A slurry bed residual oil hydroprocessing oil residue pitch and a method of making the same

Abstract

This invention discloses a slurry-bed hydrogenated oil residue asphalt and its preparation method. The asphalt comprises the following components in parts by weight: 30-60 parts of light component blending oil from slurry-bed hydrogenated oil residue, 20-50 parts of heavy component blending oil from slurry-bed hydrogenated oil residue, 5-17 parts of compatibilizer, 4-12 parts of crosslinking agent, and 0.5-1.5 parts of heat stabilizer. This invention also discloses the preparation method of this slurry-bed hydrogenated oil residue asphalt. The product of this invention utilizes slurry-bed hydrogenated oil residue as the main raw material to produce a qualified asphalt product that meets the requirements for road use, maximizing the added value of low-value slurry-bed hydrogenated oil residue. Furthermore, all performance indicators of the product meet the technical requirements for road petroleum asphalt in the "Technical Specification for Construction of Highway Asphalt Pavement" JTG F40-2004, exhibiting excellent performance and fully meeting the requirements for road construction.

Description

Technical Field

[0001] This invention relates to the field of road engineering materials technology, and in particular to a slurry-bed hydrogenated oil residue asphalt and its preparation method. Background Technology

[0002] Slurry-bed residue hydrotreating technology evolved from coal liquefaction technology. It's an innovative technology for deep conversion of residue oil, significantly improving conversion rates. In recent years, this technology has matured and begun industrial application. In 2021, Sinopec Maoming Branch officially put into operation China's first 2.6 million tons / year slurry-bed residue hydrotreating unit. This unit uses low-quality residue oil as feedstock, and through hydrocracking, produces liquefied petroleum gas (LPG), naphtha, diesel, and wax oil, with byproducts including gas and oil residue. Because the oil residue byproduct of slurry-bed residue hydrotreating has a complex composition and contains many catalyst powder impurities, its carbon residue is generally above 20%, and its properties are worse than those of low-quality residue oil. Therefore, it can currently only be processed in coking units or used directly as boiler fuel, resulting in very low economic value.

[0003] With the rapid development of my country's highway construction, a large number of high-grade asphalt roads are under construction, leading to an ever-increasing demand for asphalt and consequently, higher prices and a supply shortage. If low-value byproducts of slurry-bed sludge oil hydrotreating could be used as raw materials to produce high-value road asphalt products, it would not only improve the economic benefits of sludge but also alleviate the domestic supply-demand imbalance in road asphalt, which would be particularly significant in addressing the asphalt material supply gap in my country's highway construction. Summary of the Invention

[0004] The primary objective of this invention is to overcome the shortcomings and deficiencies of the prior art and to provide a slurry bed residue hydrogenated oil residue asphalt.

[0005] Another object of the present invention is to provide a method for preparing the above-mentioned slurry bed residue hydrogenated oil residue asphalt.

[0006] The objective of this invention is achieved through the following technical solution: a slurry-bed hydrotreated oil residue pitch, comprising the following components in parts by weight:

[0007]

[0008] In one embodiment, the slurry bed hydrotreated residue bitumen comprises the following components in parts by weight:

[0009]

[0010] In another embodiment, the slurry bed hydrotreated residue bitumen comprises the following components in parts by weight:

[0011]

[0012] The light component blended oil and heavy component blended oil of the slurry bed residue hydrotreated oil are first made by cutting the slurry bed residue hydrotreated oil into multiple narrow fractions in different temperature ranges according to the difference in boiling points of its components, and then blending the narrow fractions in a certain ratio to produce a light and heavy component blended oil that meets specific property requirements.

[0013] In a preferred embodiment, the properties of the blended oil of hydrotreated residue from slurry bed are required to be: saturated content 10%–30%, aromatic content >50%, gum content >5%, and wax content <2%.

[0014] In a preferred embodiment, the properties of the blended oil from the hydrogenated residue of the slurry bed are required to be: aromatic content > 40%, gum content > 8%, asphaltenes content 10% to 40%, and wax content < 2%.

[0015] In a preferred embodiment, the narrow fractions of the blended oil from the hydrotreated residue of the slurry bed are converted to a cutting temperature range of 380℃~430℃, 430℃~480℃, and 480℃~540℃ under normal pressure. The three narrow fractions are blended in a mass ratio of 1:(1~3):(2~4) to produce the blended oil.

[0016] In a preferred embodiment, the narrow fractions of the slurry bed residue hydrotreated residue blended oil are converted to a cutting temperature range of 540℃~580℃, 580℃~620℃, and 620℃~660℃ under normal pressure, and the three narrow fractions are blended in a mass ratio of (1~3):(1~2):1 to produce blended oil.

[0017] In a preferred embodiment, the separation of multiple narrow fractions within different specific temperature ranges is achieved through a distillation apparatus. The distillation separation process conditions for the light component blended oil from slurry bed residue hydrotreated oil are: vacuum distillation with a top vacuum degree greater than 96 kPa and a bottom temperature ≤ 320°C. The distillation separation process conditions for the heavy component blended oil from slurry bed residue hydrotreated oil are: vacuum distillation with three-stage vacuuming, a top vacuum degree greater than 99 kPa, and a bottom temperature ≤ 350°C.

