A 90a grade bitumen and a method for its production

Abstract

The application discloses a 90# A-grade asphalt and a preparation method thereof. The 90# A-grade asphalt comprises the following raw material components in parts by weight: acid anhydride reduced residue 100 parts; pretreatment component 20-80 parts; wherein the acid anhydride reduced residue comprises the following raw material components in percentage by weight: inferior reduced residue 100 parts; acid anhydride modifier 2-10 parts, polyphosphoric acid 0.1-2 parts, and initiator 0.08-0.7 parts. The 90# A-grade asphalt product with high flash point, low-temperature performance and other indicators meeting the standard requirements is obtained by using the inferior reduced residue which is difficult to handle as the raw material.

Description

Technical Field

[0001] This invention relates to a road petroleum asphalt and its preparation method, and particularly to a 90A grade asphalt and its preparation method. Background Technology

[0002] As crude oil becomes increasingly heavy, the yield of vacuum residue is gradually increasing, leading to higher levels of heavy metals and sulfur in the residue. This increases the difficulty of lightening the residue. However, using inferior vacuum residue to produce asphalt is a relatively simple and economically efficient processing method. China's asphalt production mainly employs a distillation and blending process. However, with the deterioration of vacuum residue quality, the relative content of saturated components and asphaltenes increases, while the relative content of aromatics and resins decreases. Furthermore, the asphaltenes exhibit greater association and more complex forms. Under these conditions, a simple distillation and blending process is insufficient to produce qualified road asphalt, and the production of Grade 90 A road asphalt, which requires higher crude oil properties, becomes even more challenging.

[0003] For example, Tarim River heavy oil, while an important petroleum resource, differs significantly from other oil sources in its structure, composition, and physicochemical properties. Tarim River vacuum residue yields over 70%, and is characterized by high sulfur, high residual carbon, high asphaltenes, and high heavy metal content. Tarim Refining & Chemical Co., Ltd. began producing Tarim 90A grade asphalt in 2005, when its vacuum residue had a penetration of 60-70 and a flash point between 260℃ and 270℃. However, with the passage of time, Tarim crude oil has become increasingly heavier. The asphaltenes content in vacuum residue reached 15% in 2007 and 23% in 2009, and exceeded 40% in 2019. Under these circumstances, the existing production process can no longer produce a product that simultaneously meets the requirements for 90A grade road asphalt in terms of flash point and low-temperature performance. Therefore, the refinery can only coke the residue or produce 60 grade asphalt, which significantly reduces industrial efficiency. Thus, developing a qualified 90A asphalt production method is crucial to address the increasingly deteriorating quality of crude oil.

[0004] CN109593541A discloses a Grade 90 A road petroleum asphalt and its preparation method. This Grade 90 A road asphalt is prepared from Grade 70 A road petroleum asphalt, catalytic cracking slurry fraction, and polyphosphoric acid. The penetration of the asphalt is improved by using the catalytic cracking slurry fraction, and the viscosity and softening point are improved by using polyphosphoric acid. However, this method simply blends several materials. Although it can ultimately blend Grade 70 A road petroleum asphalt into Grade 90A, the addition of catalytic cracking slurry reduces the asphalt's anti-aging properties and low-temperature elongation, and the addition of light components lowers the flash point, making this method unsuitable for producing Grade 90A asphalt.

[0005] CN110484009A discloses a No. 110 road petroleum asphalt and its preparation method. This method involves blending and stirring No. 70 road petroleum asphalt, reduced-strength wax oil, and polyphosphoric acid to obtain a product that meets the No. 110 Grade A road petroleum asphalt standard. The preparation process is simple and convenient. However, the direct addition of reduced-strength wax oil lowers the flash point of the asphalt, and the direct incorporation of polyphosphoric acid does not exert its true effect, and even inhibits the elastomeric effect of the reduced-strength wax oil to some extent.

[0006] CN103102498A discloses a method for producing styrene-butadiene rubber-modified asphalt. This method significantly increases the low-temperature elongation of asphalt, solving the problem of difficulty in modifying matrix asphalt with high asphaltene content and low aromaticity. However, this method only increases the low-temperature elongation of asphalt and does not substantially improve the flash point, anti-aging properties, etc.

[0007] In summary, none of the above methods are suitable for producing high-grade road asphalt from inferior raw materials, and traditional blending methods cannot simultaneously ensure that the resulting product meets both low-temperature performance and flash point requirements. Therefore, for raw materials with high asphalt content and low aromaticity, it is necessary to develop new asphalt production processes to increase the added value of low-quality resources. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides a Grade 90 A asphalt and its preparation method. This invention uses difficult-to-process, low-quality asphalt slag as raw material to obtain a Grade 90 A asphalt product with a high flash point, while also meeting standard requirements for low-temperature performance and other indicators.

