Method for directly preparing biological asphalt from biomass organic solid waste, biological asphalt and application

Abstract

The invention belongs to the related technical field of high-temperature asphalt, and discloses a method for directly preparing biological asphalt from biomass organic solid waste, the biological asphalt and application, the method comprises the following steps: (1) carrying out solvent heat treatment on the dried biomass organic solid waste to obtain an asphalt precursor; and (2) carrying out thermal modification on the asphalt precursor to obtain the biological asphalt. The biomass organic solid waste is actively and directly converted into the high-performance asphalt through a two-step process of'solvent heat treatment-thermal modification ', so that the high-performance asphalt becomes a unique main product, and the production process is completely optimized around the quality and quantity of the asphalt through the production mode; the core pain points that raw material supply is limited by upstream industries and properties are uncontrollable are fundamentally solved.

Description

Technical Field

[0001] This invention belongs to the technical field of high-temperature asphalt, and more specifically, relates to a method for directly preparing bio-asphalt from biomass-based organic solid waste, bio-asphalt, and its applications. Background Technology

[0002] As a precursor to high-end carbon materials used in aerospace and military industries, high-temperature coal tar pitch is a byproduct of the coking industry, accounting for only 2%-3% of the main products. Its supply is highly susceptible to fluctuations in the coking market, and it is expensive with high carbon emissions throughout its entire life cycle. Therefore, developing green, low-carbon, economically sustainable technologies with asphalt as the main product has become an urgent need for this industry. Biomass-based organic solid waste, as a green carbon source, is considered the most promising green raw material for asphalt production.

[0003] However, these raw materials are characterized by high moisture content (5%-20%), high oxygen content (10%-40%), high ash content (2%-30%), and low aromaticity. These characteristics result in poor properties and difficulty in targeted control of bioasphalt prepared from biomass-based organic solid waste. Therefore, deoxygenation and impurity removal are necessary, along with targeted conversion. To address the difficulty of converting high-impurity biomass raw materials, the traditional method for preparing bioasphalt involves pyrolyzing biomass at 500℃-550℃ to produce ash-free bio-oil, which is then modified through distillation, thermal polycondensation, and other methods to produce asphalt. However, the quality of bio-oil from different biomass pyrolysis processes varies greatly, with oxygen content ranging from 10%-40%, leading to poor properties and difficulty in targeted control of asphalt prepared from bio-oil, thus affecting its economic efficiency. Summary of the Invention

[0004] In view of the above-mentioned defects or improvement needs of the existing technology, the present invention provides a method for directly preparing bio-asphalt from biomass organic solid waste, bio-asphalt and its application, which aims to solve the problem that the asphalt prepared from bio-oil by biomass pyrolysis has poor properties.

[0005] To achieve the above objectives, according to one aspect of the present invention, a method for directly preparing bioasphalt from biomass-based organic solid waste is provided, the method comprising the following steps: (1) The dried biomass organic solid waste was subjected to solvent heat treatment to obtain asphalt precursor; (2) The asphalt precursor is thermally modified to obtain bio-asphalt.

[0006] Furthermore, the biomass organic solid waste is dried at 50℃-60℃ for 2h-6h.

[0007] Further, in step (1), the dried biomass organic solid waste raw material is mixed with the solvent and then placed in a high-pressure reactor for solvent thermal treatment under inert gas protection; after the reaction is completed, the solid residue is separated, and the liquid mixture obtained is subjected to flash evaporation to obtain the pitch precursor.

[0008] Further, the mass ratio of the biomass organic solid waste raw material to the solvent is 1: (5-15).

[0009] Further, the solvent is a mixture of one or more of 1-methylnaphthalene, crude methylnaphthalene, wash oil, quinoline, dihydronaphthalene, tetrahydronaphthalene and decahydronaphthalene.

[0010] Further, the temperature of the heat treatment is 350-400 ℃, the heating rate is 5-10 ℃ / min, and the reaction time is 30-90 min.

[0011] Further, the flash evaporation temperature of the product is 120 ℃, and the flash evaporation pressure is -0.08 to -0.1 Mpa.

[0012] Further, in step (2), the mass ratio of the pitch precursor to the solvent is 0-5.

[0013] Further, the solvent is a mixture of one or more of 1-methylnaphthalene, crude methylnaphthalene, wash oil, quinoline, dihydronaphthalene, tetrahydronaphthalene and decahydronaphthalene, wherein the proportion of dihydronaphthalene, tetrahydronaphthalene and decahydronaphthalene is 10-30%.