[0018] In a preferred embodiment, the compatibilizer is a vacuum side-stream distillate of naphthenic petroleum, which has the following properties: wax content <2%, evaporation loss <1%, and flash point >260°C; more preferably, the vacuum side-stream distillate of naphthenic petroleum is frequently refined by vacuum distillation with a distillation range between 350°C and 520°C.

[0019] In a preferred embodiment, the crosslinking agent is made from vacuum residue obtained by atmospheric and vacuum distillation of intermediate petroleum. After being processed by propane solvent deasphalting, the light component light deasphalting oil and the heavy component propane deasphalting oil are removed. The remaining intermediate component oil has the following properties: gum content > 20% and wax content < 2%.

[0020] In a preferred embodiment, the heat stabilizer is prepared by: stirring and dissolving 1,4-diaminobutane and cyanuric chloride in a dimethyl methanol solution, adding potassium hydroxide solution to adjust the pH to 7, adding potassium polysulfide to react, concentrating and recovering dimethyl methanol, and washing and drying the remaining solid to obtain the heat stabilizer.

[0021] In a preferred embodiment, the molar ratio of 1,4-diaminobutane: cyanuric chloride: potassium polysulfide is (0.3-0.7):1:(0.8-1.2).

[0022] In a preferred embodiment, the addition of potassium polysulfide is carried out by stirring for 1.5 to 2 hours.

[0023] The above-mentioned method for preparing slurry-bed hydrotreated residue asphalt includes the following steps: A method for preparing slurry-bed hydrotreated residue asphalt includes the following steps:

[0024] (1) First, heat the slurry bed residue oil hydrogenated oil residue heavy component blended oil to 130℃~160℃, then add heat stabilizer to fully carry out heat stabilization and upgrading reaction, and cool the resulting mixture to 120℃~140℃ for later use;

[0025] (2) Heat the blended oil of hydrogenated residue in slurry bed to 120℃~140℃, then add a crosslinking agent to fully mix and crosslink, and keep the resulting crosslinked mixture warm for later use.

[0026] (3) Disperse the compatibilizer and the mixture of step (1) evenly, add the fused crosslinker of step (3), and react fully at 120℃~140℃ for 1~2 hours to obtain slurry bed sludge oil hydrogenated oil sludge asphalt.

[0027] In a preferred embodiment, the thermally stable modification reaction in step (1) is promoted by stirring for 30 to 90 minutes.

[0028] In a preferred embodiment, the melting and crosslinking in step (2) is promoted by stirring for 10 to 20 minutes.

[0029] In a preferred embodiment, the dispersion in step (3) is achieved by uniformly stirring at 120°C to 140°C for 5 to 10 minutes.

[0030] In a preferred embodiment, the full reaction in step (3) is promoted by stirring.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] This invention creatively utilizes hydrogenated slurry bed residue as the main raw material to produce qualified asphalt products that meet road use requirements. The invention separates the effective components from undesirable impurities in the hydrogenated slurry bed residue. Based on the differences in the properties and boiling points of the residue components and their specific variations, the optimal narrow-fraction cutting temperature range and blending ratio between different narrow fractions are determined, maximizing the utilization of the effective components in the residue. Furthermore, the effective components are blended in a specific combination ratio to form a light and heavy component blended oil that meets specific performance requirements. Combined with a specific thermal stabilization modification reaction, the adverse effects of residual catalyst powder and other impurities in the heavy component blended oil on performance are effectively eliminated. Finally, through crosslinking and blending with crosslinking agents and compatibilizers, qualified asphalt products that meet road use requirements are produced, maximizing the added value of low-value hydrogenated slurry bed residue and improving economic efficiency. Simultaneously, this invention alleviates the supply and demand imbalance of road asphalt in China, and is particularly significant in addressing the asphalt material supply gap in my country's highway construction. Detailed Implementation

[0033] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0034] Example 1

[0035] The raw materials used and their proportions are as follows:

[0036] Blended oil of light components from slurry bed residue hydrotreated oil: 300 grams. The slurry bed residue hydrotreated oil produced by Maoming Petrochemical Company is processed using a distillation unit under specific distillation cutting conditions to extract three narrow fractions of slurry bed residue hydrotreated oil, with distillation cutting temperatures ranging from 380℃ to 430℃, 430℃ to 480℃, and 480℃ to 540℃ under atmospheric pressure. These fractions are blended at a mass ratio of 1:1:2 to produce a blended oil with the following properties: saturated fraction content = 26.7%, aromatic fraction content = 59.2%, gum content = 5.7%, and wax content = 1.8%. The distillation cutting process conditions are: vacuum distillation, top vacuum degree greater than 96 kPa, and bottom temperature ≤ 320℃.

[0037] Blended oil of hydrotreated slurry bed residue heavy fractions: 500g. This blended oil is produced by Maoming Petrochemical Company. It is made by blending three narrow fractions of hydrotreated slurry bed residue (with a distillation temperature range of 540℃~580℃, 580℃~620℃, and 620℃~660℃ under normal pressure) in a mass ratio of 3:2:1. Its properties are as follows: aromatic content = 48.7%, gum content = 12.5%, asphaltenes content = 33.6%, and wax content = 1.4%. The distillation process conditions are: vacuum distillation, three-stage vacuum, vacuum degree at the top of the column greater than 99kPa, and bottom temperature ≤350℃.

