaminepentaacetic acid, more preferably at least one of glycerol, citric acid, and ethylenediaminetetraacetic acid, and still more preferably glycerol and/or citric acid.
3. The process according to claim 1 or 2, wherein the weight ratio of solid product obtained in step 1) to organic compound is between 3 and 200: 1, more preferably 6 to 60: 1.
4. the process of any one of claims 1 to 3, wherein in step 2), the impregnation is an equal volume saturated impregnation, unsaturated impregnation or supersaturated impregnation.
5. The process of any one of claims 1 to 3, wherein in step 2), the drying conditions comprise: the temperature is 90-200 ℃ and the time is 2-10 hours.
6. The processing method according to any one of claims 1 to 5,
the conditions of the stage (1) include: treating at 200-300 deg.C for 1-3 hr, and then treating at 300-500 deg.C for 1-4 hr;
preferably, the conditions of said stage (2) comprise: the temperature is 600 ℃ and 800 ℃, and the time is 1-8 hours;
preferably, the conditions of stage (1) include: treating at the temperature of 230-280 ℃ for 1-3 hours, and then treating at the temperature of 350-450 ℃ for 1-4 hours; the conditions of the stage (2) include: the temperature is 600 ℃ and 750 ℃ and the time is 1-4 hours.
7. The process according to any one of claims 1 to 6, wherein the oxygen-containing atmosphere has a volume content of oxygen of 8 to 30%, preferably 10 to 25%.
8. The process of any one of claims 1 to 7, wherein the spent hydrogenation catalyst comprises at least one of a spent gasoline hydrogenation catalyst, a spent diesel hydrogenation catalyst, a spent kerosene hydrogenation catalyst, and a spent wax oil hydrogenation catalyst;
preferably, the carbon content of the spent hydrogenation catalyst is less than 30 wt% and the inactive metal content is less than 20 wt%, based on the total amount of the spent hydrogenation catalyst, and further preferably, the carbon content of the spent hydrogenation catalyst is less than 15 wt% and the inactive metal content is less than 10 wt%;
preferably, the spent hydrogenation catalyst has a specific surface area of from 30 to 300m2The pore volume is 0.05-0.7mL/g, and the most probable pore diameter is more than 1 nm; further preferably, the specific surface area of the spent hydrogenation catalyst is in the range of 30 to 200m2The pore volume is 0.05-0.5mL/g, and the most probable pore diameter is more than 2 nm; more preferably, the spent hydrogenation catalyst has a specific surface area of from 50 to 150m2The pore volume is 0.1-0.5mL/g, and the most probable pore diameter is 3-8 nm;
preferably, the spent hydrogenation catalyst comprises a carrier and a metal active component supported on the carrier, the metal active component comprising molybdenum and/or tungsten and nickel and/or cobalt; further preferably, the content of molybdenum and/or tungsten is 10-40 wt% and the content of nickel and/or cobalt is 1.5-8 wt% calculated on oxide basis based on the total amount of fresh catalyst corresponding to the spent hydrogenation catalyst.
9. A hydroprocessing catalyst obtained by a process for the treatment of a spent hydroprocessing catalyst as defined in any one of claims 1-8, said catalyst having a specific surface area of from 80 to 250m2The pore volume is 0.2-0.9mL/g, and the most probable pore diameter is 5-14 nm.
10. Use of the hydrogenation catalyst of claim 9 in the hydroprocessing of heavy oils and/or residues.
Technical Field
The invention relates to the field of waste hydrogenation catalyst treatment, in particular to a treatment method of a waste hydrogenation catalyst, a hydrogenation catalyst obtained by treatment and application of the hydrogenation catalyst.
Background
At present, each domestic refinery produces a large amount of waste distillate oil hydrogenation catalysts every year, and the waste catalysts are high in recovery and treatment cost and high in environmental protection pressure. If the waste catalysts can be applied after regeneration treatment, on one hand, the problem of recovery treatment of the waste catalysts can be solved, on the other hand, the cost of the existing hydrogenation catalyst can be greatly reduced, and the economic benefit is obvious.
In industrial production, the main reason for the deactivation of distillate oil hydrogenation catalysts is coke deposition, and for the deactivated catalysts, a common regeneration method is to firstly carry out carbon burning treatment on the catalysts under certain conditions, and then carry out active phase redispersion treatment on the carbon-burned catalysts by adopting a solution containing specific compound components.
