Biomass activated waste rubber powder material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of biomass and solid waste resource utilization, and particularly relates to a biomass activated waste rubber powder material and a preparation method and application thereof. Biomass, acetic acid and water are mixed, a reaction mixture is obtained through a hydrothermal reaction and acetone flushing, a moisture-containing biochar solid and a bio-oil-containing liquid are obtained through vacuum filtration, the moisture-containing biochar solid is dried to obtain biochar, a part of biochar is selected to be ground and dialyzed to obtain biomass carbon dots, and the biomass carbon dots are prepared into biomass carbon dots. Drying the liquid containing the bio-oil to obtain the bio-oil; mixing the obtained bio-oil, biochar, biomass carbon dots and waste rubber powder, and performing microwave activation to obtain biomass activated waste rubber powder. The regenerated asphalt can be obtained by doping the biomass activated waste rubber powder into the waste asphalt. The method provided by the invention can greatly reduce the stockpiling amount of biomass, waste tires and waste asphalt mixtures, improve the ecological environment of the expressway and reduce carbon emission, and has important significance for popularization and application of multi-source solid wastes in highway engineering.

Description

Technical Field

[0001] The present invention belongs to the technical field of biomass and solid waste resource utilization, and particularly relates to a biomass-activated waste rubber powder material, a preparation method thereof, and an application thereof. Background Art

[0002] Biomass resources in China are abundant, and the annual production of biomass resources can reach 3.5 billion tons. With the continuous increase in the vehicle ownership, the total weight of recyclable waste tires in China reaches 4.84 million tons, and the production of biomass and waste tires is huge. Therefore, in order to promote the conservation and intensive utilization of resources, it is urgent to develop a new method for the collaborative treatment of biomass and waste tire rubber powder.

[0003] According to statistics, by the end of 2024, the expressways in China have reached 1.691 million kilometers. Calculated at an annual repair rate of 12%, the recoverable recycled asphalt mixture can reach 200 million tons per year, and the recoverable waste asphalt can reach 10 million tons per year. After recycling and utilization, the material cost can be saved by 31.8 billion yuan. Therefore, it is urgent to develop an application method for recycling waste asphalt using a biomass-activated waste rubber powder material.

[0004] Recycling waste asphalt using a biomass-activated waste rubber powder material can significantly reduce the stockpiles of biomass, waste tires, and waste asphalt mixtures, improve the comprehensive utilization efficiency of multi-source solid waste, improve the fluorescence characteristics of waste asphalt and the ecological environment of highway engineering, reduce the emissions of volatile organic compounds in the recycling of waste asphalt with a biomass-activated waste rubber powder, and is of great significance for the popularization and application of biomass-activated waste rubber powder materials in the recycling of waste asphalt mixtures. Summary of the Invention

[0005] Aiming at the problems of large production and difficult utilization of biomass, waste tires, and waste asphalt mixtures, etc., the present invention provides a biomass-activated waste rubber powder material, a preparation method thereof, and an application thereof. The biomass-activated waste rubber powder material of the present invention has the characteristics of environmental friendliness, high waste rubber powder content, and recyclable waste asphalt. At the same time, it also has the characteristics of resource conservation, simple process, and high industrialization degree, significantly reducing the consumption of petroleum asphalt and carbon emissions, and generating significant economic, social, and ecological benefits.

[0006] To achieve the above object, the technical solution of the present invention is as follows:

[0007] In the first aspect, the present invention provides a biomass-activated waste rubber powder material, which is composed of bio-oil, biochar, biomass carbon dots, and waste rubber powder with a mass ratio of 0-20:0-20:0.1-1:59-89.9.

[0008] Further, the biomass-activated waste rubber powder material is a viscoelastic solid, and the viscosity at 60 °C is 176-900 mm 2 / s, flash point ≥ 220 °C, saturated fraction content ≤ 30%, viscosity ratio before and after thin film oven test ≤ 3, mass change after thin film oven test ≤ 4 and ≥ -4.

[0009] In a second aspect, the present invention provides a method for preparing the biomass-activated waste rubber powder material described in the first aspect, comprising the following steps: mixing bio-oil, biochar, biomass carbon dots and waste rubber powder in proportion, and subjecting them to microwave activation to obtain biomass-activated waste rubber powder.

[0010] Further, the irradiation power of the microwave activation is 1000 - 2000 W, the irradiation time is 60 - 180 s, and the irradiation temperature is 600 - 1000 °C.