[0038] Compatibilizer: 170g, a vacuum distillate oil produced by Maoming Petrochemical, which is a distillation oil with a distillation range of 350℃ to 520℃ produced by refining naphthenic petroleum through an atmospheric and vacuum distillation unit. Its properties are: wax content = 1.9%, evaporation loss = 0.57%, flash point = 269℃.

[0039] Crosslinking agent: 40 grams. Produced by Maoming Petrochemical, it is made from vacuum residue obtained by processing intermediate base petroleum through an atmospheric and vacuum distillation unit. After processing through a propane solvent deasphalting process unit to remove light components (light deasphalted oil) and heavy components (propane deasphalting), the remaining intermediate component oil has the following properties: gum content = 27.5%, wax content = 1.6%.

[0040] Heat stabilizer: 15g, self-made, preparation method: 1,4-diaminobutane and cyanuric chloride are added together to dimethyl methanol solution and stirred to dissolve. Then potassium hydroxide solution is added to adjust the pH of the mixture to 7. Potassium polysulfide is added and the reaction is continued for 2 hours. The mixed reaction solution is concentrated to recover dimethyl methanol. The remaining solid is then washed with water and dried to obtain the heat stabilizer. The molar ratio of 1,4-diaminobutane: cyanuric chloride: potassium polysulfide is 0.5:1:1.

[0041] Product manufacturing steps:

[0042] (1) First, heat the slurry bed residue oil hydrogenated oil residue heavy component blended oil to 150°C, then add the heat stabilizer and stir evenly for 60 minutes to allow the heat stabilizer and the slurry bed residue oil hydrogenated oil residue heavy component blended oil to fully undergo heat stabilization and upgrading reaction, and then cool down to 130°C for later use.

[0043] (2) Heat the blended oil of hydrogenated residue from slurry bed to 130°C, then add the crosslinking agent and stir evenly for 15 minutes to fully mix and crosslink the crosslinking agent with the blended oil of hydrogenated residue from slurry bed, and keep it at 130°C for later use.

[0044] (3) First, add the compatibilizer to the mixture of the heat stabilizer to be used in step (1) and the heavy component blended oil of hydrogenated slurry bed residue after heat stabilization and upgrading reaction. Stir evenly at 130°C for 5 minutes to make the compatibilizer fully dispersed in the mixture to improve the compatibility of the mixture. Then add the crosslinking agent to be used in step (2) and the mixed crosslinking of the light component blended oil of hydrogenated slurry bed residue. Continue to stir evenly at 130°C for 1 hour to fully react. Cool down to room temperature to obtain the hydrogenated slurry bed residue asphalt product.

[0045] Example 2

[0046] The raw materials used and their proportions are as follows:

[0047] Blended oil of light components from slurry bed residue hydrotreated oil residue: 600g. This blended oil is produced by Maoming Petrochemical Company using a distillation unit with specific distillation cutting process conditions. The three narrow fractions of slurry bed residue hydrotreated oil residue, with distillation cutting temperatures ranging from 380℃ to 430℃, 430℃ to 480℃, and 480℃ to 540℃ (converted to atmospheric pressure), are blended in a mass ratio of 1:3:4. Its properties are: saturated fraction content = 22.9%, aromatic fraction content = 63.5%, gum content = 7.9%, and wax content = 1.8%. The distillation cutting process conditions are: vacuum distillation, top vacuum degree greater than 96kPa, bottom temperature ≤320℃.

[0048] Blended oil of heavy fractions from slurry bed residue hydrotreated oil residue produced by Maoming Petrochemical Company: 200 grams. This blended oil is produced by blending three narrow fractions of slurry bed residue hydrotreated oil residue (distillation temperature range of 540℃~580℃, 580℃~620℃, and 620℃~660℃, converted to atmospheric pressure) in a 1:1:1 mass ratio using a distillation unit under specific distillation cutting conditions. Its properties are: aromatic content = 43.7%, gum content = 15.3%, asphaltenes content = 37.1%, and wax content = 1.4%. The distillation cutting process conditions are: vacuum distillation, three-stage vacuum, top vacuum degree greater than 99 kPa, and bottom temperature ≤ 350℃.

[0049] Compatibilizer: 50g, a vacuum distillate oil produced by Maoming Petrochemical, which is a distillation range of 350℃ to 520℃ produced from naphthenic petroleum through an atmospheric and vacuum distillation unit. Its properties are: wax content = 1.9%, evaporation loss = 0.57%, flash point = 269℃.

[0050] Crosslinking agent: 120 grams. Produced by Maoming Petrochemical, it is made from vacuum residue obtained by processing intermediate base petroleum through an atmospheric and vacuum distillation unit. The residue is then processed by a propane solvent deasphalting process unit. Under certain process conditions, the light components (light deasphalted oil) and heavy components (propane deasphalted oil) are removed, leaving the intermediate component oil with the following properties: gum content = 27.5%, wax content = 1.6%.

[0051] Heat stabilizer: 5 grams, self-made. Preparation method: 1,4-Diaminobutane and cyanuric chloride are added to a certain amount of dimethyl methanol solution and stirred until dissolved. Then, a certain amount of potassium hydroxide solution is added to adjust the pH of the mixture to 7. Next, potassium polysulfide is added and the reaction is continued for 2 hours. The mixed reaction solution is concentrated to recover dimethyl methanol. The remaining solid is then washed with water and dried to obtain the heat stabilizer. The molar ratio of 1,4-diaminobutane:cyanuric chloride:potassium polysulfide is 0.5:1:1.