[0009] This invention provides a Grade A 90 asphalt, comprising, by weight, the following raw material components: anhydride-based slag reduction: 100 parts; pretreatment components: 20-80 parts, preferably 40-60 parts; wherein the anhydride-based slag reduction comprises, by weight, the following raw material components:

[0010] Inferior slag reduction: 100 portions;

[0011] Anhydride modifier: 2-10 parts, preferably 2-8 parts;

[0012] Polyphosphoric acid: 0.1–2 parts, preferably 0.2–1.8 parts;

[0013] Initiator: 0.08 to 0.7 parts, preferably 0.15 to 0.7 parts.

[0014] The pretreatment components, by weight, include the following raw material components:

[0015] Inferior slag reduction: 100 portions;

[0016] Medium-quality component: 20-50 parts, preferably 25-40 parts;

[0017] Lightweight component: 5 to 20 parts, preferably 6 to 15 parts.

[0018] The inferior slag in the pretreatment component and the inferior slag in the anhydride treatment component only need to meet the following properties. The properties of the two can be exactly the same or different.

[0019] The inferior slag has the following properties: flash point of 241-256℃, sulfur content of 2.61wt%-3.65wt%, and by mass fraction, saturated matter of 26.1%-37.7%, aromatic matter of 20.2%-34.5%, resin of 18.3%-24.8%, and asphaltenes of 21.3%-30.1%, with asphaltenes preferably being 21.3%-26.0%.

[0020] The inferior slag also has the following properties: residual carbon value of 21wt% to 29wt%, nitrogen content of 0.14wt% to 0.61wt%, total nickel and vanadium content of 320 to 365μg / g, and condensation index CI of 0.26 to 0.35.

[0021] The inferior reduced slag can be Tarim River reduced slag or other reduced slag that meets the above properties, and the inferior reduced slag is a fraction with an initial boiling point greater than 425°C.

[0022] Furthermore, in the pretreatment components, the intermediate component refers to the resin obtained after solvent deasphalting, and the intermediate component has the following properties: kinematic viscosity of 50 mmHg at 100°C. 2 / s~65mm 2 / s, flash point is 206℃~220℃, by mass fraction, saturated fraction accounts for 30%~42%, aromatic fraction accounts for 48%~57%, resin accounts for 8%~13%, asphaltene content is less than 2%; weight average molecular weight is 1990~2140, molecular weight distribution width is 1.6~3.7.

[0023] Furthermore, in the pretreatment components, the light component refers to vacuum-pressed wax oil, which has the following properties: kinematic viscosity of 10 mmHg at 50°C. 2 / s~16mm 2 / s, density at 20℃ is 760~900kg / m³ 3 By mass fraction, the saturated fraction accounts for 60%–78%, the aromatic fraction accounts for 20%–32%, and the total content of resins and asphaltenes is less than 6%; the residual carbon is less than 0.15%, the sulfur content is less than 0.3%, the nitrogen content is less than 1%, and the hydrogen-to-carbon ratio is 1.5–1.8.

[0024] Furthermore, in the anhydride-induced slag reduction process, the polyphosphoric acid includes polyphosphoric acid with low phosphoric acid content and polyphosphoric acid with high phosphoric acid content.

[0025] The low-phosphoric acid content polyphosphoric acid accounts for 20% to 50% of the total mass of polyphosphoric acid, and the high-phosphoric acid content polyphosphoric acid accounts for 50% to 80% of the total mass of polyphosphoric acid.

[0026] The low-phosphoric-content polyphosphoric acid refers to polyphosphoric acid containing 105% to 125% phosphoric acid (calculated as H3PO4) by mass, preferably 110% to 120%.

[0027] The high phosphoric acid content polyphosphoric acid refers to polyphosphoric acid containing 130% to 145% phosphoric acid (calculated as H3PO4) by mass, preferably 130% to 140%.

[0028] Furthermore, in the anhydride-based slag reduction process, the anhydride modifier is one or more of maleic anhydride, polyisobutylene succinic anhydride, methyl nadic anhydride, modified methyl nadic anhydride, dodecenyl succinic anhydride, tung oil anhydride, polyazelite anhydride, polyglutaric anhydride, polyoxoanhydride, or hydrolyzed polymaleic anhydride.

[0029] Furthermore, in the anhydride-induced slag reduction process, the initiator is one or more of dicumyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, sodium metabisulfite, azobisisobutyronitrile, azobisisoheptanenitrile, and cumyl hydroperoxide.

[0030] This invention also provides a method for preparing Grade A 90 asphalt, which includes the following steps:

[0031] (1) Preparation of acid anhydride-reduced slag;

[0032] (2) Preparation of pretreatment components;

[0033] (3) The materials obtained in step (1) and step (2) are mixed and statically insulated to finally obtain No. 90 Grade A asphalt.

[0034] Furthermore, in step (1), the process for preparing the anhydride-based slag reduction is as follows:

[0035] a. Add the inferior slag and high-phosphoric acid content polyphosphoric acid, heated to a fluid state, to the reactor, heat to the reaction temperature and stir continuously, and carry out the reaction under a protective gas. After the reaction is completed, keep it at a constant temperature.

