An oil-based impregnated asphalt and its preparation method and application

Abstract

The application discloses oil-based impregnated asphalt and a preparation method and application thereof. The oil-based impregnated asphalt comprises the following components in parts by weight: pretreated aromatic hydrocarbon extract oil: 100 parts, pre-modified accelerant: 20-50 parts, and composite treatment agent: 20-60 parts. The impregnated asphalt can meet the index requirement of the No. 3 product of the Chinese coking impregnated asphalt standard GB / T 35074-2018.

Description

Technical Field

[0001] This invention belongs to the field of special asphalt processing and production, specifically relating to an oil-based impregnated asphalt, its preparation method, and its application. Background Technology

[0002] Impregnating bitumen is a common densifying and reinforcing agent in carbon material production, mainly used in the impregnation process of high-power and ultra-high-power graphite electrodes and high-tech carbon products, such as special graphite for aerospace and military applications. Carbon materials are porous materials, and carbon products contain more or less porosity, generally accounting for about 1 / 4 of the volume of the carbon product itself. The presence of pores leads to a decrease in the mechanical strength of carbon products, an increase in resistivity, and impaired thermal conductivity. Under high-temperature conditions, the oxidation rate is accelerated, corrosion resistance is drastically reduced, and it is easier for the material to be penetrated. In order to reduce porosity and improve the performance of carbon products, impregnation densification treatment is required for calcined products during the production process.

[0003] The main production methods of impregnating bitumen include: (1) Coal tar filtration method (Western Europe): Impregnating bitumen is produced directly in coal tar processing equipment. This method is simple and energy-efficient, but it has strict requirements for filter screens and demanding process conditions. (2) Coal tar solvent extraction method: The Polish National Coal Chemical Research Institute uses the coal tar solvent extraction method to prepare impregnating bitumen. This method has a good purification effect, but the amount of solvent used is large and the process energy consumption is high. (3) Thermal polymerization method: According to different raw material routes, it can also be divided into: thermal polymerization method with anthracene oil as the raw material, Cherry-T method, and soft bitumen flash polymerization method. Among them, the Cherry-T method is a relatively representative thermal polymerization method. During the tar distillation process, bitumen and heavy oil fractions are directly polymerized and modified to produce impregnating bitumen. The yield of impregnating bitumen produced by thermal polymerization method is low, the polymerization temperature is difficult to control, the polymerization effect is not good if the temperature is too low, and secondary quinoline insolubles are easily generated if the temperature is too high.

[0004] Currently, China has not widely adopted impregnating bitumen specifically for carbon materials, especially for high-power and ultra-high-power electrodes, which are still in the research and development stage. Chinese graphite electrode manufacturers generally use medium-temperature bitumen as impregnating bitumen (with a quinoline insoluble content (QI) of around 5%), reducing its viscosity and softening point by adding anthracene oil and light oil. For example, Jilin Carbon Plant used a mixture of diluted medium-temperature bitumen from Anshan Iron and Steel and Benxi Iron and Steel as impregnating bitumen, while Hefei Carbon Plant used medium-temperature coal tar pitch with a small amount of coal tar to lower the softening point. However, as Chinese graphite electrodes develop towards larger sizes and ultra-high power, graphite electrode manufacturers are placing higher demands on the quality indicators of impregnating bitumen, such as requiring a quinoline insoluble content (QI) of below 5%.

[0005] CN101289625A discloses a production process for impregnating asphalt. A mixed solvent is prepared by selecting an aliphatic hydrocarbon solvent and an aromatic hydrocarbon solvent; medium-temperature coal tar pitch or soft coal tar pitch is mixed with the mixed solvent in a certain proportion and fed into at least a three-stage mixer. After thorough mixing, the mixture is fed into an extraction tower for separation; in the extraction tower, the light phase asphalt with low quinoline insoluble content and the heavy phase asphalt are extracted and separated; the light phase asphalt is stripped in a stripping tower to obtain the impregnating asphalt. Because it requires the use of a mixed solvent and secondary distillation of the light phase (containing the solvent), the process is complex and energy-intensive.

[0006] CN112779042A discloses a method for producing high-quality impregnated bitumen. Tar is heated to a certain temperature through a two-stage heat exchanger to achieve lower viscosity and better fluidity, reducing its density. It is then separated using a disc centrifuge with a high separation factor. The centrifuge periodically discharges slag, and the intervals for slag discharge are set to ensure good fluidity of the slag phase and prevent clogging of the discs and slag chamber. The centrifuged and purified tar is then distilled with appropriately controlled parameters to meet the requirements for softening point, toluene-insoluble matter, quinoline-insoluble matter, coking value, and ash content of high-quality impregnated bitumen. This method for preparing impregnated bitumen is complex and uses coal tar as the main raw material, which is detrimental to the environment and human health.

[0007] In summary, developing a high-quality impregnated bitumen to meet China's application needs for high-end carbon material products, replace imported products, and solve the problems of high raw material prices and unreliable supply for special carbon materials has significant social and economic implications. Summary of the Invention

[0008] To address the shortcomings of existing technologies, the present invention aims to provide an oil-based impregnated bitumen, its preparation method, and its application. The impregnated bitumen of this invention meets the requirements for product No. 3 in the Chinese standard for coking impregnated bitumen, GB / T 35074-2018 Coking Impregnating Agent Bitumen.