CN1921942A reports a method for regenerating a deactivated hydrotreating catalyst, in which a hydrotreating catalyst deactivated by carbon deposition is first subjected to a carbon burning treatment under certain conditions to obtain an intermediate catalyst with a carbon content of 0.5-2.5 wt%, then the carbon-burned catalyst is contacted and aged with a nitrogen-containing chelating agent solution, and finally the regenerated catalyst is obtained by drying treatment.
CN106669866A discloses a regeneration method of a deactivated hydrogenation catalyst, which comprises the steps of carrying out charring treatment on the deactivated hydrogenation catalyst, then adopting a solution containing ammonium fluoborate and 2-amino-1, 3 propanediol to impregnate the charred catalyst, and carrying out heat treatment on the impregnated hydrogenation catalyst to obtain regeneration. The method can improve the specific surface area of the regenerated catalyst, promote the redispersion of the active components, ensure that the regenerated hydrogenation catalyst has high degree of vulcanization and improve the reaction activity.
Although the prior art is capable of achieving the treatment of spent hydrogenation catalysts, the reuse performance of the recovered catalyst is yet to be further improved.
Disclosure of Invention
The invention aims to overcome the problem that the performance of a regenerated waste hydrogenation catalyst in the prior art needs to be improved, and provides a treatment method of the waste hydrogenation catalyst, the hydrogenation catalyst obtained by treatment and application thereof.
In the research process, the inventor of the invention finds that the regenerated catalyst obtained by the existing recovery treatment method of the waste distillate oil hydrogenation catalyst can not meet the requirements of hydrogenation treatment on the performance of the catalyst when being used in the distillate oil hydrogenation treatment process again, for example, the activity and the selectivity can not completely meet the requirements, so that the effective recovery treatment of the waste distillate oil hydrogenation catalyst is limited. The inventor of the present invention changes the idea, and considers that the spent distillate hydrogenation catalyst is regenerated and then used in the heavy oil and/or residual oil hydrogenation process with slightly reduced catalyst requirements, but compared with the distillate oil, the heavy oil and/or residual oil raw material has higher molecular weight and larger molecular size of compounds, and the accessibility of the catalyst active center to macromolecular compounds in the heavy oil and/or residual oil needs to be increased, so as to improve the diffusion performance of catalyst pore channels, so the spent distillate oil hydrogenation catalyst cannot be directly used in the heavy oil and/or residual oil hydrogenation reaction after being regenerated. Therefore, upon conventional regeneration of the spent distillate hydrogenation catalyst, further treatment is required to make the regenerated distillate hydrogenation catalyst useful in heavy oil and/or residue hydrotreating processes.
In order to achieve the above object, a first aspect of the present invention provides a method for treating a spent hydrogenation catalyst, the method comprising:
1) under oxygen-containing atmosphere, carrying out charcoal burning and hole expanding treatment on the waste hydrogenation catalyst, wherein the charcoal burning and hole expanding treatment comprises optional stages (1) and (2), and the conditions of the stage (1) comprise: the temperature is 200-500 ℃ and the time is 1-10 hours, and the conditions of the stage (2) comprise: the temperature is 500-850 ℃, and the time is 1-10 hours;
2) impregnating the solid product obtained in the step 1) with a solution containing an organic compound selected from at least one of organic alcohols, organic acids, organic amines and organic ammonium salts of C1-C20, and then drying.
Preferably, the conditions of stage (1) include: treating at the temperature of 230-280 ℃ for 1-3 hours, and then treating at the temperature of 350-450 ℃ for 1-4 hours; the conditions of the stage (2) include: the temperature is 600 ℃ and 750 ℃ and the time is 1-4 hours.
The second aspect of the invention provides a hydrogenation catalyst obtained by the method for treating the waste hydrogenation catalyst, wherein the specific surface area of the catalyst is 80-250m2The pore volume is 0.2-0.9mL/g, and the most probable pore diameter is 5-14 nm.
In a third aspect, the present invention provides the use of a hydrogenation catalyst as described above in the hydroprocessing of heavy oils and/or residues.
Compared with the prior art, the hydrogenation catalyst obtained by the method for treating the waste hydrogenation catalyst can be applied to the hydrogenation reaction process of heavy oil and/or residual oil, and has better desulfurization and carbon residue removal effects.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the present invention, "optional" means "including or not including", "containing or not containing".
In a first aspect, the present invention provides a process for treating a spent hydrogenation catalyst, the process comprising:
1) under oxygen-containing atmosphere, carrying out charcoal burning and hole expanding treatment on the waste hydrogenation catalyst, wherein the charcoal burning and hole expanding treatment comprises optional stages (1) and (2), and the conditions of the stage (1) comprise: the temperature is 200-500 ℃ and the time is 1-10 hours, and the conditions of the stage (2) comprise: the temperature is 500-850 ℃, and the time is 1-10 hours;
2) impregnating the solid product obtained in the step 1) with a solution containing an organic compound selected from at least one of organic alcohols, organic acids, organic amines and organic ammonium salts of C1-C20, and then drying.