[0036] b. Add low-phosphoric acid content polyphosphoric acid to the material obtained in step a, stir evenly, then add anhydride modifier and initiator, continue stirring and heat to the reaction temperature, and carry out the reaction under protective gas. After the reaction is completed, anhydride-modified slag is obtained.

[0037] In step a, the reactor is a high-pressure reactor, and the initial temperature of the reactor is adjusted to 115-140℃.

[0038] In step a, the heating to the reaction temperature is performed using a programmed temperature rise method, with a heating rate of 1–3 °C / min, and the reaction temperature is 140 °C–180 °C, preferably 145 °C–160 °C. The reaction time is 3–6 hours. The stirring speed is 600–800 r / min.

[0039] In step a, the protective gas is an inert gas and / or N2, and the amount of the protective gas is such that the pressure inside the reactor is maintained at 0.2–0.9 MPa, preferably 0.4–0.8 MPa. The heat preservation treatment is carried out at 120–135°C for 10–16 hours.

[0040] In step b, after adding polyphosphoric acid with low phosphoric acid content, stir for 30-50 minutes at a stirring speed of 300-600 r / min.

[0041] In step b, the stirring speed after adding the anhydride modifier and initiator is 600–800 r / min. Heating to the reaction temperature is performed using a programmed temperature rise method at a rate of 1–3 °C / min. The reaction temperature is 160 °C–180 °C, and the reaction time is 6–8 h. The protective gas is an inert gas and / or N2. The amount of protective gas is such that the pressure inside the reactor is maintained at 0.3–0.9 MPa, preferably 0.5–0.9 MPa.

[0042] Furthermore, in step (2), the process for preparing the pretreatment components is as follows:

[0043] i. After heating the inferior slag to a fluid state, mix it with the medium and light components, and then perform hydrogenation treatment together with hydrogen.

[0044] ii. Perform atmospheric and vacuum distillation on the material obtained in step i to obtain the final pretreated components.

[0045] In step i, the operating conditions for the hydrogenation treatment are: reaction temperature of 365℃~390℃, reaction pressure of 12MPa~22MPa, and volume hourly space velocity of 0.5~1.8h. -1 The hydrogen-to-oil volume ratio is 400–1500; the preferred operating conditions are: reaction temperature 370–390℃, reaction pressure 13–20 MPa, and volume hourly space velocity (VHSV) 0.5–1.2 h⁻¹. -1 The hydrogen-to-oil volume ratio is 500–1100.

[0046] In step i, the reactor used for the hydrogenation treatment can be a fixed-bed hydrogenation reactor, a fluidized-bed hydrogenation reactor, or a suspended-bed hydrogenation reactor, with a fluidized-bed hydrogenation reactor being preferred.

[0047] In step i, the catalyst used for the hydrogenation treatment can be a commercially available catalyst, such as the FF, FH, and FZC series catalysts developed by the Dalian Research Institute of Petrochemical Technology, Sinopec. The catalyst gradation method can be determined according to conventional methods, and is not particularly limited in this invention.

[0048] In step ii, the atmospheric and vacuum distillation is carried out in an atmospheric and vacuum distillation kettle. Atmospheric distillation has no special requirements. The final temperature of vacuum distillation is 465–540°C, preferably 485–520°C.

[0049] Furthermore, in step (3), the stirring speed of the blending process is 700-900 r / min, the stirring time is 4-6 h, and the blending temperature is 140℃-165℃.

[0050] In step (3), the static heat preservation treatment needs to be carried out in oxygen-rich air (oxygen volume content of 40% to 55%), the temperature is maintained at 135℃ to 150℃, and the heat preservation time is 6 to 10 hours.

[0051] Compared with the prior art, the No. 90 Grade A asphalt and its preparation method of the present invention have the following advantages:

[0052] (1) This invention uses inferior asphalt residue as raw material, which is unsuitable for producing high-grade road asphalt, such as Tahe asphalt residue with high asphalt content, a very special form, and extremely poor comprehensive performance. This invention uses inferior asphalt residue in synergistic combination with polyphosphoric acid, initiator, and acid anhydride modifier to obtain anhydride-modified asphalt residue, which, when combined with pretreatment components, can be used to prepare qualified No. 90 Grade A asphalt, thus expanding the applications of inferior asphalt residue and increasing its added value.

[0053] (2) The pretreatment component of the present invention is obtained by hydrogenation treatment and secondary distillation of inferior slag, medium component and light component. The treatment process adjusts and optimizes the average molecular structure and molecular weight distribution of the material, and enhances the continuity of the material structure and composition. The inventors found that the pretreatment component can work synergistically with the anhydride slag to make up for the defects of inferior slag.