[0009] The first aspect of this invention provides an oil-based impregnated bitumen, comprising, by weight, the following components:

[0010] Pretreated aromatic extract oil: 100 parts;

[0011] Pre-modified accelerator: 20-50 parts, preferably 30-50 parts;

[0012] Composite treatment agent: 20-60 parts, preferably 20-45 parts.

[0013] The pretreated aromatic extract oil is the fraction obtained by distilling aromatic extract oil and then cutting it at a temperature greater than 300°C.

[0014] The aromatic extract oil is at least one of the following: reduced third-line distillate oil, reduced fourth-line distillate oil, and reduced fifth-line distillate oil, preferably at least one of the following: reduced fourth-line furfural refined extract oil or reduced fifth-line furfural refined extract oil.

[0015] The main properties of the aromatic extracted oil include: saturated components of 27wt%–30wt%, aromatic components of 52wt%–60wt%, resins of 13wt%–19wt%, and asphaltenes of 0wt%–0.5wt%. The four-component analysis method is T0618-1993 Asphalt Chemical Component Test (Four-component Method); H ar 15wt%–17wt%, H α 25wt%–28wt%, H β accounting for 43wt%~46t%, H γ It accounts for 14wt% to 16wt%, with a C / H molar ratio of 0.82 to 0.88, an aromatic carbon fraction of 48wt% to 51wt%, a cycloalkanes carbon fraction of 15wt% to 18wt%, and an alkyl carbon fraction of 35wt% to 37wt%.

[0016] The pre-modified accelerator comprises the following components by weight:

[0017] Aromatic hydrocarbon extract oil fraction: 100 parts;

[0018] Biochar powder: 2-10 parts, preferably 4-8 parts;

[0019] Initiator: 0.1 to 0.6 parts, preferably 0.2 to 0.5 parts.

[0020] The aromatic extract oil fraction is the fraction of aromatic extract oil between 280 and 320°C, preferably the fraction between 280 and 300°C.

[0021] The aromatic extract oil is at least one of the following: reduced third-line distillate oil, reduced fourth-line distillate oil, and reduced fifth-line distillate oil, preferably at least one of the following: reduced fourth-line furfural refined extract oil or reduced fifth-line furfural refined extract oil.

[0022] The main properties of the aromatic extracted oil include: saturated components of 27wt%–30wt%, aromatic components of 52wt%–60wt%, resins of 13wt%–19wt%, and asphaltenes of 0wt%–0.5wt%. The four-component analysis method is T0618-1993 Asphalt Chemical Component Test (Four-component Method); H ar 15wt%–17wt%, H α 25wt%–28wt%, H β accounting for 43wt%~46t%, H γIt comprises 14wt%–16wt%, with a C / H molar ratio of 0.82–0.88, an aromatic carbon fraction of 48wt%–51wt%, a cycloalkane carbon fraction of 15wt%–18wt%, and an alkyl carbon fraction of 35wt%–37wt%.

[0023] The biochar powder is prepared from plant medicinal residues.

[0024] Specifically, the biochar powder is prepared from traditional Chinese medicine residues through dehydration and drying, primary pulverization, anaerobic carbonization, secondary pulverization, and sieving.

[0025] The source of the herbal medicine residue is not particularly limited. Preferably, the herbal medicine residue, based on the dehydrated and dried dry matter, has a crude fiber content of 15% to 25% of the total mass. The herbal medicine residue, based on the dehydrated and dried dry matter, has an acid detergent fiber content of 30% to 50% of the total mass and a neutral detergent fiber content of 45% to 60% of the total mass. The herbal medicine residue, based on the dehydrated and dried dry matter, has a crude ash content of 5% to 10% of the total mass.

[0026] The biochar powder has an average particle size of 120–180 mesh, preferably 140–180 mesh. The biochar powder has a moisture content of no more than 0.5 wt% and a pore volume of no less than 0.8 cm³. 3 / g, specific surface area is 2500~3500cm² 2 / g.

[0027] The initiator is one or more of dicumyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, sodium metabisulfite, azobisisobutyronitrile, azobisisoheptanenitrile, and cumyl hydroperoxide.

[0028] The composite treatment agent comprises the following components by weight:

[0029] Medium-quality components: 100 parts;

[0030] Lightweight component: 15-30 parts, preferably 15-25 parts.

[0031] The intermediate component refers to the resin obtained after solvent deasphalting. 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.

[0032] The light component refers to vacuum-pressed wax oil. The light component has the following properties: kinematic viscosity at 50°C is 10 mmHg. 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%–35%, and the total content of resins and asphaltenes is less than 6%; the residual carbon is less than 0.15 wt%, the sulfur content is less than 0.3 wt%, the nitrogen content is less than 1 wt%, and the hydrogen-carbon molar ratio is 1.5–1.8.