[0011] Further, the methods for preparing the bio-oil, biochar, and biomass carbon dots include the following steps:

[0012] Step 1: Mix biomass, acetic acid, and water, and subject them to hydrothermal reaction to obtain a mixture of bio-oil, biochar, and biomass carbon dots;

[0013] Step 2: Rinse the mixture of bio-oil, biochar, and biomass carbon dots with acetone to obtain a reaction mixture, and subject the reaction mixture to vacuum filtration to obtain a water-containing biochar solid and a bio-oil-containing liquid;

[0014] Step 3: Dry the water-containing biochar solid to obtain biochar, and select a part of the biochar for grinding and dialysis to obtain biomass carbon dots;

[0015] Step 4: Dry the bio-oil-containing liquid to remove the acetone solvent to obtain bio-oil.

[0016] Further, the biomass in step 1 is selected from at least one of wood chips, straw, and algae.

[0017] Further, the dosage ratio of biomass, acetic acid, and water in step 1 is 10 g: 5 ml: 100 ml.

[0018] Further, the temperature of the hydrothermal reaction in step 1 is 200 °C - 280 °C, and the time is 30 min - 12 h.

[0019] In a third aspect, the present invention provides the application of the biomass-activated waste rubber powder material described in the first aspect in recycling waste asphalt.

[0020] Further, it includes the following steps: extracting waste asphalt mixture to obtain waste asphalt, adding 15-35% biomass-activated waste rubber powder, stirring at a low speed of 200-500 rpm at a high temperature of 180-190 °C for 1 h, and then shearing at a high speed of 2000-8000 rpm for 1-2 h to obtain biomass-activated waste rubber powder recycled asphalt. In this technical solution, the softening point difference of the biomass-activated waste rubber powder recycled asphalt does not exceed 2 °C, and the volatile organic compound emission is lower than 10 mg / m 3 , having good storage stability and fluorescence effect, and meeting the road use requirements.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] The method of the present invention can greatly reduce the stockpiles of biomass, waste tires, and waste asphalt mixtures, improve the comprehensive utilization efficiency of multi-source solid wastes such as biomass, waste tires, and waste asphalt mixtures, improve the ecological environment of highways, reduce carbon emissions, and is of great significance for the popularization and application of multi-source solid wastes in highway engineering. Description of the Drawings

[0023] Figure 1 It is a process route diagram for the preparation of bio-oil, biochar, and biomass carbon dots.

[0024] Figure 2 It is the infrared spectrum of the mixture of bio-oil, biochar, and biomass carbon dots in Examples 1-3.

[0025] Figure 3 It is the infrared spectrum of the biomass-activated waste rubber powder recycled asphalt in Examples 1-3.

[0026] Figure 4 It is the fluorescence diagram of the biomass-activated waste rubber powder recycled asphalt in Examples 1-3. Detailed Embodiments

[0027] To facilitate the understanding of the present invention, the present invention will be described more comprehensively below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0028] Example 1

[0029] Preparation of Biomass-Activated Waste Rubber Powder

[0030] Step 1: Mix biomass (sawdust and straw mixed in a mass ratio of 1:1, passed through a 200-mesh standard sieve, and the undersize part was taken), acetic acid, and water in a ratio of 10 g, 5 ml, and 100 ml, and keep it warm in a hydrothermal reaction kettle at a high temperature and high pressure of 200 °C for 6 h to obtain a mixture of bio-oil, biochar, and biomass carbon dots. The infrared spectrum of the mixture is asFigure 2 as shown;

[0031] Step 2: Rinse the mixture with acetone for 30 min to obtain a reaction mixture, and vacuum filter the reaction mixture to obtain a moisture-containing biochar solid and a bio-oil-containing liquid;

[0032] Step 3: Dry the moisture-containing biochar solid at 105 °C for 12 h to obtain biochar. Select a part of the biochar and grind it for 1 h, and dialyze it through a 100 Dalton dialysis bag in a distilled water system to obtain biomass carbon dots (see Figure 1 );

[0033] Step 4: Dry the bio-oil-containing liquid at 50 °C to remove the acetone solvent to obtain bio-oil. Thus, all biomass materials of bio-oil, biochar, and biomass carbon dots are obtained;

[0034] Step 5: Mix bio-oil, biochar, biomass carbon dots, and waste rubber powder in a mass ratio of 20:2:0.1:77.9, and stir at a low speed of 300 rpm for 1 h to make them fully mixed and uniform;

[0035] Step 6: Activate the waste rubber powder by microwave under the conditions of a microwave irradiation power of 1000 W, an irradiation time of 180 s, and a microwave irradiation temperature of 600 °C to obtain biomass-activated waste rubber powder.