[0054] (3) The pretreatment components introduced in this invention are well compatible with the acid anhydride slag reduction. After blending, they can take into account the high and low temperature performance of asphalt. The colloidal structure can be optimized without mixing and distillation, thereby improving the anti-aging ability of asphalt. Furthermore, it has good low temperature elongation, eliminating the step of polymer mild modification and extension. The resulting high-grade road asphalt has the characteristics of high flash point and excellent high and low temperature performance. Detailed Implementation

[0055] The technical solution of the present invention is further described below through embodiments, but these embodiments cannot limit the scope of protection of the present invention, and the wt% involved refers to the mass fraction.

[0056] Example 1

[0057] (1) 100 parts of Tahe slag heated to a fluid state (some properties are shown in Table 1) were added to a high-pressure reactor at 120°C and stirred. 0.2 parts of polyphosphoric acid with a phosphoric acid content (calculated as H3PO4) of 135% were slowly added to the reactor (to be added within 3 min). The temperature was increased to 145°C at a stirring speed of 600 r / min and a speed program of 2°C / min. After the temperature was increased, the reaction was carried out in a N2 atmosphere. The pressure in the reactor was maintained at 0.5 MPa and the reaction time was 4 h. After the reaction was completed, the reactor was placed in a reactor for heat preservation at 120°C for 10 h.

[0058] (2) Add 0.1 parts of polyphosphoric acid with a phosphoric acid content (calculated as H3PO4) of 110% to the Tahe slag after the reaction in step (1). Stir at a stirring speed of 600 r / min for 30 min, then add 4 parts of maleic anhydride and 0.5 parts of dicumyl peroxide. Stir at a stirring speed of 650 r / min and heat to 175°C at a speed program of 2°C / min. After the heating is completed, the reaction is carried out in a N2 atmosphere. The pressure in the reactor is maintained at 0.6 MPa and the reaction time is 6 h to obtain the anhydride-treated slag.

[0059] (3) 100 parts of Tahe slag heated to a fluid state (same as step (1)), 30 parts of medium-quality components (some properties are shown in Table 2), and 10 parts of light-quality components (some properties are shown in Table 3) were reacted at a reaction temperature of 380℃, a reaction pressure of 16MPa, and a volume hourly space velocity of 0.8h. -1 Hydrogenation was carried out under a hydrogen-to-oil volume ratio of 900. The hydrogenation catalyst was the FZC series catalyst developed by the Dalian Petrochemical Research Institute of Sinopec. The hydrogenation product was distilled under atmospheric and vacuum conditions. The product distilled at a temperature greater than 510℃ was the required pretreatment component.

[0060] (4) 100 parts of the acid anhydride slag obtained in (2) are blended with 40 parts of the pretreatment components obtained in (3). The stirring speed during blending is 750 r / min, the temperature is 155℃, and the stirring time is 6 h. After the stirring is completed, the mixture is statically kept at 145℃ with an oxygen volume content of 50% for 8 h to obtain the final No. 90 Grade A asphalt A1.

[0061] Example 2

[0062] (1) 100 parts of Tahe slag heated to a fluid state (properties shown in Table 1) were added to a high-pressure reactor at 120°C and stirred. 0.25 parts of polyphosphoric acid with a phosphoric acid content (calculated as H3PO4) of 135% were slowly added to the reactor (to be added within 3 min). The temperature was increased to 145°C at a stirring speed of 600 r / min and a speed program of 2°C / min. After the temperature was increased, the reaction was carried out in a N2 atmosphere. The pressure in the reactor was maintained at 0.5 MPa and the reaction time was 6 h. After the reaction was completed, the reactor was placed in a reactor for heat preservation at 120°C for 16 h.

[0063] (2) Add 0.1 parts of polyphosphoric acid with a phosphoric acid content (calculated as H3PO4) of 110% to the Tahe slag after the reaction in step (1). Stir at a stirring speed of 600 r / min for 30 min, then add 4.75 parts of tung oil anhydride and 0.6 parts of dicumyl peroxide. Stir at a stirring speed of 650 r / min and heat up to 175°C at a speed program of 2°C / min. After the heating is completed, the reaction is carried out in a N2 atmosphere. The pressure in the reactor is maintained at 0.8 MPa and the reaction time is 6 h to obtain the anhydride-treated slag.

[0064] (3) 100 parts of Tahe slag heated to a fluid state (same as step (1)), 25 parts of medium-quality components (some properties are shown in Table 2), and 15 parts of light-quality components (some properties are shown in Table 3) were reacted at a reaction temperature of 380℃, a reaction pressure of 16MPa, and a volume hourly space velocity of 0.8h. -1 Hydrogenation was carried out under a hydrogen-to-oil volume ratio of 900. The hydrogenation catalyst was the FZC series catalyst developed by the Dalian Petrochemical Research Institute of Sinopec. The hydrogenation product was distilled under atmospheric and vacuum conditions. The distillation product at a temperature greater than 515℃ was the required pretreatment component.

