Low-volatility environment-friendly softening oil, and preparation method and application thereof

Abstract

The present application belongs to the technical field of building materials, and discloses a low-volatility environment-friendly softening oil, a preparation method and application thereof. The low-volatility environment-friendly softening oil comprises the following raw materials in mass fraction: 100 parts of FCC oil slurry, 10-40 parts of reduced line oil, and 1-10 parts of coffee residue biochar loaded with nano zero-valent metal. The present application blends the FCC oil slurry rich in aromatic components with the reduced line oil rich in saturated components as the base raw material of the softening oil, and uses coffee residue biochar as the smoke suppressant matrix, and uses the green and environment-friendly process to load the nano zero-valent metal on the coffee residue biochar, thereby improving the adsorption and degradation of the volatile smoke of the FCC oil slurry and the reduced line oil, so as to form the low-volatility environment-friendly softening oil. The polymer modified asphalt waterproof roll material using the softening oil has excellent high and low temperature performance and aging resistance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of building materials, and particularly relates to a low-volatility environment-friendly softening oil as well as a preparation method and application thereof. BACKGROUND

[0002] Polymer modified bitumen waterproofing membrane has been widely used in building waterproofing engineering due to its excellent high and low temperature performance and easy construction characteristics. The main raw materials of polymer modified bitumen waterproofing membrane include bitumen, polymer modifier (such as SBS, rubber powder, etc.), softening oil, filler and polyester base, wherein the role of softening oil is to improve the low temperature flexibility of waterproofing membrane. Commonly used softening oils include thread-cutting oil, naphthenic oil and recycled waste engine oil, etc. However, these softening oils have high saturated content and relatively low aromatic content, resulting in low joint peeling strength and poor aging resistance of waterproofing membrane.

[0003] Heavy oil produced in the process of petroleum refining can be converted into gasoline, diesel and liquefied gas and other light oils through catalytic cracking (FCC). FCC slurry is part of the material separated from the catalytic cracking unit to improve the yield and processing capacity of light oil, and the main components are aromatic, saturated and resin, wherein the content of aromatic is more than 50%. Since FCC slurry contains a large amount of aromatic, it can be blended with vacuum distillation side cut oil (thread-cutting oil) with high saturated content to adjust the ratio of saturated and aromatic in thread-cutting oil, thereby providing high-quality softening oil for polymer modified bitumen waterproofing membrane. However, FCC slurry contains a large amount of volatile components, which will release harmful smoke during the preparation of waterproofing membrane, not only having an adverse effect on human health, but also accelerating the aging of waterproofing membrane, thereby limiting its application. SUMMARY

[0004] The technical problem to be solved by the present application is to provide a low-volatility environment-friendly softening oil, a preparation method and application thereof, aiming at the deficiencies in the prior art. The aromatic-rich FCC slurry is blended with the saturated-rich thread-cutting oil, coffee grounds biochar is used as a smoke suppressant matrix, and green and environmentally friendly process is used to load nano zero-valent metal on the coffee grounds biochar, thereby improving the adsorption and degradation of volatile smoke of FCC slurry and thread-cutting oil, and improving the aging resistance of polymer modified bitumen waterproofing membrane.

[0005] To solve the technical problems proposed in the present application, the present application provides a low-volatility environment-friendly softening oil, which comprises the following raw materials in mass fraction: 100 parts of FCC slurry, 50-150 parts of thread-cutting oil and 1-5 parts of nano zero-valent metal loaded coffee grounds biochar.

[0006] Preferably, the low-volatility environment-friendly softening oil comprises the following raw materials in mass fraction: 100 parts of FCC slurry, 80-120 parts of thread-cutting oil and 2-3 parts of nano zero-valent metal loaded coffee grounds biochar.

[0007] In the scheme, the FCC oil slurry has a condensation point of 15-25 DEG C, a density of 1.03-1.07 g / cm 3 , a saturated fraction content of 20-30%, and an aromatic fraction content of 50-65%.

[0008] In the scheme, the reduced oil is a second reduced oil or a third reduced oil, has a condensation point of -5 to -20 DEG C, a density of 0.8-1.0 g / cm 3 , a saturated fraction content of 50-65%, and an aromatic fraction content of 20-40%.

[0009] In the scheme, the preparation method of the nano zero-valent metal loaded coffee grounds biochar comprises the following steps:

[0010] 1) Sohxlet extraction is performed on the coffee grounds by using an ethanol solution as an extractant to obtain an extraction liquid and an extraction residue;

[0011] 2) After drying the extraction residue, carbonization is performed under sealed anaerobic conditions at a temperature rising to obtain coffee grounds biochar;

[0012] 3) After dissolving a metal salt in water and adjusting the pH by using a sodium hydroxide solution, the coffee grounds biochar and the extraction liquid are uniformly mixed, and then polyethylene glycol is added, and then temperature rising and stirring are performed for reaction, after which solid-liquid separation is performed, and the solid is dried to obtain the nano zero-valent metal loaded coffee grounds biochar.

[0013] Further, the volume fraction of the ethanol solution is 60-80%.

[0014] Further, the mass of the coffee grounds to the volume of the ethanol solution is (5-10) g:200 mL.

[0015] Further, the particle size of the coffee grounds is 100-500 mesh.

[0016] Further, the extraction temperature of the Sohxlet extraction is 95-105 DEG C, and the extraction time is 2-4 h.

[0017] Further, the extraction residue is dried by using a vacuum drying method, the drying temperature is 70-90 DEG C, and the drying time is 6-12 h.