[0014] Further, the temperature of the heat modification is 350-400 ℃, the heating rate is 5-10 ℃ / min, and the reaction time is 60-120 min.

[0015] The application also provides a bio-pitch prepared by the method for directly preparing a bio-pitch from biomass organic solid waste as described above.

[0016] The application also provides the use of the bio-pitch as described above in aerospace, military and electrode carbon materials.

[0017] Overall, compared with the prior art, the method for directly preparing a bio-pitch from biomass organic solid waste, the bio-pitch and the use provided by the application mainly have the following beneficial effects: 1. The direct conversion path with asphalt as the main product is proposed, realizing the efficiency and economy of the process: the existing high-temperature coal pitch is a byproduct of the coking process in the coking industry, its yield (only 2%-3% of the coke output) and properties are strictly restricted by the main coking process, and cannot be flexibly adjusted according to the demand for asphalt. The invention overturns this passive mode, and actively converts biomass organic solid waste into high-performance asphalt through a two-step process of "solvent thermal treatment-thermal modification", making it the only main product. This production method optimizes the production process around the quality and quantity of asphalt, and fundamentally solves the core problem of raw material supply being subject to upstream industry and uncontrollable properties.

[0018] 2. The process conditions are mild and efficient, significantly reducing energy consumption and equipment cost, and the green and low-carbon advantages are prominent: the solvent thermal treatment step of the invention is carried out at a lower temperature range (350-400℃), which is much lower than the high temperature of 500-550℃ required by traditional pyrolysis oil production. Low-temperature reaction conditions greatly reduce energy consumption, reduce the harsh requirements for reaction equipment, and directly reduce investment and operating costs. At the same time, the mild reaction conditions effectively inhibit the coking and excessive cracking side reactions that easily occur at high temperatures, improving the yield and quality of the target product, and the carbon emissions of the entire process are significantly lower than the coal pitch production process based on fossil energy, in line with the development direction of green chemical industry.

[0019] 3. The raw material has strong applicability and can realize the high-value and resource utilization of various biomass organic solid waste: the solvent system used in the invention has strong solubility and mass transfer capacity, and has high inclusiveness for the types and qualities of raw materials. Whether it is straw, sawdust and other agricultural and forestry waste, or peel, waste paper and other urban organic solid waste, or even complex algae, one or a mixture of them can be used as raw material without complex pretreatment. This feature perfectly solves the industry problem of dispersed biomass raw material sources and uneven composition, providing a universal technical platform for large-scale and low-cost disposal of various organic solid waste and converting them into high-value-added products, realizing the true "waste to treasure".

[0020] 4. The product performance is flexible and adjustable, and the quality is excellent, which has great potential to replace high-end coal pitch: by accurately adjusting the key parameters such as temperature, time, and solvent ratio in the two-step process, the key performance indicators of the final bio-pitch product can be "directionally regulated". The softening point can be flexibly designed in a wide range of 95-250°C, so as to produce customized products that meet the needs of different application scenarios such as impregnation, bonding, and electrode. The obtained bio-pitch has excellent characteristics such as high carbon content (>85%), low heteroatom content (oxygen content <10%), and extremely low ash content (<0.05%), and its comprehensive performance is equivalent to that of expensive high-temperature coal tar pitch. It not only solves the risk of "neck" in the raw material field of high-end carbon materials, but also has broad market application prospects and competitiveness. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 is a flow chart of a method for directly preparing bio-pitch from biomass organic solid waste provided by the present application. DETAILED DESCRIPTION

[0022] In order to make the purpose, technical scheme and advantages of the present application clearer, the present application will be further described in detail below in combination with the drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application and do not limit the present application. In addition, the technical features involved in each embodiment of the present application described below can be combined with each other as long as they do not conflict with each other.

[0023] Please refer to Figure 1 The present application provides a method for directly preparing bio-pitch from biomass organic solid waste, which is a green and low-carbon, low-cost method with pitch as the main product. It can convert high-oxygen and high-ash biomass organic solid waste into high-quality bio-pitch, and realize directional regulation of pitch performance, solving the problem of "neck" in the upstream of pitch-based high-end carbon materials.

[0024] The method adopts two steps: first, through solvent thermal treatment, the biomass raw material is converted into a bio-pitch precursor with thermoplasticity, high carbon and low oxygen; then, through a thermal modification process, the bio-pitch precursor is modified to realize directional regulation of product performance, and high-temperature bio-pitch is obtained.

[0025] The method mainly includes the following steps: S1, drying of biomass organic solid waste.