[0065] (4) 100 parts of the acid anhydride slag obtained in (2) were blended with 45 parts of the pretreatment components obtained in (3). The stirring speed during blending was 750 r / min, the temperature was 155℃, and the stirring time was 6 h. After the stirring was completed, the mixture was statically kept at 145℃ with an oxygen volume content of 50% for 8 h to obtain the final No. 90 Grade A asphalt A2.

[0066] Example 3

[0067] (1) 100 parts of Tahe slag heated to a fluid state (properties shown in Table 1) were added to a high-pressure reactor at 120°C and stirred. 0.2 parts of polyphosphoric acid with a phosphoric acid content (calculated as H3PO4) of 135% were slowly added to the reactor (to be added within 3 min). The temperature was increased to 145°C at a stirring speed of 600 r / min and a speed program of 2°C / min. After the temperature was increased, the reaction was carried out in a N2 atmosphere. The pressure in the reactor was maintained at 0.5 MPa and the reaction time was 4 h. After the reaction was completed, the reactor was placed in a reactor for heat preservation at 120°C for 10 h.

[0068] (2) Add 0.2 parts of polyphosphoric acid with a phosphoric acid content (calculated as H3PO4) of 110% to the Tahe slag after the reaction in step (1). Stir at a stirring speed of 600 r / min for 30 min, then add 5 parts of maleic anhydride, 0.5 parts of dicumyl peroxide and 0.1 parts of azobisisobutyronitrile. Stir at a stirring speed of 650 r / min and heat to 180°C at a speed program of 2°C / min. After the heating is completed, the reaction is carried out in a N2 atmosphere. The pressure in the reactor is maintained at 0.6 MPa and the reaction time is 6 h to obtain the anhydride-treated slag.

[0069] (3) 100 parts of Tahe slag heated to a fluid state (same as step (1)), 35 parts of medium-quality components (some properties are shown in Table 2), and 8 parts of light-quality components (some properties are shown in Table 3) were reacted at a reaction temperature of 385℃, a reaction pressure of 15MPa, and a volume hourly space velocity of 1.0h. -1 Hydrogenation was carried out under a hydrogen-to-oil volume ratio of 1000. The hydrogenation catalyst was selected from the FH series catalyst developed by the Dalian Petrochemical Research Institute of Sinopec. The hydrogenation product was distilled under atmospheric and vacuum conditions. The distillation product at a temperature greater than 520℃ was the required pretreatment component.

[0070] (4) 100 parts of the acid anhydride slag obtained in (2) are blended with 50 parts of the pretreatment components obtained in (3). The stirring speed during blending is 750 r / min, the temperature is 155℃, and the stirring time is 6h. After the stirring is completed, the mixture is statically kept at 145℃ with an oxygen volume content of 50% for 8h to obtain the final No. 90 Grade A asphalt A3.

[0071] Example 4

[0072] (1) 100 parts of Tahe slag heated to a fluid state (properties shown in Table 1) were added to a high-pressure reactor at 125°C and stirred. 0.4 parts of polyphosphoric acid with a phosphoric acid content (calculated as H3PO4) of 140% were slowly added to the reactor (to be added within 5 min). The temperature was increased to 160°C at a stirring speed of 600 r / min and a speed program of 2°C / min. After the temperature was increased, the reaction was carried out in a N2 atmosphere. The pressure in the reactor was maintained at 0.5 MPa and the reaction time was 6 h. After the reaction was completed, the reactor was placed in a reactor for heat preservation at 120°C for 16 h.

[0073] (2) Add 0.3 parts of polyphosphoric acid with a phosphoric acid content (calculated as H3PO4) of 110% to the Tahe slag after the reaction in step (1). Stir at a stirring speed of 600 r / min for 30 min, then add 4.75 parts of maleic anhydride, 0.5 parts of dicumyl peroxide and 0.2 parts of benzoyl peroxide. Stir at a stirring speed of 700 r / min and heat to 175°C at a speed program of 2°C / min. After the heating is completed, the reaction is carried out in a N2 atmosphere. The pressure in the reactor is maintained at 0.6 MPa and the reaction time is 8 h to obtain the anhydride-treated slag.

[0074] (3) 100 parts of Tahe slag heated to a fluid state (same as step (1)), 40 parts of medium-quality components (some properties are shown in Table 2), and 15 parts of light-quality components (some properties are shown in Table 3) were reacted at a reaction temperature of 385℃, a reaction pressure of 15MPa, and a volume hourly space velocity of 1.0h. -1 Hydrogenation was carried out under a hydrogen-to-oil volume ratio of 1000. The hydrogenation catalyst was selected from the FH series catalyst developed by the Dalian Petrochemical Research Institute of Sinopec. The hydrogenation product was distilled under atmospheric and vacuum conditions. The distillation product at a temperature greater than 520℃ was the required pretreatment component.