In the present invention, the spent hydrogenation catalyst refers to a catalyst whose performance (which may include at least one of activity, selectivity and stability) deteriorates after use, and includes both a spent hydrogenation catalyst that cannot meet the requirement of the activity of the hydrotreatment even after being regenerated by the existing means for a long period of time and a used hydrogenation catalyst that can be used again after being regenerated by the existing means. Because the spent hydrotreating catalyst has the characteristics of carbon deposit and/or high content of inactive metals (such as vanadium, sodium, iron and calcium) and the like relative to the fresh agent, the invention expresses whether the catalyst is the spent hydrotreating catalyst by the content of carbon and/or the content of inactive metals. Typically, the carbon content and the inactive metal content of the fresh agent are both substantially 0, whereas the carbon content of the spent hydrogenation catalyst may be as high as 30 wt.%, and the inactive metal content may even be as high as 50 wt.%.
According to a preferred embodiment of the present invention, the carbon content of the spent hydrogenation catalyst is less than 30 wt% and the inactive metal content is less than 20 wt%, further preferably the carbon content of the spent hydrogenation catalyst is less than 15 wt% and the inactive metal content is less than 10 wt%, further preferably the carbon content of the spent hydrogenation catalyst is 5-15 wt% and the inactive metal content is 1.5-10 wt%, based on the total amount of the spent hydrogenation catalyst.
In the present invention, unless otherwise specified, the carbon content of the spent hydrogenation catalyst is determined by a carbon-sulfur analyzer, and the content of the inactive metal is determined by X-ray fluorescence spectroscopy.
In the present invention, the spent hydrogenation catalyst may be any hydrogenation catalyst conventionally used for various oils in the art, and the present invention is not particularly limited thereto. According to an embodiment of the present invention, the spent hydrogenation catalyst of the present invention includes, but is not limited to, at least one of a spent gasoline hydrogenation catalyst, a spent diesel hydrogenation catalyst, a spent kerosene hydrogenation catalyst, and a spent wax oil hydrogenation catalyst. The embodiment of the invention is exemplified by a hydrogenation catalyst of waste diesel oil and a hydrogenation catalyst of waste wax oil.
According to the present invention, preferably, the spent hydrogenation catalyst comprises a carrier and a metal active component comprising molybdenum and/or tungsten and nickel and/or cobalt supported on the carrier. The content of molybdenum and/or tungsten and nickel and/or cobalt in the invention is selected widely, and can be adjusted by those skilled in the art according to the actual situation, and further preferably, based on the total amount of fresh catalyst corresponding to the waste hydrogenation catalyst, the content of molybdenum and/or tungsten is 10-40 wt% and the content of nickel and/or cobalt is 1.5-8 wt% calculated by oxide. It should be noted that the spent hydrogenation catalyst contains the above-mentioned inactive metal and carbon deposited by long-term recycling, in addition to the carrier and the metal active component supported on the carrier. The phrase "based on the total amount of fresh catalyst corresponding to the spent hydrogenation catalyst" as used herein means that the molybdenum and/or tungsten content and the nickel and/or cobalt content are based on fresh catalyst, i.e., the above-mentioned inactive metals and carbon are not included. The conventional selection ranges of the metal active components molybdenum and/or tungsten and nickel and/or cobalt in the waste gasoline hydrogenation catalyst, the waste diesel oil hydrogenation catalyst, the waste kerosene hydrogenation catalyst and the waste wax oil hydrogenation catalyst may be different, and a person skilled in the art can select the metal active components according to the conventional means, and the details are not repeated herein.
According to a preferred embodiment of the present invention, the spent hydrogenation catalyst has a specific surface area of 30 to 300m2The pore volume is 0.05-0.7mL/g, and the most probable pore diameter is more than 1 nm; further preferred isThe specific surface area of the waste hydrogenation catalyst is 30-200m2The pore volume is 0.05-0.5mL/g, and the most probable pore diameter is more than 2 nm; more preferably, the spent hydrogenation catalyst has a specific surface area of from 50 to 150m2The pore volume is 0.1-0.5mL/g, and the most probable pore diameter is 3-8 nm.
In the present invention, specific surface area, pore volume and the most probable pore diameter of the spent hydrogenation catalyst are measured by a low-temperature nitrogen adsorption method, unless otherwise specified.