[0026] The biomass organic solid waste is dried at 50-60°C for 2-6h to reduce its moisture, which is beneficial to reduce the pressure increase caused by water vapor in the solvent thermal treatment step of the biomass organic solid waste, and reduces the pressure of the reaction system.

[0027] S2, solvent thermal treatment is performed on the dried biomass-based organic solid waste to prepare pitch precursor.

[0028] After mixing the dried biomass-based organic solid waste raw material with the solvent in a certain mass ratio, the mixture is placed in a high-pressure reaction kettle and subjected to solvent thermal treatment under the protection of an inert atmosphere. After the reaction is completed, the solid residue is separated, and the low-oxygen and low-ash pitch precursor rich in aromatic compounds is obtained after flash evaporation.

[0029] In one embodiment, the biomass-based organic solid waste raw material is mixed with the solvent at a mass ratio of 1: (5-15) to prepare a slurry, and the solvent is a mixture of one or more of 1-methylnaphthalene, crude methylnaphthalene, wash oil, quinoline, dihydronaphthalene, tetrahydronaphthalene, and decalin. The slurry is added to the reaction kettle for reaction. Nitrogen is introduced to replace the air in the reaction kettle to prevent oxygen from participating in the reaction. The stirring is started and the stirring speed is set to 100 r / min. The reaction is carried out at a reaction temperature of 350-400 ℃ for 30-90 min. After the reaction is completed, the solid residue is separated, and the obtained liquid mixture is flash evaporated at -0.08 MPa to -0.1 MPa and heated to 120 ℃. The obtained solid product is the bio-pitch precursor. The heating rate used is preferably 5-10 ℃ / min.

[0030] The biomass-based organic solid waste raw material covers a mixture of one or more of almost all biomasses such as leftovers, fruit peels, tree bark, wood chips, waste paper, and algae.

[0031] S3, the obtained pitch precursor is subjected to thermal modification to obtain high-temperature bio-pitch.

[0032] Specifically, the obtained pitch precursor is placed in a reactor, solvent is added, and programmed temperature rising is performed under an inert atmosphere. By precisely controlling the thermal treatment temperature and time, the precursor molecules undergo directional reaction. After the reaction is completed, vacuum flash evaporation is performed to finally obtain high-performance bio-pitch.

[0033] In one embodiment, after the biomass pitch precursor is added to the modification device, 0-5 times of solvent is added to prepare the reaction. The main components of the solvent are 1-methylnaphthalene, crude methylnaphthalene, wash oil, quinoline, dihydronaphthalene, tetrahydronaphthalene and decalin, and the like, and the mixture of two or more of the above double aromatic ring solvents. The proportion of dihydronaphthalene, tetrahydronaphthalene and decalin needs to reach 10%-30%. The oxygen in the reactor is replaced by inert gas, the equipment is heated to 350-400℃ at a heating rate of 5-10℃ / min, and the temperature is kept for 60-120 min. The stirring is started and the stirring paddle speed is set to 100 r / min. After the reaction is completed, the liquid mixture is flashed at -0.08MPa to -0.1MPa and heated to 120℃.

[0034] The application provides a bio-asphalt, which is prepared by the method for directly preparing bio-asphalt from biomass organic solid waste.

[0035] The application also provides application of the bio-asphalt in aerospace, military industry and electrode carbon materials.

[0036] The performance indexes of the high-temperature bio-asphalt prepared include softening point, coking value, ash content, carbon content and oxygen content, and the corresponding test methods are as follows: The test method of the softening point is GB / T 4507-2014, which is a commonly used method for determining the softening point of asphalt materials. The softening point of asphalt samples is determined by measuring the temperature at which the asphalt sample softens and falls a certain distance under specific conditions.

[0037] The test method of the coking value is GB / T 8727-2008, which provides a method for determining the coking value of coal pitch. The method is to heat a certain amount of coal pitch sample in a muffle furnace at 550±10℃ for 2 hours under the condition of air isolation, and the coking value is expressed by the percentage of the mass of the residual coke in the mass of the original sample. The coking value of the prepared green pitch is determined by this method.

[0038] The test method of the ash content is the slow ashing method in the industrial analysis method (GB / T 212-2008) of coal. The method is to put a certain mass of asphalt sample into a muffle furnace, slowly heat from room temperature to 815±10℃, and burn at this temperature until the mass is constant. The ash content is expressed by the percentage of the residual mass in the mass of the original sample.

[0039] The method for testing the carbon content is in accordance with the national standard GB / T 30733-2014. In this method, a certain amount of asphalt sample is fully burned in a high-temperature oxygen stream, and the carbon element is completely converted into carbon dioxide. The generated carbon dioxide is quantitatively analyzed using an infrared detection cell or a thermal conductivity detector, so as to calculate the mass percentage of carbon element in the sample.