[0075] (4) 100 parts of the anhydride slag obtained in (2) are blended with 40 parts of the pretreatment components obtained in (3). The stirring speed during blending is 800 r / min, the temperature is 160℃, and the stirring time is 6h. After the stirring is completed, the mixture is statically kept at 150℃ with an oxygen volume content of 45% for 7h to obtain the final No. 90 Grade A asphalt A4.

[0076] Comparative Example 1

[0077] (1) Prepare the acid anhydride slag according to Example 1.

[0078] (2) 100 parts of Tahe slag heated to a fluid state (same as step (1)), 40 parts of medium components (some properties are shown in Table 2), and 15 parts of light components are directly mixed to obtain a mixture.

[0079] (3) 100 parts of the acid anhydride slag in (1) are directly mixed with 40 parts of the mixture obtained in (2). The mixing speed is 800 r / min, the temperature is 160℃, and the mixing time is 6h. After the mixing is completed, the mixture is statically kept at 150℃ with an oxygen volume content of 45% for 7h to obtain the final asphalt B1.

[0080] Comparative Example 2

[0081] Same as Example 1, except that the slag is not pretreated with anhydride during the preparation process to obtain the final asphalt B2, specifically:

[0082] (1) 100 parts of Tahe slag heated to a fluid state (same as in Example 1), 30 parts of medium-weight components (some properties are shown in Table 2), and 10 parts of light-weight components (some properties are shown in Table 3) were reacted at a reaction temperature of 380°C, a reaction pressure of 16 MPa, and a volume hourly space velocity of 0.8 h⁻¹. -1 Hydrogenation was carried out under a hydrogen-to-oil volume ratio of 900. The hydrogenation catalyst was the FZC series catalyst developed by the Dalian Petrochemical Research Institute of Sinopec. The hydrogenation product was distilled under atmospheric and vacuum conditions. The product distilled at a temperature greater than 510℃ was the required pretreatment component.

[0083] (2) 100 parts of Tahe slag reduction (same as in Example 1) and 40 parts of the pretreatment components obtained in (1) were blended. The stirring speed during blending was 750 r / min, the temperature was 155℃, and the stirring time was 6 h. After the stirring was completed, the mixture was statically kept at 145℃ with an oxygen volume content of 50% for 8 h to obtain the final asphalt B2.

[0084] Comparative Example 3

[0085] Same as Example 1, except that polyphosphoric acid is not introduced during the slag reduction anhydride treatment, ultimately yielding B3. Specifically:

[0086] (1) Add 100 parts of Tahe slag heated to a fluid state (some properties are shown in Table 1), stir at a stirring speed of 600 r / min for 30 min, then add 4 parts of maleic anhydride and 0.5 parts of dicumyl peroxide, stir at a stirring speed of 650 r / min, and heat to 175 °C at a speed program of 2 °C / min. After the heating is completed, the reaction is carried out in a N2 atmosphere, the pressure in the reactor is maintained at 0.6 MPa, and the reaction time is 6 h to obtain anhydride-treated slag.

[0087] (2) 100 parts of Tahe slag heated to a fluid state (same as step (1)), 30 parts of medium-quality components (some properties are shown in Table 2), and 10 parts of light-quality components (some properties are shown in Table 3) were reacted at a reaction temperature of 380℃, a reaction pressure of 16MPa, and a volume hourly space velocity of 0.8h. -1Hydrogenation was carried out under a hydrogen-to-oil volume ratio of 900. The hydrogenation catalyst was the FZC series catalyst developed by the Dalian Petrochemical Research Institute of Sinopec. The hydrogenation product was distilled under atmospheric and vacuum conditions. The product distilled at a temperature greater than 510℃ was the required pretreatment component.

[0088] (3) 100 parts of the acid anhydride slag obtained in (1) are blended with 40 parts of the pretreatment components obtained in (2). The stirring speed during blending is 750 r / min, the temperature is 155℃, and the stirring time is 6 h. After the stirring is completed, the mixture is statically kept at 145℃ with an oxygen volume content of 50% for 8 h to obtain the final asphalt B3.

[0089] Comparative Example 4

[0090] Same as Example 1, except that no pretreatment components are introduced during the preparation process, ultimately yielding B4. Specifically:

[0091] (1) 100 parts of Tahe slag heated to a fluid state (some properties are shown in Table 1) were added to a high-pressure reactor at 120°C and stirred. 0.2 parts of polyphosphoric acid with a phosphoric acid content (calculated as H3PO4) of 135% were slowly added to the reactor (to be added within 3 min). The temperature was increased to 145°C at a stirring speed of 600 r / min and a speed program of 2°C / min. After the temperature was increased, the reaction was carried out in a N2 atmosphere. The pressure in the reactor was maintained at 0.5 MPa and the reaction time was 4 h. After the reaction was completed, the reactor was placed in a reactor for heat preservation at 120°C for 10 h.