[0052] Product manufacturing steps:

[0053] (1) First, heat the slurry bed residue oil hydrogenated oil residue heavy component blended oil to 150°C, then add the heat stabilizer and stir evenly for 60 minutes to allow the heat stabilizer and the slurry bed residue oil hydrogenated oil residue heavy component blended oil to fully undergo heat stabilization and upgrading reaction, and then cool down to 130°C for later use.

[0054] (2) Heat the blended oil of hydrogenated residue from slurry bed to 130°C, then add the crosslinking agent and stir evenly for 15 minutes to fully mix and crosslink the crosslinking agent with the blended oil of hydrogenated residue from slurry bed, and keep it at 130°C for later use.

[0055] (3) First, add the compatibilizer to the mixture of the heat stabilizer to be used in step (1) and the heavy component blended oil of hydrogenated slurry bed residue oil after heat stabilization and upgrading reaction. Stir evenly at 130°C for 5 minutes to make the compatibilizer fully dispersed in the mixture to improve the compatibility of the mixture. Then add the crosslinking agent to be used in step (2) and the mixed crosslinking agent of light component blended oil of hydrogenated slurry bed residue oil. Continue to stir evenly at 130°C for 1 hour to fully react. Cool down to room temperature to obtain the hydrogenated slurry bed residue oil asphalt product.

[0056] Example 3

[0057] The raw materials used and their proportions are as follows:

[0058] Blended oil of light components from slurry bed residue hydrotreated oil residue: 350 grams. This blended oil is produced by Maoming Petrochemical Company. It is made by blending three narrow fractions of slurry bed residue hydrotreated oil residue (distillation temperature ranges of 380℃~430℃, 430℃~480℃, and 480℃~540℃, converted to atmospheric pressure) in a 1:1:2 mass ratio using a distillation cutting process. The properties are: saturated fraction = 26.7%, aromatic fraction = 59.2%, gum content = 5.7%, and wax content = 1.8%. The distillation cutting process conditions are: vacuum distillation, top vacuum degree > 96 kPa, bottom temperature ≤ 320℃.

[0059] Blended oil of heavy fractions from slurry bed residue hydrotreated oil residue produced by Maoming Petrochemical Company: 450 grams. This blended oil is produced by blending three narrow fractions of slurry bed residue hydrotreated oil residue (distillation temperature ranges of 540℃~580℃, 580℃~620℃, and 620℃~660℃, converted to atmospheric pressure) in a mass ratio of 3:2:1, using specific distillation cutting process conditions. Its properties are: aromatic content = 48.7%, gum content = 12.5%, asphaltenes content = 33.6%, and wax content = 1.4%. The distillation cutting process conditions are: vacuum distillation, three-stage vacuum, top vacuum degree greater than 99 kPa, and bottom temperature ≤ 350℃.

[0060] Compatibilizer: 70g, a vacuum distillate oil produced by Maoming Petrochemical, which is a distillation range of 350℃ to 520℃ produced from naphthenic petroleum through an atmospheric and vacuum distillation unit. Its properties are: wax content = 1.9%, evaporation loss = 0.57%, flash point = 269℃.

[0061] Crosslinking agent: 100 grams. Produced by Maoming Petrochemical, it is made from vacuum residue obtained by processing intermediate base petroleum through an atmospheric and vacuum distillation unit. The residue is then processed by a propane solvent deasphalting process unit. Under certain process conditions, the light components (light deasphalted oil) and heavy components (propane deasphalting) are removed, leaving the intermediate component oil with the following properties: gum content = 27.5%, wax content = 1.6%.

[0062] Heat stabilizer: 7 grams, self-made. Preparation method: 1,4-Diaminobutane and cyanuric chloride are added to a certain amount of dimethyl methanol solution and stirred until dissolved. Then, a certain amount of potassium hydroxide solution is added to adjust the pH of the mixture to 7. Next, potassium polysulfide is added and the reaction is continued for 2 hours. The mixed reaction solution is concentrated to recover dimethyl methanol. The remaining solid is then washed with water and dried to obtain the heat stabilizer. The molar ratio of 1,4-diaminobutane:cyanuric chloride:potassium polysulfide is 0.5:1:1.

[0063] Product manufacturing steps:

[0064] (1) First, heat the slurry bed residue oil hydrogenated oil residue heavy component blended oil to 150°C, then add the heat stabilizer and stir evenly for 60 minutes to allow the heat stabilizer and the slurry bed residue oil hydrogenated oil residue heavy component blended oil to fully undergo heat stabilization and upgrading reaction, and then cool down to 130°C for later use.

[0065] (2) Heat the blended oil of hydrogenated residue from slurry bed to 130°C, then add the crosslinking agent and stir evenly for 15 minutes to fully mix and crosslink the crosslinking agent with the blended oil of hydrogenated residue from slurry bed, and keep it at 130°C for later use.