[0033] A second aspect of the present invention provides a method for preparing the above-mentioned oil-based impregnated bitumen, comprising:

[0034] (1) Preparation of pre-modified accelerator;

[0035] (2) The pretreated aromatic extract oil and the pre-modified accelerator are blended, oxidized and condensed to obtain a carbon-rich component;

[0036] (3) Preparation of composite treatment agent;

[0037] (4) The composite treatment agent obtained in step (3) is mixed with the carbon-rich component obtained in step (2) and subjected to vacuum distillation to obtain the impregnated asphalt.

[0038] In step (1), the method for preparing the pre-modified accelerator includes:

[0039] i. Preparation of biochar powder;

[0040] ii. Mix the aromatic extract oil fraction with biochar powder and shear to obtain a mixture of aromatic extract oil fraction and biochar powder;

[0041] iii. Add the initiator to the mixture obtained in ii, continue shearing, and let it stand after shearing to obtain the pre-modified accelerator.

[0042] The preparation process of biochar powder in step i includes:

[0043] a. Dehydrate, dry, and pulverize the residue of Chinese medicinal herbs in one step;

[0044] b. Perform anaerobic carbonization on the residue after step a.

[0045] c. Cool the residue after carbonization in step b, pulverize it again, and sieve it to obtain biochar powder.

[0046] Step a can be carried out in a dehydration and drying machine for medicinal residues. The primary pulverization involves pulverizing the medicinal residues to 50-80 mesh. The dehydration and drying conditions are not particularly limited, but generally the moisture content of the medicinal residues after step a should not exceed 15%.

[0047] In step b, the anaerobic carbonization is carried out in a continuous slag carbonization furnace. The temperature of the anaerobic carbonization is 500–750℃, the heating rate is 8–15℃ / min, the carbonization time is 50–90min, and the carbonization process is carried out in an atmosphere of N2 and / or inert gas.

[0048] In step c, cooling simply means cooling to room temperature. After secondary crushing and sieving, the resulting biochar powder has a particle size of 140–180 mesh.

[0049] In step c, the cooling, secondary crushing, and sieving must be carried out in a dry environment to ensure that the moisture content of the obtained biochar powder does not exceed 0.5 wt%.

[0050] In step ii, the shearing conditions are: shearing at 180-200℃ for 30-60 minutes, with a shearing rate of 2500-4000 r / min.

[0051] In step iii, the shearing conditions are: shearing at 200-240℃ for 5-15 minutes, with a shearing rate of 2500-4000 r / min.

[0052] In step iii, the conditions for settling are: settling at 120-150°C for 2-6 hours, and the settling process is carried out in an N2 atmosphere.

[0053] In step (2), the pretreatment process of the pretreated aromatic extract oil is distillation, wherein the pretreated aromatic extract oil is the fraction of the aromatic extract oil that is distilled and then cut off at a temperature greater than 300°C.

[0054] In step (2), the pretreated aromatic extract oil and pre-modified accelerator are blended at 180℃~200℃. The stirring speed during the blending process is 700~900r / min, and the time is 4~6h. After blending, oxidation and condensation are carried out in a reactor. The oxidation process temperature is 270℃~320℃, and the gas flow rate is 0.05~0.15m³ / h. 3 The oxidation time is 60–120 min, and the gas is oxygen-enriched air with an oxygen volume content of 60%–75%. The condensation process temperature is 360℃–400℃, and the inert gas flow rate is 0.10–0.25 m³ / h. 3 / (kg·h), condensation time is 240-300 min, and the inert gas is preferably N2.

[0055] In step (3), the process for preparing the composite treatment agent is as follows:

[0056] I. After mixing the medium and light components heated to a fluid state, hydrogen is added for hydrogenation treatment.

[0057] II. The material obtained in step I is subjected to atmospheric and vacuum distillation to obtain the composite treatment agent.

[0058] 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.

[0059] In step I, the reactor used for the hydrogenation treatment can be at least one of a fixed-bed hydrogenation reactor, a fluidized-bed hydrogenation reactor, or a suspended-bed hydrogenation reactor, with a fluidized-bed hydrogenation reactor being preferred.

[0060] In step I, the catalyst used for the hydrogenation treatment can be a commercially available catalyst, such as one or more of 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.

[0061] 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.

[0062] In step (4), the final temperature of the vacuum distillation is 520-580℃, preferably 520-560℃.

[0063] A third aspect of the present invention provides the application of the above-mentioned oil-based impregnated pitch in a graphite electrode.

[0064] Compared with the prior art, the present invention has the following characteristics:

[0065] (1) This invention uses pretreated aromatic extract oil and pre-modified accelerator as raw materials. By controlling the process conditions of distillation, blending, oxidation and condensation, carbon-rich components can be obtained, which lays the foundation for the next step of blending and preparing impregnated asphalt with moderate softening point and qualified other indicators. Moreover, the preparation of carbon-rich components adopts traditional process, which does not require high pressure or ultra-high pressure environment and is easy to realize.