[0040] The method for testing the oxygen content is calculated by using the difference method. First, the carbon, hydrogen and nitrogen contents are determined according to GB / T 30733-2014, and the ash content is determined according to GB / T 212-2008, and then the oxygen content (%) = 100%-C%-H%-N%-Ash% is calculated.

[0041] The application will be further described in detail below with specific examples.

[0042] Example 1 In Example 1 of the application, sawdust, an industrial waste, is used as a typical biomass organic solid waste, and 1-methylnaphthalene and tetrahydronaphthalene are used as raw materials for the experiment.

[0043] 50 parts of 100-mesh sawdust and 500 parts of 1-methylnaphthalene are weighed and prepared into a slurry, which is then added into a reaction kettle. The stirring is started, and the temperature is raised to 350℃ at a rate of 10℃ / min, and then the temperature is kept for 60 min. After the reaction is completed, the solid residue is separated, and the liquid mixture obtained is subjected to flash evaporation. The solid product obtained is a bio-asphalt precursor. The bio-asphalt precursor is added into a modification device, and 2.5 times the mass of the precursor is added into the device as a solvent. In the solvent, 1-methylnaphthalene accounts for 80%, and tetrahydronaphthalene accounts for 20%. Subsequently, the device is heated to 350℃ at a rate of 10℃ / min, and then the temperature is kept for 60 min. The stirring is started, and the stirring paddle speed is set to 100 r / min. After the reaction is completed, the liquid mixture is subjected to flash evaporation, and the solid product obtained is a high-temperature bio-asphalt.

[0044] After detection, 31.8% of the mass of the raw material is obtained as asphalt. The softening point of the asphalt is 192.3℃, the coking value is 58.7%, the ash content is 0.04%, the carbon content is 87.8%, and the oxygen content is 9.2%.

[0045] Example 2 In the embodiment 2 of the present application, 50 parts of 100 mesh sawdust and 500 parts of 1-methylnaphthalene are weighed and prepared into a slurry, which is added into a reaction kettle. Stirring is started and heating is performed at a rate of 10 ℃ / min to 375 ℃, and the temperature is kept for 60 min. After the reaction is completed, the solid residue is separated, and the liquid mixture is flashed. The obtained solid product is a bio-asphalt precursor. The bio-asphalt precursor is added into a modification device, and 2.5 times the mass of the precursor of solvent is added, in which 1-methylnaphthalene accounts for 80% and tetrahydronaphthalene accounts for 20%. Subsequently, the device is heated to 350 ℃ at a heating rate of 10 ℃ / min, and the temperature is kept for 60 min. Stirring is started and the stirring paddle rate is set to 100 r / min. After the reaction is completed, the obtained liquid mixture is flashed, and the obtained solid product is a high-temperature bio-asphalt.

[0046] It is detected that 41.2% of the mass of the raw material is obtained as asphalt, which has a softening point of 182.5 ℃, a coking value of 57.1%, an ash content of 0.03%, a carbon content of 90.3%, and an oxygen content of 7.9%.

[0047] Embodiment 3 In the embodiment 3 of the present application, 50 parts of 100 mesh sawdust and 500 parts of 1-methylnaphthalene are weighed and prepared into a slurry, which is added into a reaction kettle. Stirring is started and heating is performed at a rate of 10 ℃ / min to 400 ℃, and the temperature is kept for 60 min. After the reaction is completed, the solid residue is separated, and the obtained liquid mixture is flashed. The obtained solid product is a bio-asphalt precursor. The bio-asphalt precursor is added into a modification device, and 2.5 times the mass of the precursor of solvent is added, in which 1-methylnaphthalene accounts for 80% and tetrahydronaphthalene accounts for 20%. Subsequently, the device is heated to 350 ℃ at a heating rate of 10 ℃ / min, and the temperature is kept for 60 min. Stirring is started and the stirring paddle rate is set to 100 r / min. After the reaction is completed, the obtained liquid mixture is flashed, and the obtained solid product is a high-temperature bio-asphalt.

[0048] It is detected that 33.7% of the mass of the raw material is obtained as asphalt, which has a softening point of 142.8 ℃, a coking value of 55.6%, an ash content of 0.02%, a carbon content of 90.8%, and an oxygen content of 7.7%.