[0036] The above-mentioned biomass-activated waste rubber powder material is a viscoelastic solid, with a viscosity of 250 mm 2 / s at 60 °C, a flash point of 250 °C, a saturated fraction content of 28%, a viscosity ratio before and after the thin film oven test of 2.5, and a mass change of 1.2 after the thin film oven test.

[0037] Application of biomass-activated waste rubber powder

[0038] Step 1: Extract waste asphalt mixture using a fully automatic asphalt extractor to obtain waste asphalt;

[0039] Step 2: Incorporate 15% of biomass-activated waste rubber powder, stir at a low speed of 300 rpm at 185 °C for 1 h, and then shear at a high speed of 3000 rpm for 1 h to obtain biomass-activated waste rubber powder recycled asphalt.

[0040] The basic properties of the above-mentioned biomass-activated waste rubber powder recycled asphalt are shown in Table 1.

[0041] Table 1. Basic properties of biomass-activated waste rubber powder recycled asphalt

[0042]

[0043] As can be seen from Table 1, the density of the biomass-activated waste rubber powder recycled asphalt is 2.58 g / cm 3, the penetration is 61 dmm, the softening point is 57 °C, the ductility at 5 °C is 32 cm, the softening point difference is 1.5 °C, and the VOCs emission is 5.2 mg / m3, meeting the parameter requirements of medium-temperature rubber-modified asphalt in the CJJ-T 273-2019 Technical Standard for Rubber Asphalt Pavement, and having good storage stability and fluorescence effect. As Figure 3 shown, the infrared spectrum of biomass-activated waste rubber powder recycled asphalt shows that alkyl C-H stretching vibration appears at 2850 - 2920 cm -1 , C-H stretching vibration peak appears at 2700 - 2750 cm -1 , aldehyde group C=O stretching vibration appears at 1720 - 1740 cm -1 , S=O characteristic absorption peak appears at 1300 cm -1 , S=S characteristic absorption peak appears at 1030 cm -1 , and the characteristic absorption peak of natural rubber appears at 835 cm -1 . The fluorescence diagram of biomass-activated waste rubber powder recycled asphalt is as Figure 4 shown.

[0044] Example 2

[0045] Preparation of Biomass-Activated Waste Rubber Powder

[0046] Step 1: Mix biomass (sawdust and straw are mixed at a mass ratio of 1:1, passed through a 200-mesh standard sieve, and the undersize part is taken), acetic acid, and water in a ratio of 10 g, 5 ml, and 100 ml, and keep it at 280 °C under high temperature and high pressure in a hydrothermal reaction kettle for 12 h to obtain a mixture of bio-oil, biochar, and biomass carbon dots. The infrared spectrum of the mixture is as Figure 2 shown;

[0047] Step 2: Rinse the mixture with acetone for 30 min to obtain a reaction mixture, and the reaction mixture is vacuum filtered to obtain a water-containing biochar solid and a bio-oil-containing liquid;

[0048] Step 3: Dry the water-containing biochar solid at 105 °C for 12 h to obtain biochar. Select part of the biochar, grind it for 1 h, and dialyze it through a 100-Dalton dialysis bag in a distilled water system to obtain biomass carbon dots;

[0049] Step 4: Dry the bio-oil-containing liquid at 50 °C to remove the acetone solvent to obtain bio-oil. Thus, all biomass materials of bio-oil, biochar, and biomass carbon dots are obtained;

[0050] Step 5: Mix bio-oil, biochar, biomass carbon dots, and waste rubber powder in a mass ratio of 20:20:1:59, and stir at a low speed of 300 rpm for 1 h to make them fully mixed and uniform;

[0051] Step 6: Microwave activate waste rubber powder under the conditions of microwave irradiation power of 2000 W, irradiation time of 60 s, and microwave irradiation temperature of 1000 °C using a microwave oven to obtain biomass-activated waste rubber powder.

[0052] The above biomass-activated waste rubber powder material is a viscoelastic solid with a viscosity of 320 mm 2 / s at 60 °C, a flash point of 315 °C, a saturated fraction content of 27%, a viscosity ratio before and after the thin film oven test of 2.8, and a mass change of 1.1 after the thin film oven test.