[0066] (2) The composite treatment agent introduced in this invention is obtained by hydrogenation and secondary distillation of medium and light components with special properties. The treatment process adjusts and optimizes the composition and structure of the material so that the material can simultaneously meet the mutual constraints of low softening point and high coking value. The composite treatment agent and carbon-rich components can be compounded and fractionated again to obtain impregnated asphalt that meets the index requirements.

[0067] (3) The pre-modified accelerator used in this invention is prepared by modifying specially made biochar. It can promote the polymerization between CC without increasing quinoline insolubles, thereby increasing the coking value and toluene insoluble content of asphalt, and meeting the requirements of impregnated asphalt for low softening point and high coking value. The biochar used is prepared from Chinese medicine residues. The raw materials are widely available and inexpensive, which has a certain cost advantage. Furthermore, converting Chinese medicine residues into pre-modified accelerators avoids the environmental pollution caused by direct combustion and meets the requirements of low carbon and environmental protection.

[0068] (4) The present invention uses petroleum-based and bio-based raw materials to prepare impregnated bitumen. Compared with traditional coal-based raw materials, the average molecular weight of each component of petroleum-based and bio-based raw materials is small, the microporous impregnation effect is better, the thermochemical reactivity is high, the content of native quinoline insoluble matter is low, the amount of harmful impurities is low, the harm to the environment and human body is small, and the economic value and environmental protection effect are higher. Detailed Implementation

[0069] 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.

[0070] In this invention, the contents of crude fiber, acid detergent fiber, and neutral detergent fiber in the biochar powder were determined according to the methods of GB / T 6434-2006, NY / T 1459-2007, and GB / T 20806-2006, respectively, using an FT12 fully automatic fiber analyzer. The crude ash content was determined according to the method described in *Zhang LY. Technologies of Feed Analysis and Feed Quality Detection, 2nd Ed. Beijing: Chinese Agricultural University Press, 2003.*

[0071] This invention uses a Bruker Avance II 400 nuclear magnetic resonance spectrometer (Germany) to analyze the H and C content at different locations. Specifically, H... ar H represents hydrogen directly bonded to an aromatic carbon. α H represents the hydrogen atom bonded to the α-carbon of the aromatic ring. β H represents the hydrogen on the β-carbon of the aromatic ring and the hydrogen on the CH2 or CH groups attached to the β-carbon.γ This represents the hydrogen on the γ-carbon of the aromatic ring and the hydrogen on the CH3 group attached to the γ-carbon. 1 H-NMR can directly provide information on the distribution of hydrogen or carbon atoms at different positions by measuring differences in chemical shift values.

[0072] Example 1

[0073] (1) i. The Chinese herbal medicine residue (containing 19.74% crude fiber, 32.68% acid detergent fiber, 55.44% neutral detergent fiber, and 7.52% crude ash) was dehydrated, dried, and pulverized once using a herbal medicine residue dehydration dryer to obtain a Chinese herbal medicine residue with a particle size of 50-80 mesh and a moisture content of 12.6%. The pre-treated residue was then subjected to anaerobic carbonization in a continuous herbal medicine residue carbonization furnace at a carbonization temperature of 550℃, a heating rate of 12℃ / min, and a carbonization time of 60min, all within an N2 atmosphere. The carbonized residue was then cooled and pulverized to obtain biochar powder with a particle size of 140-180 mesh to be modified. Cooling, secondary pulverization, and sieving were carried out in a dry environment, resulting in biochar powder with a moisture content of 0.3% and a pore volume of 0.82 cm³. 3 / g, specific surface area is 2506.41cm² 2 / g.

[0074] ii. The aromatic extract oil (main properties are shown in Table 1) is first pretreated by distillation to obtain an aromatic extract oil fraction. 100 parts of the aromatic extract oil fraction (the fraction between 280 and 300°C in the aromatic extract oil) are mixed with 6 parts of biochar powder and sheared at 180°C for 400 min at a shear rate of 4000 r / min to obtain a mixture of aromatic extract oil fraction and biochar powder.

[0075] iii. Add 0.3 parts of benzoyl peroxide to the mixture obtained in ii, and continue shearing at 200°C for 15 min. After shearing, let it stand at 130°C for 4 h. The standing process is carried out under N2 atmosphere. After standing, the pre-modified accelerator is obtained.

[0076] (2) The aromatic extract oil (main properties are shown in Table 1) is first pretreated by distillation. Then, 100 parts of the pretreated aromatic extract oil (fraction above 300℃) and 35 parts of the pre-modified accelerator are blended at 185℃ and 800 r / min for 5 h to ensure uniform mixing. The mixture is then oxidized in a reactor at a temperature of 280℃ and an oxygen-enriched air flow rate of 0.10 m³ / min. 3 / / (kg·h), oxidation time is 90 min, oxygen volume content in oxygen-enriched air is 70%; after oxidation, condensation reaction is carried out at a temperature of 370℃ and a nitrogen flow rate of 0.20 m³ / h. 3 / / (kg.h), the condensation time is 260min, and the desired carbon-rich component is obtained after the reaction is completed.