[0049] Embodiment 4 In the embodiment 4 of the present application, 50 parts of 100 mesh sawdust and 500 parts of 1-methylnaphthalene are weighed and prepared into a slurry, which is added into a reaction kettle. Stirring is started and heating is performed at a rate of 10 ℃ / min to 375 ℃, and the temperature is kept for 30 min. After the reaction is completed, the solid residue is separated, and the liquid mixture is subjected to flash evaporation. The obtained solid product is a bio-asphalt precursor. The bio-asphalt precursor is added into a modification device, and 2.5 times the mass of the precursor of solvent is added, in which 1-methylnaphthalene accounts for 80% and tetrahydronaphthalene accounts for 20%. Subsequently, the device is heated to 350 ℃ at a heating rate of 10 ℃ / min, and the temperature is kept for 60 min. Stirring is started and the stirring paddle rate is set to 100 r / min. After the reaction is completed, the liquid mixture is subjected to flash evaporation, and the obtained solid product is a high-temperature bio-asphalt.

[0050] It is detected that 36.2% of the mass of the raw material is asphalt, the softening point of the asphalt is 192.5 ℃, the coking value is 57.3%, the ash content is 0.00%, the carbon content is 90.7%, and the oxygen content is 7.6%.

[0051] Embodiment 5 In the embodiment 5 of the present application, 50 parts of 100 mesh sawdust and 500 parts of 1-methylnaphthalene are weighed and prepared into a slurry, which is added into a reaction kettle. Stirring is started and heating is performed at a rate of 10 ℃ / min to 375 ℃, and the temperature is kept for 90 min. After the reaction is completed, the solid residue is separated, and the liquid mixture is subjected to flash evaporation. The obtained solid product is a bio-asphalt precursor. The bio-asphalt precursor is added into a modification device, and 2.5 times the mass of the precursor of solvent is added, in which 1-methylnaphthalene accounts for 80% and tetrahydronaphthalene accounts for 20%. Subsequently, the device is heated to 350 ℃ at a heating rate of 10 ℃ / min, and the temperature is kept for 60 min. Stirring is started and the stirring paddle rate is set to 100 r / min. After the reaction is completed, the liquid mixture is subjected to flash evaporation, and the obtained solid product is a high-temperature bio-asphalt.

[0052] It is detected that 36.2% of the mass of the raw material is asphalt, the softening point of the asphalt is 192.5 ℃, the coking value is 57.3%, the ash content is 0.00%, the carbon content is 90.7%, and the oxygen content is 7.6%.

[0053] Embodiment 6 In the embodiment 6 of the present application, 50 parts of 100-mesh sawdust and 500 parts of 1-methylnaphthalene are weighed and prepared into a slurry, which is added into a reaction kettle. Stirring is started and heating is performed at a rate of 10 ℃ / min to 375 ℃, and the temperature is kept for 60 min. After the reaction is completed, the solid residue is separated, and the liquid mixture obtained is subjected to flash evaporation. The solid product obtained is a bio-asphalt precursor. The bio-asphalt precursor is added into a modification device, and no solvent is added. Subsequently, the device is heated to 350 ℃ at a heating rate of 10 ℃ / min, and the temperature is kept for 60 min. Stirring is started and the stirring paddle rate is set to 100 r / min. After the reaction is completed, the liquid mixture is subjected to flash evaporation, and the solid product obtained is a high-temperature asphalt.

[0054] It is detected that 39.5% of the mass of the raw material is asphalt, the softening point of the asphalt is 242.5 ℃, the coking value is 61.3%, the ash content is 0.04%, the carbon content is 86.3%, and the oxygen content is 9.9%.

[0055] Embodiment 7 In the embodiment 7 of the present application, 50 parts of 100-mesh sawdust and 500 parts of 1-methylnaphthalene are weighed and prepared into a slurry, which is added into a reaction kettle. Stirring is started and heating is performed at a rate of 10 ℃ / min to 375 ℃, and the temperature is kept for 60 min. After the reaction is completed, the solid residue is separated, and the liquid mixture obtained is subjected to flash evaporation. The solid product obtained is a bio-asphalt precursor. The bio-asphalt precursor is added into a modification device, and 5 times the mass of the precursor of solvent is added. The 1-methylnaphthalene accounts for 100% in the solvent, and tetrahydronaphthalene accounts for 0%. Subsequently, the device is heated to 350 ℃ at a heating rate of 10 ℃ / min, and the temperature is kept for 60 min. Stirring is started and the stirring paddle rate is set to 100 r / min. After the reaction is completed, the liquid mixture obtained is subjected to flash evaporation, and the solid product obtained is a high-temperature asphalt.