[0053] Application of biomass-activated waste rubber powder

[0054] Step 1: Extract waste asphalt from waste asphalt mixture using a fully automatic asphalt extractor to obtain waste asphalt;

[0055] Step 2: Incorporate 35% biomass-activated waste rubber powder and stir at a low speed of 300 rpm for 1 h at a high temperature of 190 °C, and then shear at a high speed of 8000 rpm for 1 h to obtain biomass-activated waste rubber powder recycled asphalt.

[0056] The basic properties of the above biomass-activated waste rubber powder recycled asphalt are shown in Table 2.

[0057] Table 2. Basic properties of biomass-activated waste rubber powder recycled asphalt

[0058]

[0059] As can be seen from Table 2, the density of the biomass-activated waste rubber powder recycled asphalt is 2.65 g / cm 3 , the penetration is 48 dmm, the softening point is 72 °C, the ductility at 5 °C is 18 cm, the softening point difference is 1.9 °C, the VOCs emission is 3.5 mg / m3, meeting the parameter requirements of the hot zone rubber modified asphalt in the CJJ-T 273-2019 Rubber Asphalt Pavement Technical Standard, and having good storage stability and fluorescence effect. As Figure 3 shown, the infrared spectrum of the biomass-activated waste rubber powder recycled asphalt shows that alkyl C-H stretching vibration appears at 2860-2900 cm -1 , C-H stretching vibration peak appears at 2700-2750 cm -1 , aldehyde group C=O stretching vibration appears at 1710 cm -1 , alkyl C-C stretching vibration appears at 1420-1480 cm -1 , S=O characteristic absorption peak appears at 1300 cm -1 , and S=S characteristic absorption peak does not appear at 1030 cm -1 , proving that the S=S bond is completely broken. The fluorescence diagram of the biomass-activated waste rubber powder recycled asphalt is as Figure 4 shown.

[0060] Example 3

[0061] Preparation of Biomass-Activated Waste Rubber Powder

[0062] Step 1: Mix biomass (sawdust and straw mixed at a mass ratio of 1:1, passed through a 200-mesh standard sieve, and the undersize part was taken), acetic acid, and water in a ratio of 10 g, 5 ml, and 100 ml, and keep it at 200 °C under high temperature and pressure in a hydrothermal reactor for 30 min to obtain a mixture of bio-oil, biochar, and biomass carbon dots. The infrared spectrum of the mixture is as shown in Figure 2 shown;

[0063] Step 2: Rinse the mixture with acetone for 30 min to obtain a reaction mixture, and the reaction mixture is vacuum filtered to obtain a biochar solid containing moisture and a liquid containing bio-oil;

[0064] Step 3: Dry the biochar solid containing moisture at 105 °C for 12 h to obtain biochar. Select a part of the biochar, grind it for 1 h, and dialyze it through a 100-Dalton dialysis bag in a distilled water system to obtain biomass carbon dots;

[0065] Step 4: Dry the liquid containing bio-oil at 50 °C to remove the acetone solvent to obtain bio-oil. Thus, all biomass materials of bio-oil, biochar, and biomass carbon dots are obtained;

[0066] Step 5: Mix bio-oil, biochar, biomass carbon dots, and waste rubber powder in a mass ratio of 20:1:0.1:78.9, and stir at a low speed of 300 rpm for 1 h to make them fully mixed evenly;

[0067] Step 6: Activate the waste rubber powder by microwave under the conditions of a microwave irradiation power of 1500 W, an irradiation time of 120 s, and a microwave irradiation temperature of 800 °C to obtain biomass-activated waste rubber powder.

[0068] The above biomass-activated waste rubber powder material is a viscoelastic solid, with a viscosity of 300 mm 2 / s at 60 °C, a flash point of 308 °C, a saturate content of 26%, a viscosity ratio before and after the thin film oven test of 2.5, and a mass change of 1.5 after the thin film oven test.

[0069] Application of Biomass-Activated Waste Rubber Powder

[0070] Step 1: Extract waste asphalt mixture using a fully automatic asphalt extractor to obtain waste asphalt;

[0071] Step 2: Incorporate 20% of biomass-activated waste rubber powder, stir at a low speed of 300 rpm at 180 °C for 1 h, and then shear at a high speed of 2000 rpm for 1 h to obtain biomass-activated waste rubber powder recycled asphalt.

[0072] The basic properties of the above biomass-activated waste rubber powder recycled asphalt are shown in Table 3.