[0077] (3) 100 parts of the medium component (main properties shown in Table 2) heated to a fluid state and 20 parts of the light component (main properties 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 selected was FZC-301 catalyst developed by the Dalian Petrochemical Research Institute of Sinopec. The hydrogenation product was distilled under atmospheric and vacuum conditions, and the product distilled at a temperature greater than 510℃ was the desired composite treatment agent.

[0078] (4) Mix the carbon-rich component obtained in step (2) with 35 parts of the composite treatment agent obtained in step (3) and perform vacuum distillation to obtain a fraction with a temperature greater than 530°C, which is the impregnated asphalt A1.

[0079] Example 2

[0080] (1) i. The Chinese herbal medicine residue (containing 19.74% crude fiber, 32.68% acid detergent fiber, 55.44% neutral detergent fiber, and 7.52% crude ash) was dehydrated, dried, and pulverized once using a herbal medicine residue dehydration dryer to obtain a Chinese herbal medicine residue with a particle size of 50-80 mesh and a moisture content of 12.6%. The pre-treated residue was then subjected to anaerobic carbonization in a continuous herbal medicine residue carbonization furnace at a carbonization temperature of 600℃, a heating rate of 15℃ / min, and a carbonization time of 70min, all within an N2 atmosphere. The carbonized residue was then cooled and pulverized to obtain biochar powder with a particle size of 140-180 mesh to be modified. Cooling, secondary pulverization, and sieving were carried out in a dry environment, resulting in biochar powder with a moisture content of 0.25% and a pore volume of 0.86 cm³. 3 / g, with a specific surface area of ​​2551.26cm². 2 / g.

[0081] ii. The aromatic extract oil (main properties are shown in Table 1) is first pretreated by distillation to obtain an aromatic extract oil fraction. 100 parts of the aromatic extract oil fraction (the fraction between 280 and 300°C in the aromatic extract oil) are mixed with 6 parts of biochar powder and sheared at 180°C for 400 min at a shear rate of 4000 r / min to obtain a mixture of aromatic extract oil fraction and biochar powder.

[0082] iii. Add 0.15 parts of benzoyl peroxide and 0.15 parts of azobisisobutyronitrile to the mixture obtained in ii, and continue shearing at 200°C for 15 min. After shearing, let it stand at 130°C for 4 h. The standing process is carried out under N2 atmosphere. After standing, the pre-modified accelerator is obtained.

[0083] (2) The aromatic extract oil (main properties are shown in Table 1) was first pretreated by distillation. Then, 100 parts of the pretreated aromatic extract oil (fraction above 300℃) and 40 parts of the pre-modified accelerator were blended at 185℃ and 800 r / min for 5 h to ensure uniform mixing. The mixture was first oxidized in a reactor at a temperature of 270℃ and an oxygen-enriched air flow rate of 0.12 m³ / min. 3 / / (kg·h), oxidation time is 100 min, oxygen volume content in oxygen-enriched air is 70%; after oxidation, condensation reaction is carried out at a temperature of 380℃ and a nitrogen flow rate of 0.20 m³ / h. 3 / / (kg.h), the condensation time is 270 min, and the desired carbon-rich component is obtained after the reaction is completed.

[0084] (3) 100 parts of the medium component (main properties shown in Table 2) heated to a fluid state and 20 parts of the light component (main properties 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 selected was FZC-301 catalyst developed by the Dalian Petrochemical Research Institute of Sinopec. The hydrogenation product was distilled under atmospheric and vacuum conditions, and the product distilled at a temperature greater than 510℃ was the desired composite treatment agent.

[0085] (4) Mix the carbon-rich component obtained in step (2) with 30 parts of the composite treatment agent obtained in step (3) and perform vacuum distillation to obtain a fraction with a temperature greater than 532°C, which is impregnated asphalt A2.

[0086] Example 3

[0087] (1) i. The Chinese herbal medicine residue (containing 17.35% crude fiber, 33.57% acid detergent fiber, 52.61% neutral detergent fiber, and 8.44% crude ash) was dehydrated, dried, and pulverized once using a herbal medicine residue dehydration dryer to obtain a Chinese herbal medicine residue with a particle size of 50-80 mesh and a moisture content of 13.1%. The pre-treated residue was then subjected to anaerobic carbonization in a continuous herbal medicine residue carbonization furnace at a carbonization temperature of 650℃, a heating rate of 15℃ / min, and a carbonization time of 65min, all within an N2 atmosphere. The carbonized residue was then cooled and pulverized to obtain biochar powder with a particle size of 140-180 mesh to be modified. Cooling, secondary pulverization, and sieving were carried out in a dry environment, resulting in biochar powder with a moisture content of 0.26% and a pore volume of 0.93 cm³. 3 / g, with a specific surface area of ​​2577.42cm². 2 / g.

[0088] ii. The aromatic extract oil (main properties are shown in Table 1) is first pretreated by distillation to obtain an aromatic extract oil fraction. 100 parts of the aromatic extract oil fraction (the fraction between 280 and 300°C in the aromatic extract oil) are mixed with 5 parts of biochar powder and sheared at 180°C for 400 min at a shear rate of 4000 r / min to obtain a mixture of aromatic extract oil fraction and biochar powder.