[0056] It is detected that 38.5% of the mass of the raw material is asphalt, the softening point of the asphalt is 200.4 ℃, the coking value is 53.9%, the ash content is 0.02%, the carbon content is 86.8%, and the oxygen content is 9.2%.

[0057] Embodiment 8 In the embodiment 8 of the present application, 50 parts of 100 mesh sawdust and 500 parts of 1-methylnaphthalene are weighed and prepared into a slurry, which is added into a reaction kettle. Stirring is started and heating is performed at a rate of 10 ℃ / min to 375 ℃, and the temperature is kept for 60 min. After the reaction is completed, the solid residue is separated, and the liquid mixture is subjected to flash evaporation. The obtained solid product is a bio-asphalt precursor. The bio-asphalt precursor is added into a modification device, and 5 times the mass of the precursor of solvent is added, in which 1-methylnaphthalene accounts for 80% and tetrahydronaphthalene accounts for 20%. Subsequently, the device is heated to 350 ℃ at a heating rate of 10 ℃ / min, and the temperature is kept for 60 min. Stirring is started and the stirring paddle rate is set to 100 r / min. After the reaction is completed, the liquid mixture is subjected to flash evaporation, and the obtained solid product is high-temperature asphalt.

[0058] It is detected that 37.8% of the mass of the raw material is obtained as asphalt, which has a softening point of 182.5 ℃, a coking value of 53.6%, an ash content of 0.00%, a carbon content of 90.8%, and an oxygen content of 6.8%.

[0059] Embodiment 9 In the embodiment 9 of the present application, 50 parts of 100 mesh sawdust and 500 parts of 1-methylnaphthalene are weighed and prepared into a slurry, which is added into a reaction kettle. Stirring is started and heating is performed at a rate of 10 ℃ / min to 375 ℃, and the temperature is kept for 60 min. After the reaction is completed, the solid residue is separated, and the liquid mixture is subjected to flash evaporation. The obtained solid product is a bio-asphalt precursor. The bio-asphalt precursor is added into a modification device, and 2.5 times the mass of the precursor of solvent is added, in which 1-methylnaphthalene accounts for 80% and tetrahydronaphthalene accounts for 20%. Subsequently, the device is heated to 375 ℃ at a heating rate of 10 ℃ / min, and the temperature is kept for 60 min. Stirring is started and the stirring paddle rate is set to 100 r / min. After the reaction is completed, the obtained liquid mixture is subjected to flash evaporation, and the obtained solid product is high-temperature asphalt.

[0060] It is detected that 35.7% of the mass of the raw material is obtained as asphalt, which has a softening point of 137.5 ℃, a coking value of 56.3%, an ash content of 0.03%, a carbon content of 90.7%, and an oxygen content of 6.7%.

[0061] Embodiment 10 In the embodiment 10 of the present application, 50 parts of 100 mesh sawdust and 500 parts of 1-methylnaphthalene are weighed and prepared into a slurry, which is added into a reaction kettle. Stirring is started and heating is performed at a rate of 10 ℃ / min to 375 ℃, and the temperature is kept for 60 min. After the reaction is completed, the solid residue is separated, and the liquid mixture obtained is subjected to flash evaporation. The solid product obtained is a bio-asphalt precursor. The asphalt precursor is added into a modification device, and 2.5 times the mass of the precursor of solvent is added, in which 1-methylnaphthalene accounts for 80% and tetrahydronaphthalene accounts for 20%. Subsequently, the device is heated to 400 ℃ at a heating rate of 10 ℃ / min, and the temperature is kept for 60 min. Stirring is started and the stirring paddle rate is set to 100 r / min. After the reaction is completed, the liquid mixture is subjected to flash evaporation, and the solid product obtained is high-temperature asphalt.

[0062] It is detected that 33.9% of the mass of the raw material is obtained as asphalt, which has a softening point of 110.2 ℃, a coking value of 48.9%, an ash content of 0.00%, a carbon content of 90.5%, and an oxygen content of 7.3%.

[0063] Embodiment 11 In the embodiment 11 of the present application, 50 parts of 100 mesh sawdust and 500 parts of 1-methylnaphthalene are weighed and prepared into a slurry, which is added into a reaction kettle. Stirring is started and heating is performed at a rate of 10 ℃ / min to 375 ℃, and the temperature is kept for 60 min. After the reaction is completed, the solid residue is separated, and the liquid mixture obtained is subjected to flash evaporation. The solid product obtained is a bio-asphalt precursor. The asphalt precursor is added into a modification device, and 2.5 times the mass of the precursor of solvent is added, in which 1-methylnaphthalene accounts for 90% and tetrahydronaphthalene accounts for 10%. Subsequently, the device is heated to 375 ℃ at a heating rate of 10 ℃ / min, and the temperature is kept for 60 min. Stirring is started and the stirring paddle rate is set to 100 r / min. After the reaction is completed, the liquid mixture is subjected to flash evaporation, and the solid product obtained is high-temperature asphalt.