[0066] (3) First, add the compatibilizer to the mixture of the heat stabilizer to be used in step (1) and the heavy component blended oil of hydrogenated slurry bed residue oil after heat stabilization and upgrading reaction. Stir evenly at 130°C for 5 minutes to make the compatibilizer fully dispersed in the mixture to improve the compatibility of the mixture. Then add the crosslinking agent to be used in step (2) and the mixed crosslinking agent of light component blended oil of hydrogenated slurry bed residue oil. Continue to stir evenly at 130°C for 1 hour to fully react. Cool down to room temperature to obtain the hydrogenated slurry bed residue oil asphalt product.

[0067] Example 4

[0068] The raw materials used and their proportions are as follows:

[0069] Blended oil of light components from slurry bed residue hydrotreated oil residue: 550g. This blended oil is produced by Maoming Petrochemical Company. It is made by blending three narrow fractions of slurry bed residue hydrotreated oil residue (distillation temperature range of 380℃~430℃, 430℃~480℃, and 480℃~540℃, converted to atmospheric pressure) in a 1:1:2 mass ratio using a distillation cutting process. The properties are: saturated fraction = 26.7%, aromatic fraction = 59.2%, gum content = 5.7%, and wax content = 1.8%. The distillation cutting process conditions are: vacuum distillation, top vacuum degree > 96kPa, bottom temperature ≤ 320℃.

[0070] Blended oil of heavy fractions from slurry bed residue hydrotreated oil residue produced by Maoming Petrochemical Company: 250 grams. This blended oil is produced by blending three narrow fractions of slurry bed residue hydrotreated oil residue (distillation temperature ranges of 540℃~580℃, 580℃~620℃, and 620℃~660℃, converted to atmospheric pressure) in a mass ratio of 3:2:1, using specific distillation cutting process conditions. Its properties are: aromatic content = 48.7%, gum content = 12.5%, asphaltenes content = 33.6%, and wax content = 1.4%. The distillation cutting process conditions are: vacuum distillation, three-stage vacuum, top vacuum degree greater than 99 kPa, and bottom temperature ≤ 350℃.

[0071] Compatibilizer: 150g, a vacuum distillate oil produced by Maoming Petrochemical, which is a distillation oil with a distillation range of 350℃ to 520℃ produced by refining naphthenic petroleum through an atmospheric and vacuum distillation unit. Its properties are: wax content = 1.9%, evaporation loss = 0.57%, flash point = 269℃.

[0072] Crosslinking agent: 60 grams. Produced by Maoming Petrochemical, it is made from vacuum residue obtained by processing intermediate base petroleum through an atmospheric and vacuum distillation unit. The residue is then processed by a propane solvent deasphalting process unit. Under certain process conditions, the light components (light deasphalted oil) and heavy components (propane deasphalted oil) are removed, leaving the intermediate component oil with the following properties: gum content = 27.5%, wax content = 1.6%.

[0073] Heat stabilizer: 13g, self-made. Preparation method: 1,4-Diaminobutane and cyanuric chloride are added to a certain amount of dimethyl methanol solution and stirred to dissolve. Then, a certain amount of potassium hydroxide solution is added to adjust the pH of the mixture to 7. Next, potassium polysulfide is added and the reaction is continued for 2 hours. The mixed reaction solution is concentrated to recover dimethyl methanol. The remaining solid is then washed with water and dried to obtain the heat stabilizer. The molar ratio of 1,4-diaminobutane:cyanuric chloride:potassium polysulfide is 0.5:1:1.

[0074] Product manufacturing steps:

[0075] (1) First, heat the slurry bed residue oil hydrogenated oil residue heavy component blended oil to 150°C, then add the heat stabilizer and stir evenly for 60 minutes to allow the heat stabilizer and the slurry bed residue oil hydrogenated oil residue heavy component blended oil to fully undergo heat stabilization and upgrading reaction, and then cool down to 130°C for later use.

[0076] (2) Heat the blended oil of hydrogenated residue from slurry bed to 130°C, then add the crosslinking agent and stir evenly for 15 minutes to fully mix and crosslink the crosslinking agent with the blended oil of hydrogenated residue from slurry bed, and keep it at 130°C for later use.

[0077] (3) First, add the compatibilizer to the mixture of the heat stabilizer to be used in step (1) and the heavy component blended oil of hydrogenated slurry bed residue oil after heat stabilization and upgrading reaction. Stir evenly at 130°C for 5 minutes to make the compatibilizer fully dispersed in the mixture to improve the compatibility of the mixture. Then add the crosslinking agent to be used in step (2) and the mixed crosslinking agent of light component blended oil of hydrogenated slurry bed residue oil. Continue to stir evenly at 130°C for 1 hour to fully react. Cool down to room temperature to obtain the hydrogenated slurry bed residue oil asphalt product.

[0078] Example 5

[0079] The raw materials used and their proportions are as follows:

[0080] Blended oil of light components from slurry bed residue hydrotreated oil residue: 450 grams. This blended oil is produced by Maoming Petrochemical Company. It is made by blending three narrow fractions of slurry bed residue hydrotreated oil residue (distillation temperature ranges of 380℃~430℃, 430℃~480℃, and 480℃~540℃, converted to atmospheric pressure) in a 1:1:2 mass ratio using a distillation cutting process. The properties are: saturated fraction = 26.7%, aromatic fraction = 59.2%, gum content = 5.7%, and wax content = 1.8%. The distillation cutting process conditions are: vacuum distillation, top vacuum degree > 96 kPa, bottom temperature ≤ 320℃.