[0089] iii. Add 0.3 parts of dicumyl peroxide to the mixture obtained in ii, and continue shearing at 200°C for 15 min. After shearing, let it stand at 130°C for 4 h. The standing process is carried out under N2 atmosphere. After standing, the pre-modified accelerator is obtained.

[0090] (2) The aromatic extract oil (main properties are shown in Table 1) is first pretreated by distillation. Then, 100 parts of the pretreated aromatic extract oil (fraction above 300℃) and 35 parts of the pre-modified accelerator are blended at 185℃ and 800 r / min for 5 h to ensure uniform mixing. The mixture is then oxidized in a reactor at a temperature of 280℃ and an oxygen-enriched air flow rate of 0.10 m³ / min. 3 / / (kg·h), oxidation time is 90 min, oxygen volume content in oxygen-enriched air is 70%; after oxidation, condensation reaction is carried out at a temperature of 370℃ and a nitrogen flow rate of 0.20 m³ / h. 3 / / (kg.h), the condensation time is 260min, and the desired carbon-rich component is obtained after the reaction is completed.

[0091] (3) 100 parts of the medium component (main properties shown in Table 2) and 15 parts of the light component (main properties shown in Table 3) heated to a fluid state 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 selected was FZC-301 catalyst developed by the Dalian Petrochemical Research Institute of Sinopec. The hydrogenation product was then subjected to atmospheric and vacuum distillation. The product distilled at a temperature greater than 520℃ was the desired composite treatment agent.

[0092] (4) Mix the carbon-rich component obtained in step (2) with 35 parts of the composite treatment agent obtained in step (3) and perform vacuum distillation to obtain a fraction with a temperature greater than 535°C, which is impregnated asphalt A3.

[0093] Example 4

[0094] Same as Example 1, except that the properties of the aromatic extract oil, medium component and light component used are shown in Tables 4 to 6, respectively, to obtain impregnated bitumen A4.

[0095] Example 5

[0096] Same as Example 2, except that the properties of the aromatic extract oil, medium component and light component used are shown in Tables 4 to 6, respectively, to obtain impregnated bitumen A5.

[0097] Comparative Example 1

[0098] Same as Example 1, except that in step (2) the 100 parts of pretreated aromatic extract oil (fraction above 300°C) and 35 parts of premodified accelerator are replaced with 135 parts of pretreated aromatic extract oil (fraction above 300°C) to obtain impregnated asphalt B1.

[0099] Comparative Example 2

[0100] Same as Example 1, except that in step (2) the 100 parts of pretreated aromatic extract oil (fraction greater than 300°C) and 35 parts of premodified accelerator are replaced with 135 parts of premodified accelerator to obtain impregnated asphalt B2.

[0101] Comparative Example 3

[0102] Same as Example 1, except that no initiator (benzoyl peroxide) is added during step iii in the preparation of the pre-modified accelerator, resulting in impregnated asphalt B3.

[0103] Comparative Example 4

[0104] Same as Example 1, except that step (3) is omitted and no composite treatment agent is added during the preparation process of step (4) to obtain impregnated asphalt B4.

[0105] Comparative Example 5

[0106] Same as Example 1, except that no light components are added during the preparation of the composite treatment agent in step (3), and impregnated asphalt B5 is obtained.

[0107] Comparative Example 6

[0108] Same as Example 1, except that no medium-quality component is added during the preparation of the composite treatment agent in step (3), and impregnated asphalt B6 is obtained.

[0109] Test case

[0110] The main properties of the raw materials used in the examples and comparative examples were analyzed and tested, as shown in Tables 1 to 6. The main property indicators of the impregnated bitumen prepared in the examples and comparative examples were analyzed. The analysis method was in accordance with the requirements of GB / T35074-2018 Coking Impregnating Agent Bitumen. The results are shown in Table 7.

[0111] Table 1. Properties of the aromatic extract oils used in Examples 1-3 and the comparative examples.

[0112] Saturated fraction / wt% 27.31 Aromatic components / wt% 54.22 Gel / wt% 18.36 Asphalt / wt% 0.11 <![CDATA[H ar / wt%]]> 15.24 <![CDATA[H α / wt%]]> 27.15 <![CDATA[H β / wt%]]> 43.36 <![CDATA[H γ / wt%]]> 14.25 C / H (molar ratio) 0.87 Aromatic carbon fraction / wt% 49 Cycloalkanes carbon fraction / wt% 16 Alkyl carbon fraction / wt% 35

[0113] Table 2. Partial properties of the medium-sized components used in Examples 1-3 and Comparative Examples.