The inventor of the invention finds that the hydrogenation catalyst obtained by adopting the waste hydrogenation catalyst meeting the physicochemical characteristics to process is preferably used for heavy oil and/or residual oil hydrogenation treatment, and has higher desulfurization and carbon residue removal performance.
The inventors of the present invention have also found that the use of a spent hydrogenation catalyst having a particle size of 10 to 30 mesh, preferably 14 to 20 mesh, and more preferably 16 to 20 mesh, can further improve the desulfurization and carbon residue removal performance of the resulting hydrogenation catalyst. Spent hydrogenation catalyst may be screened prior to use to yield a spent hydrogenation catalyst meeting the preferred particle size requirements described above. Therefore, the method provided by the invention preferably further comprises the step of screening the waste hydrogenation catalyst before the step 1).
According to the invention, in the step 1), the oxygen-containing atmosphere provides oxygen for the charcoal burning and pore expanding treatment of the waste hydrogenation catalyst, and the invention has a wide selection range of the content of the oxygen in the oxygen-containing atmosphere, for example, the volume content of the oxygen in the oxygen-containing atmosphere can be 8-30%, and preferably 10-25%. The oxygen-containing atmosphere according to the present invention can be provided by different methods according to different requirements of the oxygen volume content, for example, the oxygen-containing atmosphere can be provided by air, when the requirement for the oxygen content of the oxygen-containing atmosphere is high, the oxygen-containing atmosphere can be provided by air and oxygen together, and when the requirement for the oxygen content of the oxygen-containing atmosphere is low, the oxygen-containing atmosphere can be provided by air and inert atmosphere (for example, nitrogen) together. The embodiment of the present invention is exemplified by using air to provide the oxygen-containing atmosphere, which is more favorable for cost saving, but the present invention is not limited thereto.
The charring and reaming processes of the present invention may be carried out in conventional equipment, provided that step 1) is carried out in an oxygen-containing atmosphere under optional stage (1) and stage (2) conditions, for example in a muffle furnace.
In the invention, the step 1) can be optionally performed in the stage (1), that is, the step 1) of the invention comprises the stage (1) and the stage (2), or the step 1) of the invention comprises only the stage (2). The conditions of the stage (2) of the step 1) of the invention comprise: the temperature is 500-850 ℃ and the time is 1-10 hours, while in the prior art, the coke-burning treatment of the spent hydrogenation catalyst is generally carried out without and without being above 500 ℃, for example, the coke-burning temperature disclosed in CN1921942A is not more than 500 ℃, preferably 350-425 ℃, and the coke-burning temperature disclosed in CN106669866A is below 480 ℃. The inventor of the invention finds that the spent hydrogenation catalyst is subjected to carbon burning and pore-expanding treatment under the conditions of the temperature of 500-850 ℃ and the time of 1-10 hours, and the hydrogenation catalyst obtained by combining the treatment of the step 2) is particularly suitable for the heavy oil and/or residual oil hydrogenation treatment process. Preferably, the charking and pore-expanding treatment in step 1) of the present invention comprises a stage (1) and a stage (2), and this preferred embodiment is more beneficial to improve the desulfurization and carbon residue removal activity of the obtained hydrogenation catalyst in the heavy oil and/or residual oil hydrotreating process.
According to the invention, preferably, the conditions of said stage (1) comprise: the treatment is carried out at a temperature of 200-300 ℃ for 1-3 hours and then at a temperature of 300-500 ℃ for 1-4 hours.
According to the invention, preferably, the conditions of said phase (2) comprise: the temperature is 600 ℃ and 800 ℃, and the time is 1-8 hours;
further preferably, the conditions of stage (1) include: treating at the temperature of 230-280 ℃ for 1-3 hours, and then treating at the temperature of 350-450 ℃ for 1-4 hours; the conditions of the stage (2) include: the temperature is 600 ℃ and 750 ℃ and the time is 1-4 hours. The hydrogenation catalyst obtained by adopting the optimized conditions of carbon burning and hole expanding increases the accessibility of the active center of the catalyst to macromolecular compounds in heavy oil and/or residual oil, improves the diffusion performance of the catalyst pore passage, and can obtain better desulfurization and carbon residue removal effects when the obtained hydrogenation catalyst is used in the heavy oil and/or residual oil hydrogenation treatment process.