[0081] Blended oil of heavy fractions from slurry bed residue hydrotreated oil residue produced by Maoming Petrochemical Company: 350 grams. This blended oil is produced by blending three narrow fractions of slurry bed residue hydrotreated oil residue (distillation temperature ranges of 540℃~580℃, 580℃~620℃, and 620℃~660℃, converted to atmospheric pressure) in a mass ratio of 3:2:1. Its properties are: aromatic content = 48.7%, gum content = 12.5%, asphaltenes content = 33.6%, and wax content = 1.4%. The distillation cutting process conditions are: vacuum distillation, three-stage vacuum, top vacuum degree greater than 99 kPa, and bottom temperature ≤ 350℃.

[0082] Compatibilizer: 110 grams, a vacuum distillate oil produced by Maoming Petrochemical, which is a distillation range of 350℃ to 520℃ produced from naphthenic petroleum through an atmospheric and vacuum distillation unit. Its properties are: wax content = 1.9%, evaporation loss = 0.57%, flash point = 269℃.

[0083] Crosslinking agent: 80 grams. Produced by Maoming Petrochemical, it is made from vacuum residue obtained by processing intermediate base petroleum through an atmospheric and vacuum distillation unit. The residue is then processed by a propane solvent deasphalting process unit. Under certain process conditions, the light components (light deasphalted oil) and heavy components (propane deasphalted oil) are removed, leaving the intermediate component oil with the following properties: gum content = 27.5%, wax content = 1.6%.

[0084] Heat stabilizer: 10g, self-made. Preparation method: 1,4-Diaminobutane and cyanuric chloride are added to a certain amount of dimethyl methanol solution and stirred to dissolve. Then, a certain amount of potassium hydroxide solution is added to adjust the pH of the mixture to 7. Next, potassium polysulfide is added and the reaction is continued for 2 hours. The mixed reaction solution is concentrated to recover dimethyl methanol. The remaining solid is then washed with water and dried to obtain the heat stabilizer. The molar ratio of 1,4-diaminobutane:cyanuric chloride:potassium polysulfide is 0.5:1:1.

[0085] Product manufacturing steps:

[0086] (1) First, heat the slurry bed residue oil hydrogenated oil residue heavy component blended oil to 150°C, then add the heat stabilizer and stir evenly for 60 minutes to allow the heat stabilizer and the slurry bed residue oil hydrogenated oil residue heavy component blended oil to fully undergo heat stabilization and upgrading reaction, and then cool down to 130°C for later use.

[0087] (2) Heat the blended oil of hydrogenated residue from slurry bed to 130°C, then add the crosslinking agent and stir evenly for 15 minutes to fully mix and crosslink the crosslinking agent with the blended oil of hydrogenated residue from slurry bed, and keep it at 130°C for later use.

[0088] (3) First, add the compatibilizer to the mixture of the heat stabilizer to be used in step (1) and the heavy component blended oil of hydrogenated slurry bed residue oil after heat stabilization and upgrading reaction. Stir evenly at 130°C for 5 minutes to make the compatibilizer fully dispersed in the mixture to improve the compatibility of the mixture. Then add the crosslinking agent to be used in step (2) and the mixed crosslinking agent of light component blended oil of hydrogenated slurry bed residue oil. Continue to stir evenly at 130°C for 1 hour to fully react. Cool down to room temperature to obtain the hydrogenated slurry bed residue oil asphalt product.

[0089] Comparative Example 1

[0090] The difference from Example 1 is as follows:

[0091] The raw materials and their proportions are as follows: 200g of light component blended oil from slurry bed residue hydrogenated oil residue, 600g of heavy component blended oil from slurry bed residue hydrogenated oil residue, 170g of compatibilizer, 40g of crosslinking agent, and 15g of heat stabilizer.

[0092] Comparative Example 2

[0093] The difference from Example 1 is as follows:

[0094] The raw materials and their proportions are as follows: 700g of blended oil of light component from hydrogenated slurry bed residue oil, 100g of blended oil of heavy component from hydrogenated slurry bed residue oil, 170g of compatibilizer, 40g of crosslinking agent, and 15g of heat stabilizer.

[0095] Comparative Example 3

[0096] The difference from Example 1 is as follows:

[0097] The raw materials and their proportions are as follows: 300g of blended oil of light component from hydrogenated slurry bed residue oil, 500g of blended oil of heavy component from hydrogenated slurry bed residue oil, 180g of compatibilizer, 10g of crosslinking agent, and 15g of heat stabilizer.

[0098] Comparative Example 4

[0099] The difference from Example 1 is as follows:

[0100] The raw materials and their proportions are as follows: 300g of blended oil of light component from hydrogenated slurry bed residue oil, 500g of blended oil of heavy component from hydrogenated slurry bed residue oil, 170g of compatibilizer, 86g of crosslinking agent, and 4g of heat stabilizer.

[0101] Comparative Example 5

[0102] The difference from Example 1 is as follows:

[0103] The blended oil of light components from slurry bed residue hydrotreated oil used was a blended oil produced by Maoming Petrochemical Company. It was made by blending three narrow fractions of slurry bed residue hydrotreated oil treated oil, which were cut from the hydrotreated oil treated oil treated oil under atmospheric pressure and had a distillation cutting temperature range of 380℃~430℃, 430℃~480℃, and 480℃~540℃, in a mass ratio of 1:1:2. Its properties are as follows: saturated fraction content = 8.9%, aromatic fraction content = 76.2%, gum content = 4.5%, and wax content = 1.9%.