[0114]

[0115]

[0116] Table 3. Partial properties of the lightweight components used in Examples 1-3 and Comparative Examples

[0117] Saturated fraction / wt% 69.21 Aromatic components / wt% 26.36 Gel / wt% 4.32 Asphalt / wt% 0.11 Carbon residue value / wt% 0.13 Sulfur content / wt% 0.24 Nitrogen content / wt% 0.18 Hydrogen-carbon molar ratio 1.8 <![CDATA[50℃ kinematic viscosity / mm 2 / s]]> 13 <![CDATA[Density at 20°C / kg / m 3 > 817

[0118] Table 4. Properties of the aromatic extract oils used in Examples 4-5

[0119] Saturated fraction / wt% 29.22 Aromatic components / wt% 56.48 Gel / wt% 14.11 Asphalt / wt% 0.19 <![CDATA[H ar / wt%]]> 15.72 <![CDATA[H α / wt%]]> 27.21 <![CDATA[H β / wt%]]> 43.05 <![CDATA[H γ / wt%]]> 14.02 C / H (molar ratio) 0.88 Aromatic carbon fraction / wt% 49.5 Cycloalkanes carbon fraction / wt% 15.4 Alkyl carbon fraction / wt% 35.1

[0120] Table 5. Some properties of the medium-sized components used in Examples 4 and 5

[0121] Saturated fraction / wt% 33.41 Aromatic components / wt% 56.65 Gel / wt% 9.92 Asphalt / wt% 0.02 <![CDATA[100℃ kinematic viscosity / mm 2 / s]]> 55 Flash point / °C 217 weight average molecular weight 2138 Molecular weight distribution width 2.1

[0122] Table 6. Properties of some of the lightweight components used in Examples 4 and 5

[0123] Saturated fraction / wt% 66.07 Aromatic components / wt% 28.44 Gel / wt% 5.46 Asphalt / wt% 0.03 Carbon residue value / wt% 0.12 Sulfur content / wt% 0.21 Nitrogen content / wt% 0.06 Hydrogen-carbon molar ratio 1.7 <![CDATA[50℃ kinematic viscosity / mm 2 / s]]> 13 <![CDATA[Density at 20°C / kg / m 3 > 856

[0124] Table 7 Properties of impregnated bitumen prepared in the examples and comparative examples

[0125]

[0126]

[0127] 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. An oil-based impregnated bitumen, characterized in that, The oil-based impregnated bitumen comprises, by weight, the following components: Pretreated aromatic extract oil: 100 parts; Pre-modified accelerator: 20-50 parts, preferably 30-50 parts; Composite treatment agent: 20-60 parts, preferably 20-45 parts.

2. The oil-based impregnated bitumen according to claim 1, characterized in that, The pretreated aromatic extract oil is the fraction obtained at a temperature greater than 300°C after distillation of the aromatic extract oil. Preferably, the aromatic extract oil is at least one of reduced third-line distillate oil, reduced fourth-line distillate oil, and reduced fifth-line distillate oil, and more preferably at least one of reduced fourth-line furfural refined extract oil or reduced fifth-line furfural refined extract oil. Preferably, the aromatic extracted oil has the following properties: 27wt%–30wt% saturated content, 52wt%–60wt% aromatic content, 13wt%–19wt% gum content, and 0wt%–0.5wt% asphaltenes; H ar 15wt%–17wt%, H α 25wt%–28wt%, H β accounting for 43wt%~46t%, H γ It accounts for 14wt% to 16wt%, with a C / H molar ratio of 0.82 to 0.88, an aromatic carbon fraction of 48wt% to 51wt%, a cycloalkanes carbon fraction of 15wt% to 18wt%, and an alkyl carbon fraction of 35wt% to 37wt%.

3. The oil-based impregnated bitumen according to claim 1, characterized in that, The pre-modified accelerator comprises the following components by weight: Aromatic extract oil fraction: 100 parts; Biochar powder: 2-10 parts, preferably 4-8 parts; Initiator: 0.1 to 0.6 parts, preferably 0.2 to 0.5 parts.

4. The oil-based impregnated bitumen according to claim 3, characterized in that, The aromatic extract oil fraction is the fraction of the aromatic extract oil between 280 and 320°C, preferably the fraction between 280 and 300°C; And / or, the aromatic extract oil is at least one of reduced third-line distillate oil, reduced fourth-line distillate oil, and reduced fifth-line distillate oil, preferably at least one of reduced fourth-line furfural refined extract oil or reduced fifth-line furfural refined extract oil. And / or, the properties of the aromatic extracted oil include: 27wt%–30wt% saturated content, 52wt%–60wt% aromatic content, 13wt%–19wt% resin content, and 0wt%–0.5wt% asphaltenes; H ar 15wt%–17wt%, H α 25wt%–28wt%, H β accounting for 43wt%~46t%, H γ It accounts for 14wt% to 16wt%, with a C / H molar ratio of 0.82 to 0.88, an aromatic carbon fraction of 48wt% to 51wt%, a cycloalkanes carbon fraction of 15wt% to 18wt%, and an alkyl carbon fraction of 35wt% to 37wt%.

5. The oil-based impregnated bitumen according to claim 3, characterized in that, The biochar powder is prepared from plant-based medicinal residues; specifically, the biochar powder is prepared from medicinal residues through dehydration and drying, primary pulverization, anaerobic carbonization, secondary pulverization, and sieving.

6. The oil-based impregnated bitumen according to claim 3, characterized in that, The herbal residue, based on the dehydrated and dried dry matter, has a crude fiber content of 15% to 25% of the total mass; the herbal residue, based on the dehydrated and dried dry matter, has an acid detergent fiber content of 30% to 50% of the total mass and a neutral detergent fiber content of 45% to 60% of the total mass; the herbal residue, based on the dehydrated and dried dry matter, has a crude ash content of 5% to 10% of the total mass.