[0092] (2) Add 0.1 parts of polyphosphoric acid with a phosphoric acid content (calculated as H3PO4) of 110% to the Tahe slag after the reaction in step (1). Stir at a stirring speed of 600 r / min for 30 min, then add 4 parts of maleic anhydride and 0.5 parts of dicumyl peroxide. Stir at a stirring speed of 650 r / min and heat to 175°C at a speed program of 2°C / min. After the heating is completed, the reaction is carried out in a N2 atmosphere. The pressure in the reactor is maintained at 0.6 MPa and the reaction time is 6 h to obtain the anhydride-treated slag.

[0093] (3) 100 parts of the anhydride slag obtained in (2) were blended. The stirring speed was 750 r / min, the temperature was 155℃, and the stirring time was 6 h. After the stirring was completed, the mixture was statically kept at 145℃ with an oxygen volume content of 50% for 8 h to obtain the final asphalt B4.

[0094] Test case

[0095] Key index tests were conducted on the Tarim Basin reduced slag, medium component, light component, and 90A asphalt obtained from the examples and comparative examples (in accordance with the Test Procedure for Asphalt and Asphalt Mixtures in Highway Engineering JTG E20-2011). All indicators of qualified 90A asphalt products must meet the relevant requirements of the Technical Requirements for Road Petroleum Asphalt JTG F40-2004.

[0096] Table 1. Properties of the Tarim Basin Slag Reduction Section Used in Examples and Comparative Examples

[0097]

[0098]

[0099] Table 2. Partial properties of the medium-sized components used in the examples and comparative examples.

[0100] Saturated fraction / wt% 32.37 Aromatic components / wt% 56.15 Gel / wt% 11.41 Asphalt / wt% 0.07 <![CDATA[100℃ kinematic viscosity / mm 2 / s]]> 53 Flash point / °C 213 weight average molecular weight 2135 Molecular weight distribution width 2.2

[0101] Table 3. Partial Properties of Lightweight Components Used in Examples and Comparative Examples

[0102]

[0103]

[0104] Table 4. Main properties of the examples and comparative examples

[0105]

[0106] The scope of protection of this invention is not limited to the above embodiments, but is defined by the claims. Those skilled in the art can make appropriate modifications to these embodiments without departing from the technical concept and spirit of this invention, and these modified embodiments are also included within the scope of protection of this invention.

Claims

1. A type of Grade A 90 asphalt, comprising the following raw material components by weight: acid anhydride slag reduction: 100 parts; pretreatment components: 20-80 parts; The acid anhydride slag reduction process, by weight, includes the following raw material components: Inferior slag reduction: 100 portions; Anhydride modifier: 2-10 parts; Polyphosphoric acid: 0.1~2 parts; Initiator: 0.08~0.7 parts; In the anhydride-based slag reduction process, the polyphosphoric acid includes polyphosphoric acid with low phosphoric acid content and polyphosphoric acid with high phosphoric acid content; the low phosphoric acid content polyphosphoric acid refers to polyphosphoric acid containing 105%~125% phosphoric acid by mass (H3PO4), and the high phosphoric acid content polyphosphoric acid refers to polyphosphoric acid containing 130%~145% phosphoric acid by mass (H3PO4); the low phosphoric acid content polyphosphoric acid accounts for 20%~50% of the total mass of polyphosphoric acid, and the high phosphoric acid content polyphosphoric acid accounts for 50%~80% of the total mass of polyphosphoric acid; The pretreatment components, by weight, include the following raw material components: Inferior slag reduction: 100 portions; Medium-quality components: 20-50 parts; Light components: 5-20 parts; The inferior reduced-pressure residue has the following properties: flash point of 241~256℃, sulfur content of 2.61wt%~3.65wt%, and by mass fraction, saturated fraction of 26.1%~37.7%, aromatic fraction of 20.2%~34.5%, resin of 18.3%~24.8%, asphaltenes of 21.3%~30.1%, carbon residue of 21wt%~29wt%, nitrogen content of 0.14wt%~0.61wt%, total nickel and vanadium content of 320~365μg / g, and condensation index CI of 0.26~0.35; the inferior reduced-pressure residue is a fraction with an initial boiling point greater than 425℃. The intermediate component refers to the resin obtained after solvent deasphalting, and the intermediate component has the following properties: kinematic viscosity of 50 mmHg at 100°C. 2 / s~65mm 2 / s, flash point is 206℃~220℃, by mass fraction, saturated fraction accounts for 30%~42%, aromatic fraction accounts for 48%~57%, resin accounts for 8%~13%, asphaltene content is less than 2%; weight average molecular weight is 1990~2140, molecular weight distribution width is 1.6~3.7; The light component refers to vacuum-pressed wax oil, which has the following properties: kinematic viscosity at 50°C is 10 mmHg. 2 / s~16mm 2 / s, density at 20℃ is 760~900 kg / m³ 3 By mass fraction, the saturated fraction accounts for 60%~78%, the aromatic fraction accounts for 20%~32%, the total content of resins and asphaltenes is less than 6%; the residual carbon is less than 0.15%, the sulfur content is less than 0.3%, the nitrogen content is less than 1%, and the hydrogen-to-carbon ratio is 1.5~1.