[0064] It is detected that 35.7% of the mass of the raw material is obtained as asphalt, which has a softening point of 147.5 ℃, a coking value of 58.1%, an ash content of 0.04%, a carbon content of 89.9%, and an oxygen content of 7.5%.

[0065] Embodiment 12 In the embodiment 12 of the present application, 50 parts of 100 mesh sawdust and 500 parts of 1-methylnaphthalene are weighed and prepared into a slurry, which is added into a reaction kettle. Stirring is started and heating is performed at a rate of 10 ℃ / min to 375 ℃, and the temperature is kept for 60 min. After the reaction is completed, the solid residue is separated, and the liquid mixture obtained is subjected to flash evaporation. The solid product obtained is a bio-asphalt precursor. The asphalt precursor is added into a modification device, and 2.5 times the mass of the precursor of solvent is added, in which 1-methylnaphthalene accounts for 70% and tetrahydronaphthalene accounts for 30%. Subsequently, the device is heated to 375 ℃ at a heating rate of 10 ℃ / min, and the temperature is kept for 60 min. Stirring is started and the stirring paddle rate is set to 100 r / min. After the reaction is completed, the liquid mixture is subjected to flash evaporation. The solid product obtained is high-temperature asphalt.

[0066] It is detected that 31.9% of the mass of the raw material is obtained as asphalt, which has a softening point of 132.5 ℃, a coking value of 54.0%, an ash content of 0.02%, a carbon content of 89.2%, and an oxygen content of 8.7%.

[0067] Embodiment 13 In the embodiment 13 of the present application, 50 parts of 100 mesh sawdust and 500 parts of 1-methylnaphthalene are weighed and prepared into a slurry, which is added into a reaction kettle. Stirring is started and heating is performed at a rate of 10 ℃ / min to 375 ℃, and the temperature is kept for 60 min. After the reaction is completed, the solid residue is separated, and the liquid mixture obtained is subjected to flash evaporation. The solid product obtained is a bio-asphalt precursor. The asphalt precursor is added into a modification device, and 2.5 times the mass of the precursor of solvent is added, in which 1-methylnaphthalene accounts for 80% and tetrahydronaphthalene accounts for 20%. Subsequently, the device is heated to 375 ℃ at a heating rate of 10 ℃ / min, and the temperature is kept for 90 min. Stirring is started and the stirring paddle rate is set to 100 r / min. After the reaction is completed, the liquid mixture is subjected to flash evaporation. The solid product obtained is high-temperature asphalt.

[0068] It is detected that 35.8% of the mass of the raw material is obtained as asphalt, which has a softening point of 122.5 ℃, a coking value of 53.0%, an ash content of 0.01%, a carbon content of 90.4%, and an oxygen content of 7.4%.

[0069] Embodiment 14 In the embodiment 14 of the present application, 50 parts of 100 mesh sawdust and 500 parts of 1-methylnaphthalene are weighed and prepared into a slurry, which is added into a reaction kettle, stirring is started and heating is performed at a rate of 10 ℃ / min to 375 ℃, and the temperature is kept for 60 min. After the reaction is completed, the solid residue is separated, the liquid mixture obtained is flashed, and the solid product obtained is a bio-asphalt precursor. The asphalt precursor is added into a modification device, 2.5 times the mass of the precursor of solvent is added, 1-methylnaphthalene accounts for 80% and tetrahydronaphthalene accounts for 20% in the solvent. Then, the device is heated to 375 ℃ at a heating rate of 10 ℃ / min, and the temperature is kept for 120 min, stirring is started and the stirring paddle rate is set to 100 r / min. After the reaction is completed, the liquid mixture is flashed, and the solid product obtained is high-temperature asphalt.

[0070] It is detected that 35.6% of the mass of the raw material is obtained as asphalt, the softening point of the asphalt is 122.5 ℃, the coking value is 52.7%, the ash content is 0.04%, the carbon content is 90.3%, and the oxygen content is 7.6%.