7. The oil-based impregnated bitumen according to claim 3, characterized in that, The biochar powder has an average particle size of 120–180 mesh, preferably 140–180 mesh; the water content of the biochar powder is not higher than 0.5 wt%, and the pore volume is not less than 0.8 cm³. 3 / g, specific surface area is 2500~3500cm² 2 / g.

8. The oil-based impregnated bitumen according to claim 3, characterized in that, The initiator is one or more of dicumyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, sodium metabisulfite, azobisisobutyronitrile, azobisisoheptanenitrile, and cumyl hydroperoxide.

9. The oil-based impregnated bitumen according to claim 1, characterized in that, The composite treatment agent comprises the following components by weight: Medium-quality components: 100 parts; Light component: 15-30 parts, preferably 15-25 parts; The intermediate component is a resin obtained after solvent deasphalting; 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; And / or, the light component is a vacuum-pressed wax oil; the light component has the following properties: kinematic viscosity at 50°C is 10 mmHg. 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%–35%, and the total content of resins and asphaltenes is less than 6%; the residual carbon is less than 0.15 wt%, the sulfur content is less than 0.3 wt%, the nitrogen content is less than 1 wt%, and the hydrogen-carbon molar ratio is 1.5–1.

8.

10. A method for preparing oil-based impregnated bitumen according to any one of claims 1-9, comprising: (1) Preparation of pre-modified accelerator; (2) The pretreated aromatic extract oil and the pre-modified accelerator are blended, oxidized and condensed to obtain a carbon-rich component; (3) Preparation of composite treatment agent; (4) The composite treatment agent obtained in step (3) is mixed with the carbon-rich component obtained in step (2) and subjected to vacuum distillation to obtain the impregnated asphalt.

11. The method according to claim 10, characterized in that, In step (1), the method for preparing the pre-modified accelerator includes: i. Preparation of biochar powder; ii. Mix the aromatic extract oil fraction with biochar powder and shear to obtain a mixture of aromatic extract oil fraction and biochar powder; iii. Add the initiator to the mixture obtained in ii, continue shearing, and let it stand after shearing to obtain the pre-modified accelerator.

12. The method according to claim 11, characterized in that, The preparation process of biochar powder in step i includes: a. Dehydrate, dry, and pulverize the residue of Chinese medicinal herbs in one step; b. Perform anaerobic carbonization on the residue after step a. c. Cool the residue after carbonization in step b, pulverize it again, and sieve it to obtain biochar powder.

13. The method according to claim 12, characterized in that, In step a, the first pulverization refers to pulverizing the Chinese herbal medicine residue to 50-80 mesh; In step b, the temperature of the oxygen-free carbonization is 500-750℃, the heating rate is 8-15℃ / min, the carbonization time is 50-90min, and the carbonization process is carried out in an atmosphere of N2 and / or inert gas. After secondary crushing and sieving in step c, the resulting biochar powder has a particle size of 140-180 mesh.

14. The method according to claim 11, characterized in that, In step ii, the shearing conditions are: shearing at 180-200℃ for 30-60 minutes, with a shearing rate of 2500-4000 r / min; And / or, in step iii, the shearing conditions are: shearing at a temperature of 200-240°C for 5-15 minutes, with a shearing rate of 2500-4000 r / min.

15. The method according to claim 10, characterized in that, In step (2), the pretreatment process of the pretreated aromatic extract oil is distillation, wherein the pretreated aromatic extract oil is the fraction of the aromatic extract oil that is distilled and then cut off at a temperature greater than 300°C. And / or, the pretreated aromatic extract oil and the pre-modified accelerator are blended at 180℃~200℃, the stirring speed of the blending process is 700~900r / min, and the time is 4~6h; And / or, the oxidation process is carried out at a temperature of 270℃~320℃ and a gas flow rate of 0.05~0.15m³. 3 / (kg·h), oxidation time is 60-120 min, the gas is oxygen-enriched air with an oxygen volume content of 60%-75%; And / or, the condensation process is carried out at a temperature of 360℃~400℃ and an inert gas flow rate of 0.10~0.25m³. 3 / (kg·h), condensation time is 240-300 min.

16. The method according to claim 10, characterized in that, In step (3), the process for preparing the composite treatment agent is as follows: I. After mixing the medium and light components heated to a fluid state, hydrogen is added for hydrogenation treatment. II. The material obtained in step I is subjected to atmospheric and vacuum distillation to obtain the composite treatment agent.

17. The method according to claim 16, characterized in that, 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; And / or, in step II, the final temperature of vacuum distillation is 465–540°C, preferably 485–520°C.

18. The method according to claim 10, characterized in that, In step (4), the final temperature of the vacuum distillation is 520-580℃, preferably 520-560℃.

19. The use of the oil-based impregnated bitumen according to any one of claims 1-9 or the oil-based impregnated bitumen prepared by any one of claims 10-18 in a graphite electrode.

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