The impregnation in step 2) according to the present invention is not particularly limited, and for example, the impregnation may be an equal volume of saturated impregnation, unsaturated impregnation or supersaturated impregnation, that is, step 2) may impregnate the solid product obtained in step 1) with an equal volume of saturated impregnation, unsaturated impregnation or supersaturated impregnation of a solution containing an organic compound. The equal-volume saturated impregnation, unsaturated impregnation or supersaturated impregnation method can be carried out according to the conventional technical means in the field, and the method is not particularly limited in this respect and is not described in detail any more. According to a preferred embodiment of the invention, the impregnation is an isovolumetric saturation impregnation.
In the present invention, the impregnation may be carried out at room temperature (e.g., 20 to 40 ℃) for 1 to 10 hours.
According to the invention, preferably, the weight ratio of the solid product obtained in step 1) to the organic compound is 3 to 200: 1, more preferably 6 to 150: 1, more preferably 6 to 60: 1, more preferably 8 to 10: 1. the preferred ratio is more favorable for achieving more uniform redispersion of the active metal in the solid product. It should be noted that, the weight ratio of the solid product obtained in step 1) to the organic compound and the concentration of the solution containing the organic compound can be determined by those skilled in the art by the impregnation method described above, and for example, when the solid product obtained in step 1) is impregnated with an equal volume of the solution containing the organic compound, the concentration of the solution containing the organic compound can be determined based on the water absorption of the solid product obtained in step 1) and the weight ratio of the solid product obtained in step 1) to the organic compound.
According to the present invention, specifically, the organic alcohol may be at least one of a monohydric alcohol, a dihydric alcohol and a trihydric alcohol, and the present invention is not particularly limited thereto, and preferably, the organic alcohol is ethylene glycol and/or glycerol, and most preferably, the organic alcohol is glycerol; the organic acid may be at least one of a monobasic acid, a dibasic acid and a polybasic acid, preferably, the organic acid includes an aminocarboxylic acid, and further preferably, the organic acid includes at least one of citric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid and diethylenetriaminepentaacetic acid. According to a preferred embodiment of the present invention, the organic compound is at least one selected from the group consisting of glycerol, citric acid, ethylenediaminetetraacetic acid, monoethanolamine, diethylenetriamine, hydroxyethylethylenediamine, nitrilotriacetic acid and diethylenetriaminepentaacetic acid, more preferably at least one selected from the group consisting of glycerol, citric acid and ethylenediaminetetraacetic acid, and most preferably glycerol and/or citric acid. The adoption of the preferable organic compound is more beneficial to improving the desulfurization and carbon residue removal performance of the obtained hydrogenation catalyst.
In the present invention, the drying conditions in step 2) are not particularly limited, and for example, the drying conditions include: the temperature is 90-200 ℃ and the time is 2-10 hours, preferably, the temperature is 100-170 ℃ and the time is 2-5 hours.
The second aspect of the invention provides a hydrogenation catalyst obtained by the method for treating the waste hydrogenation catalyst, wherein the specific surface area of the catalyst is 80-250m2The pore volume is 0.2-0.9mL/g, and the most probable pore diameter is 5-14 nm. The hydrogenation catalyst obtained by the treatment method is used in the heavy oil and/or residual oil hydrogenation treatment process, and has high desulfurization and carbon residue removal performances.
Accordingly, a third aspect of the present invention provides the use of a hydrogenation catalyst as described above in the hydroprocessing of heavy oils and/or residues. Specifically, the hydrogenation catalyst is contacted and reacted with heavy oil and/or residual oil under the condition of heavy oil and/or residual oil hydrotreating and in the presence of hydrogen.
The hydrogenation catalyst provided by the invention is suitable for treating various heavy oils and residual oils. In the present invention, "residue" means a component remaining at the bottom of a distillation tower in the distillation of crude oil, including atmospheric residue and vacuum residue. The heavy oil refers to heavy raw oil blended from residual oil and coker gas oil. The crude oil refers to natural petroleum produced from underground, and is a liquid mineral product with hydrocarbon as a main component. The heavy oil and/or oil residue has a high sulfur content and a high carbon residue content, for example, a sulfur content of at least 1 wt% and a carbon residue content of at least 10 wt% in the heavy oil and/or oil residue.
The heavy oil and/or residue hydrotreating conditions of the present invention are not particularly limited, and preferably, the heavy oil and/or residue hydrotreating conditions include: the temperature is 330--1The volume ratio of hydrogen to oil is 500-1200.
The present invention will be described in detail below by way of examples.
In the following examples, the specific surface area, pore volume and most probable pore diameter were measured by a low-temperature nitrogen adsorption method.
The carbon content in the catalyst was determined by a carbon sulfur analyzer.
The carbon residue content (wt%) in the oil product was determined according to the method of GB 17144.