[0071] Embodiment 15 In the embodiment 15 of the present application, 10 parts of 100 mesh green leaves, 10 parts of bark, 10 parts of fruit peel, 10 parts of waste paper, 10 parts of green algae and 500 parts of 1-methylnaphthalene are weighed and prepared into a slurry, which is added into a reaction kettle, stirring is started and heating is performed at a rate of 10 ℃ / min to 375 ℃, and the temperature is kept for 60 min. After the reaction is completed, the solid residue is separated, the liquid mixture obtained is flashed, and the solid product obtained is a bio-asphalt precursor. The asphalt precursor is added into a modification device, 2.5 times the mass of the precursor of solvent is added, 1-methylnaphthalene accounts for 80% and tetrahydronaphthalene accounts for 20% in the solvent. Then, the device is heated to 375 ℃ at a heating rate of 10 ℃ / min, and the temperature is kept for 90 min, stirring is started and the stirring paddle rate is set to 100 r / min. After the reaction is completed, the liquid mixture is flashed, and the solid product obtained is high-temperature asphalt.

[0072] It is detected that 38.4% of the mass of the raw material is obtained as asphalt, the softening point of the asphalt is 112.5 ℃, the coking value is 51.4%, the ash content is 0.02%, the carbon content is 89.5%, and the oxygen content is 8.2%.

[0073] Embodiment 16 In the embodiment 16 of the present application, 1 part of the bio-asphalt prepared in the embodiment 13 is mixed with polyacrylonitrile at a mass ratio of 1:1, and then mixed with a commonly used solvent DMF (N-N dimethylformamide) for electrospinning, and the solvent is used in an amount of 19 parts. The obtained mixed solution is subjected to electrospinning to prepare nanofibers, and after oxidation and carbonization, nanocarbon fibers are prepared, which can be used as high-performance catalyst carriers in the field of aerospace.

[0074] The diameter of the carbon fiber is 200 nm, the specific surface area is 714 m 2 / g, the specific volume is 164.10 m 3 / g, the average pore size is 2.02 nm, and the carbon fiber is an excellent catalyst carrier.

[0075] Those skilled in the art can understand that the above description is only a preferred embodiment of the present application, and is not intended to limit the present application. Any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for directly preparing bioasphalt from biomass-based organic solid waste, characterized in that, The method includes the following steps: (1) The dried biomass organic solid waste was subjected to solvent heat treatment to obtain asphalt precursor; (2) The asphalt precursor is thermally modified to obtain bio-asphalt.

2. The method for directly preparing bioasphalt from biomass-based organic solid waste as described in claim 1, characterized in that: In step (1), the dried biomass organic solid waste raw material and solvent are mixed and placed in a high-pressure reactor for solvent heat treatment under an inert atmosphere. After the reaction is completed, the solid residue is separated and the resulting liquid mixture is flash-evaporated to obtain the asphalt precursor.

3. The method for directly preparing bioasphalt from biomass-based organic solid waste as described in claim 2, characterized in that: The mass ratio of biomass organic solid waste raw materials to solvents is 1:(5-15).

4. The method for directly preparing bioasphalt from biomass-based organic solid waste as described in claim 2, characterized in that: In step (1), the solvent is one or a mixture of 1-methylnaphthalene, crude methylnaphthalene, wash oil, quinoline, dihydronaphthalene, tetrahydronaphthalene and decahydronaphthalene.

5. The method for directly preparing bioasphalt from biomass-based organic solid waste as described in claim 2, characterized in that: In step (1), the heat treatment temperature is 350℃-400℃, the heating rate is 5℃ / min-10℃ / min, and the reaction time is 30 min-90 min.

6. The method for directly preparing bioasphalt from biomass-based organic solid waste as described in claim 1, characterized in that: In step (2), the mass ratio of asphalt precursor to solvent is 0-5.

7. The method for directly preparing bioasphalt from biomass-based organic solid waste as described in claim 6, characterized in that: In step (2), the solvent is one or a mixture of 1-methylnaphthalene, crude methylnaphthalene, wash oil, quinoline, dihydronaphthalene, tetrahydronaphthalene and decahydronaphthalene, wherein the mass percentage of dihydronaphthalene, tetrahydronaphthalene and decahydronaphthalene needs to reach 10%-30%.

8. The method for directly preparing bioasphalt from biomass-based organic solid waste as described in claim 6, characterized in that: In step (2), the heat treatment temperature is 350℃-400℃, the heating rate is 5℃ / min-10℃ / min, and the reaction time is 60 min-120 min.

9. A type of bio-asphalt, characterized in that: The bio-asphalt is prepared by the method described in any one of claims 1-8, which involves directly preparing bio-asphalt from biomass-based organic solid waste.

10. The application of the bio-asphalt as described in claim 9 in aerospace, military and electrode carbon materials.

Images