[0104] Comparative Example 6

[0105] The difference from Example 1 is as follows:

[0106] The blended oil of light components from slurry bed residue hydrotreated oil used was a blended oil produced by Maoming Petrochemical Company. It was made by blending three narrow fractions of slurry bed residue hydrotreated oil treated oil, which were cut from the hydrotreated oil treated oil treated oil under atmospheric pressure and had a distillation cutting temperature range of 380℃~430℃, 430℃~480℃, and 480℃~540℃, in a mass ratio of 1:4:5. Its properties are as follows: saturated fraction content = 15.8%, aromatic fraction content = 68.9%, gum content = 9.6%, and wax content = 1.8%.

[0107] Comparative Example 7

[0108] The difference from Example 1 is as follows:

[0109] The blended oil of hydrotreated slurry residue used was a blended oil produced by Maoming Petrochemical Company. It was made by blending three narrow fractions of hydrotreated slurry residue produced by Maoming Petrochemical Company through a distillation unit. The distillation temperature ranges under atmospheric pressure: 540℃~580℃, 580℃~620℃, and 620℃~660℃. The blended oil was blended in a mass ratio of 3:2:1. Its properties are as follows: aromatic content = 37.5%, gum content = 15.6%, asphaltenes content = 34.2%, and wax content = 1.5%.

[0110] Comparative Example 8

[0111] The difference from Example 1 is as follows:

[0112] The blended oil of hydrotreated slurry residue used was a blended oil produced by Maoming Petrochemical Company. It was made by blending three narrow fractions of hydrotreated slurry residue produced by Maoming Petrochemical Company through a distillation unit. The distillation temperature ranges were 540℃~580℃, 580℃~620℃, and 620℃~660℃ under atmospheric pressure. The blended oil was blended in a mass ratio of 1:1:2. Its properties are as follows: aromatic content = 41.9%, gum content = 13.1%, asphaltenes content = 37.7%, and wax content = 1.4%.

[0113] Comparative Example 9

[0114] The difference from Example 1 is as follows:

[0115] The compatibilizer used is a vacuum distillate oil produced by Maoming Petrochemical, which is a distillation range of 350℃ to 520℃ produced from non-cycloalkyl petroleum through an atmospheric and vacuum distillation unit. Its properties are: wax content = 2.6%, evaporation loss = 1.07%, and flash point = 209℃.

[0116] Comparative Example 10

[0117] The difference from Example 1 is as follows:

[0118] The crosslinking agent used is vacuum residue oil produced by Maoming Petrochemical, which is obtained by processing non-intermediate base petroleum through an atmospheric and vacuum distillation unit. After processing through a propane solvent deasphalting process unit to remove light components (light deasphalted oil) and heavy components (propane deasphalting), the remaining intermediate component oil has the following properties: gum content = 18.9% and wax content = 2.7%.

[0119] Comparative Example 11

[0120] The difference from Example 1 is that it does not contain a heat stabilizer.

[0121] Test case

[0122] The performance of the samples from Examples 1 to 5 and Comparative Examples 1 to 11 of the present invention were tested in accordance with the technical standards of JTG E20-2011 "Test Procedures for Asphalt and Asphalt Mixtures in Highway Engineering" and the index requirements of JTG F40-2004 "Technical Specifications for Construction of Asphalt Pavement on Highway". The test results are shown in Table 1.

[0123] Table 1. Performance test results of each embodiment and comparative sample.

[0124]

[0125]

[0126]

[0127] The test results in Table 1 show that the performance indicators of the products in all embodiments of the present invention meet the technical requirements for road petroleum asphalt in the "Technical Specification for Construction of Highway Asphalt Pavement" JTG F40-2004. Specifically, the performance indicators of Embodiments 1, 3, and 5 meet the technical requirements for Grade 70 B road asphalt, while the performance indicators of Embodiments 2 and 4 meet the technical requirements for Grade 90 B road asphalt. Through comprehensive performance comparison, especially considering the residual penetration ratio and residual ductility, under the same penetration range, the performance of Embodiment 5 (Grade 70 road asphalt) is superior to Embodiment 3, and the performance of Embodiment 3 is superior to Embodiment 1. The performance of Embodiment 4 (Grade 90 road asphalt) is superior to Embodiment 2. However, the residual penetration ratio and residual ductility of Comparative Examples 1 to 11 fail to meet the road asphalt performance requirements for their corresponding penetration ranges. Therefore, the test results of Embodiments 1 to 5 prove that the products of the present invention have excellent performance and fully meet the requirements for road construction.

[0128] The above description represents the preferred embodiments of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications are also considered to be within the scope of protection of the present invention.