8. The preparation process of the pretreatment components is as follows: i. After heating the inferior slag to a fluid state, mix it with the medium and light components, and then perform hydrogenation treatment together with hydrogen. ii. The material obtained in step i is subjected to atmospheric and vacuum distillation to obtain the final pretreated component; In step i, the operating conditions for the hydrogenation treatment are: reaction temperature of 365℃~390℃, reaction pressure of 12MPa~22MPa, and volume hourly space velocity of 0.5~1.8h. -1 The hydrogen-to-oil volume ratio is 400-1500.

2. The No. 90 Grade A asphalt according to claim 1, characterized in that, The No. 90 Grade A asphalt, by weight, comprises the following raw material components: acid anhydride slag reduction: 100 parts; pretreatment components: 40-60 parts.

3. The No. 90 Grade A asphalt according to claim 1 or 2, characterized in that, The anhydride slag reduction process comprises, by weight, the following raw material components: Inferior slag reduction: 100 portions; Anhydride modifier: 2-8 parts; Polyphosphoric acid: 0.2~1.8 parts; Initiator: 0.15~0.7 parts.

4. The No. 90 Grade A asphalt according to claim 1, characterized in that, The pretreatment components, by weight, include the following raw material components: Inferior slag reduction: 100 portions; Medium-quality components: 25-40 parts; Light components: 6-15 parts.

5. The No. 90 Grade A asphalt according to claim 1, characterized in that, In the anhydride-based slag reduction process, the anhydride modifier is one or more of the following: maleic anhydride, polyisobutylene succinic anhydride, methyl nadic anhydride, modified methyl nadic anhydride, dodecenyl succinic anhydride, tung oil anhydride, polyazelite anhydride, polyglutaric anhydride, polyoxoanhydride, or hydrolyzed polymaleic anhydride.

6. The No. 90 Grade A asphalt according to claim 1, characterized in that, In the acid anhydride slag reduction process, the initiator is one or more of dicumyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, sodium metabisulfite, azobisisobutyronitrile, azobisisoheptanenitrile, and cumyl hydroperoxide.

7. A method for preparing Grade A 90 bitumen according to any one of claims 1-6, characterized in that, Includes the following steps: (1) Preparation of acid anhydride-based slag reduction; (2) Preparation of pretreatment components; (3) The materials obtained in step (1) and step (2) are mixed and subjected to static heat preservation treatment to finally obtain No. 90 Grade A asphalt; In step (2), the process for preparing the pretreatment components is as follows: i. After heating the inferior slag to a fluid state, mix it with the medium and light components, and then perform hydrogenation treatment together with hydrogen. ii. The material obtained in step i is subjected to atmospheric and vacuum distillation to obtain the final pretreated component; In step i, the operating conditions for the hydrogenation treatment are: reaction temperature of 365℃~390℃, reaction pressure of 12MPa~22MPa, and volume hourly space velocity of 0.5~1.8h. -1 The hydrogen-to-oil volume ratio is 400-1500.

8. The method according to claim 7, characterized in that, In step (1), the process of preparing the anhydride-based slag is as follows: a. Add the inferior slag and high-phosphoric acid content polyphosphoric acid, heated to a fluid state, to the reactor, heat to the reaction temperature and stir continuously, and carry out the reaction under a protective gas. After the reaction is completed, keep it at a constant temperature. b. Add low-phosphoric acid content polyphosphoric acid to the material obtained in step a, stir evenly, then add anhydride modifier and initiator, continue stirring and heat to the reaction temperature, and carry out the reaction under protective gas. After the reaction is completed, anhydride-modified slag is obtained.

9. The method according to claim 8, characterized in that, In step a, the heating to the reaction temperature is performed by programmed heating at a rate of 1-3°C / min, the reaction temperature is 140°C-180°C, the reaction time is 3-6 hours, and the stirring speed is 600-800 r / min.

10. The method according to claim 8, characterized in that, In step b, the stirring speed after adding the anhydride modifier and initiator is 600~800 r / min; the heating to the reaction temperature is performed using programmed temperature rise at a rate of 1~3℃ / min; the reaction temperature is 160℃~180℃, and the reaction time is 6~8h; the protective gas is an inert gas and / or N2; the amount of protective gas is such that the pressure inside the reactor is maintained at 0.3~0.9MPa.

11. The method according to claim 7, characterized in that, In step (3), the stirring speed during the blending process is 700~900 r / min, the stirring time is 4~6 h, and the blending temperature is 140℃~165℃.

12. The method according to claim 7, characterized in that, In step (3), the static heat preservation treatment needs to be carried out in oxygen-rich air, maintaining the temperature at 135℃~150℃, and the heat preservation time is 6~10h.

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