[0073] Table 3. Basic properties of biomass-activated waste rubber powder recycled asphalt

[0074]

[0075] As can be seen from Table 3, the density of the biomass-activated waste rubber powder recycled asphalt is 2.62 g / cm 3 , the penetration is 65 dmm, the softening point is 52 °C, the ductility at 5 °C is 38 cm, the softening point difference is 0.8 °C, and the VOCs emission is 4.5 mg / m3, meeting the parameter requirements of the cold-region rubber modified asphalt in the Technical Standard for Rubber Asphalt Pavement CJJ-T 273-2019, and having good storage stability and fluorescence effect. As Figure 3 shown, the infrared spectrum of the biomass-activated waste rubber powder recycled asphalt shows that alkyl C-H stretching vibration appears at 2860-2900 cm -1 , C-H stretching vibration peak appears at 2700-2750 cm -1 , aldehyde group C=O stretching vibration appears at 1720 cm -1 , alkyl C-C stretching vibration appears at 1420-1480 cm -1 , S=O characteristic absorption peak appears at 1300 cm -1 , S=S characteristic absorption peak appears at 1030 cm -1 , and the characteristic absorption peak of natural rubber appears at 835 cm -1 , indicating that the rubber is not fully vulcanized. The fluorescence diagram of the biomass-activated waste rubber powder recycled asphalt is as Figure 4 shown.

[0076] The above is only an example for better explaining the present invention, and it is not a limitation thereof. Any modification or equivalent replacement that does not depart from the spirit and scope of the present invention shall fall within the scope covered by the present invention.

Claims

1. A biomass-activated waste rubber powder material, characterized in that, The biomass-activated waste rubber powder material is composed of bio-oil, biochar, biomass carbon dots and waste rubber powder with a mass ratio of 0-20:0-20:0.1-1:59-89.

9.

2. The biomass-activated waste rubber powder material according to claim 1, wherein The biomass-activated waste rubber powder material is a viscoelastic solid with a viscosity of 176 - 900 mm 2 / s at 60 °C, a flash point of ≥220 °C, a saturated fraction content of ≤30%, a viscosity ratio before and after the thin film oven test of ≤3, and a mass change after the thin film oven test of ≤4 and ≥ -4.

3. The preparation method of the biomass-activated waste rubber powder material according to claim 1 or 2, characterized in that, It includes the following steps: Mix bio-oil, biochar, biomass carbon dots and waste rubber powder in proportion, and obtain biomass-activated waste rubber powder through microwave activation.

4. The preparation method of the biomass-activated waste rubber powder material according to claim 3, characterized in that, The irradiation power of the microwave activation is 1000-2000W, the irradiation time is 60-180s, and the irradiation temperature is 600-1000°C.

5. The preparation method of the biomass-activated waste rubber powder material according to claim 3, characterized in that, The preparation methods of the bio-oil, biochar and biomass carbon dots include the following steps: Step 1: Mix biomass, acetic acid and water, and obtain a mixture of bio-oil, biochar and biomass carbon dots through hydrothermal reaction; Step 2: Rinse the mixture of bio-oil, biochar and biomass carbon dots with acetone to obtain a reaction mixture, and the reaction mixture is vacuum filtered to obtain a water-containing biochar solid and a bio-oil-containing liquid; Step 3: Dry the water-containing biochar solid to obtain biochar, and select part of the biochar to grind and dialyze to obtain biomass carbon dots; Step 4: Dry the bio-oil-containing liquid to remove the acetone solvent to obtain bio-oil.

6. The preparation method of the biomass-activated waste rubber powder material according to claim 5, characterized in that, The biomass in Step 1 is selected from at least one of wood chips, straws and algae.

7. The preparation method of the biomass-activated waste rubber powder material according to claim 5, characterized in that, The dosage ratio of biomass, acetic acid and water in Step 1 is 10g:5ml:100ml.

8. The preparation method of the biomass-activated waste rubber powder material according to claim 5, characterized in that, The temperature of the hydrothermal reaction in Step 1 is 200°C - 280°C, and the time is 30min - 12h.

9. Application of the biomass-activated waste rubber powder material according to Claim 1 or 2 in recycling waste asphalt.

10. Use of the biomass-activated waste rubber powder material according to claim 9, characterized in that, It includes the following steps: Extract waste asphalt mixture to obtain waste asphalt, incorporate 15-35% of biomass-activated waste rubber powder, stir at a low speed of 200-500rpm at a high temperature of 180-190°C for 1h, and then perform high-speed shearing at 2000-8000rpm for 1-2h to obtain biomass-activated waste rubber powder recycled asphalt.

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