Claims

1. A slurry bed residual hydrooil sludge pitch, characterized in that, The components include the following parts by mass: 30-60 parts of blended oil of light components from hydrotreated residue in slurry bed; 20-50 parts of blended oil from hydrotreated residue in slurry bed; 5-17 parts of compatibilizer; 4-12 parts of crosslinking agent; Heat stabilizer 0.5–1.5 parts; The properties of the blended oil of light components from hydrotreated residue in the slurry bed are required to be: saturated content 22.9%–30%, aromatic content 50%–63.5%, gum content 5.7%–7.9%, and wax content <2%. The properties of the blended oil from the hydrogenated residue of the slurry bed are required to be: aromatic content ≥43.7%, gum content >8%, asphaltene content 10%–40%, and wax content <2%. The compatibilizer is a vacuum distillate oil with a distillation range of 350°C to 520°C, produced by refining naphthenic petroleum through an atmospheric and vacuum distillation unit. The crosslinking agent is made from vacuum residue oil obtained by processing intermediate base petroleum through an atmospheric and vacuum distillation unit, which is then processed by a propane solvent deasphalting process to remove light and heavy components, leaving the intermediate component oil. The heat stabilizer is prepared by adding 1,4-diaminobutane and cyanuric chloride together into a dimethyl methanol solution and stirring to dissolve them. Then, potassium hydroxide solution is added to adjust the pH of the mixture to 7. Next, potassium polysulfide is added and the reaction is continued for 2 hours. The mixed reaction solution is then concentrated to recover dimethyl methanol. The remaining solid is then washed with water and dried to obtain the heat stabilizer.

2. The slurry bed residual hydroprocessing oil residue asphalt of claim 1, wherein, The components include the following parts by mass: 35-55 parts of blended oil of light components from hydrotreated residue in slurry bed; 25-45 parts of blended oil from hydrotreated residue in slurry bed; 7-15 parts compatibilizer; Crosslinking agent 6-10 parts; Heat stabilizer 0.7 to 1.3 parts.

3. The slurry-bed hydrotreated oil residue bitumen according to claim 2, characterized in that, The components include the following parts by mass: 40-50 parts of blended oil of light components from hydrotreated residue in slurry bed; 30-40 parts of blended oil from hydrotreated residue in slurry bed; 9-13 parts compatibilizer; 7-9 parts of crosslinking agent; Heat stabilizer 0.9 to 1.1 parts.

4. The slurry bed residual hydroprocessing oil residue asphalt of claim 1 wherein, Includes at least one of the following: The narrow fractions of the blended oil from the hydrogenated residue of the slurry bed residue are converted to cut-off temperatures of 380℃~430℃, 430℃~480℃, and 480℃~540℃ under normal pressure. The three narrow fractions are blended in a mass ratio of 1:(1~3):(2~4) to produce the blended oil. The narrow fractions of the slurry bed residue hydrotreated residue blended oil are converted to cut-off temperatures of 540℃~580℃, 580℃~620℃, and 620℃~660℃ under normal pressure. The three narrow fractions are blended in a mass ratio of (1~3):(1~2):1 to produce blended oil.

5. The slurry bed residual hydroprocessing oil residue asphalt of claim 4, wherein, Includes at least one of the following: Distillation apparatus is used to separate multiple narrow fractions within different specific temperature ranges. The distillation and cutting process conditions for the slurry bed residue hydrogenated residue light component blended oil are as follows: vacuum distillation is used, the vacuum degree at the top of the column is greater than 96 kPa, and the temperature at the bottom of the vessel is ≤320℃. The distillation and cutting process conditions for the hydrogenated residue heavy fraction blended oil from the slurry bed are as follows: vacuum distillation is used, with three-stage vacuuming, a top vacuum degree greater than 99 kPa, and a bottom temperature ≤350℃.

6. The slurry bed residual hydroprocessing oil residue asphalt of claim 1 wherein, Includes at least one of the following: The compatibilizer must meet the following properties: wax content <2%, evaporation loss <1%, flash point >260℃; The crosslinking agent must meet the following properties: gum content > 20%, wax content < 2%.

7. The slurry bed residual hydroprocessing oil residue asphalt of claim 6, wherein, Includes at least one of the following: The vacuum side-stream distillate of the naphthenic petroleum is often refined by vacuum distillation, with a distillation range between 350°C and 520°C. In the preparation of the heat stabilizer, the molar ratio of 1,4-diaminobutane: cyanuric chloride: potassium polysulfide is (0.3-0.7): 1: (0.8-1.2). The reaction conditions for adding potassium polysulfide are: stirring for 1.5 to 2 hours.

8. The process for the production of a slurry bed residual hydrocarbon oil residuum asphalt according to any one of claims 1 to 7, characterized in that, Includes the following steps: A method for preparing hydrotreated residue asphalt in a slurry bed includes the following steps: (1) First, heat the slurry bed residue oil hydrogenated oil residue heavy component blended oil to 130℃~160℃, then add heat stabilizer to fully carry out heat stabilization and upgrading reaction, and cool the resulting mixture to 120℃~140℃ for later use; (2) Heat the blended oil of hydrogenated residue in slurry bed to 120℃~140℃, then add a crosslinking agent to fully mix and crosslink, and keep the resulting crosslinked mixture warm for later use. (3) Disperse the compatibilizer and the mixture of step (1) evenly, add the fused crosslinker of step (2), and react fully at 120℃~140℃ for 1~2 hours to obtain slurry bed sludge oil hydrogenated oil sludge asphalt.

9. The preparation method according to claim 8, characterized in that, Includes at least one of the following: The thermally stable modification reaction described in step (1) is promoted by stirring for 30 to 90 minutes; In step (2), the reaction is promoted by stirring for 10 to 20 minutes. The dispersion in step (3) is achieved by uniformly stirring at 120℃~140℃ for 5~10 minutes.