[0018] Further, the temperature rising rate of the carbonization is 10-15 DEG C / min, the carbonization temperature is 400-600 DEG C, and the carbonization time is 2-4 h.

[0019] Further, the particle size of the coffee grounds biochar is 100-500 mesh.

[0020] Further, the metal salt is one of an iron salt, a copper salt, and a zinc salt.

[0021] Preferably, the metal salt is one of FeSO4.7H2O, CuSO4.6H2O, ZnSO4.7H2O.

[0022] Further, the mass of the metal salt and the volume of water are in a ratio of (0.01-0.05) mol:100 mL.

[0023] Further, the concentration of the sodium hydroxide solution is 0.1-0.2 mol / L, the pH is adjusted to 5-6, and after adjustment, ultrasonic treatment is performed for 5-15 min.

[0024] Further, the molar amount of the metal salt and the mass of the coffee grounds are in a ratio of (0.02-0.06) mol:10 g.

[0025] Further, the mass of the polyethylene glycol and the volume of water are in a ratio of (0.1-2 g):100 mL.

[0026] Further, the reaction temperature in step 3) is 60-80 DEG C, and the reaction time is 2-4 h.

[0027] Further, the drying temperature in step 3) is 100-115 DEG C, and the drying time is 2-4 h.

[0028] In the above scheme, the particle size of the nano zero-valent metal loaded coffee grounds biochar is 100-500 mesh, the specific surface area is 300-800 m 2 / g, and the total pore volume is 0.1-0.5 cm 3 / g.

[0029] The application also provides a preparation method of low-volatile environment-friendly softening oil, comprising the following steps:

[0030] The FCC oil slurry, the reduced line oil, and the nano zero-valent metal loaded coffee grounds biochar are placed in a stirrer for blending, the blending temperature is 60-90 DEG C, the blending time is 20-60 min, and the low-volatile environment-friendly softening oil is obtained.

[0031] The application also provides an application of the low-volatile environment-friendly softening oil in polymer modified asphalt waterproof roll materials.

[0032] In the above scheme, the addition amount of the low-volatile environment-friendly softening oil in the polymer modified asphalt waterproof roll materials is 10-40% of the mass of the asphalt.

[0033] Compared with the prior art, the application has the following beneficial effects:

[0034] Firstly, traditional polymer-modified bitumen waterproof membranes use softening oils (such as line-reducing oil, waste engine oil, and naphthenic oil) with high saturation content and low aromatic content, resulting in low joint peel strength and poor aging resistance. This invention blends aromatic-rich FCC slurry with saturated line-reducing oil to adjust the content of each component in the softening oil, providing a high-quality softening oil for polymer-modified bitumen waterproof membranes.

[0035] Secondly, the biochar prepared from coffee grounds in this invention has a large specific surface area and porous structure, exhibiting excellent adsorption effects on volatile organic compounds released from FCC oil slurry and anti-corrosion oil. Simultaneously, coffee grounds are rich in natural antioxidants—polyphenols (tannins, catechins, and flavonoids, etc.) and organic acids (cinnamic acid and vanillic acid, etc.)—which can significantly improve the anti-aging properties of polymer-modified bitumen waterproof membranes.

[0036] Thirdly, this invention utilizes polyphenolic hydroxyl compounds such as tannins and catechins in coffee grounds extract to reduce FeSO4·7H2O, CuSO4·6H2O, or ZnSO4·7H2O, thus preparing nano-zero-valent metals. These nano-zero-valent metals possess a unique "shell-core" structure, with a thin layer of metal oxide on the surface and a dense zero-valent metal core inside. They exhibit a large specific surface area and high reactivity, enabling the adsorption and degradation of small-molecule fumes from FCC slurry and reduced-strength oil. The nano-zero-valent metals in softened oil can also terminate the free radicals formed during asphalt aging through redox reactions, thereby improving the anti-aging performance of waterproof membranes. However, nano-zero-valent metals are prone to agglomeration. This invention loads the nano-zero-valent metals onto coffee grounds biochar, achieving uniform dispersion of the nano-zero-valent metals on the coffee grounds biochar. This not only solves the problem of agglomeration of nano-zero-valent metals, enhancing their dispersibility and stability, but also improves the adsorption efficiency and capacity of coffee grounds biochar for FCC slurry fumes. Attached Figure Description

[0037] Figure 1 The image shown is a scanning electron microscope (SEM) image of the coffee grounds biochar prepared in step 2) of Example 1.

[0038] Figure 2 Scanning electron microscope image of pure nano-zero valent iron.

[0039] Figure 3 Scanning electron microscope image of coffee grounds biochar supported on nano-zero valent iron prepared in Example 1. Detailed Implementation

[0040] To better understand the present invention, the following embodiments further illustrate the content of the present invention, but the content of the present invention is not limited to the following embodiments.

[0041] The raw materials used in the following examples of the present application are all commercially available, and all reagents used in the examples are commercially available or are synthesized according to conventional methods and can be used directly without further treatment, and the instruments used in the examples are all commercially available.

[0042] Example 1

[0043] A low-volatility environmentally friendly softening oil comprises the following raw materials by mass fraction: 100 parts of FCC slurry, 120 parts of thread-cutting oil, and 3 parts of nano zero-valent iron-loaded coffee grounds biochar. The FCC slurry, thread-cutting oil, and nano zero-valent metal-loaded coffee grounds biochar are placed in a blender for blending, the blending temperature is 90°C, and the blending time is 20 min, thereby obtaining the low-volatility environmentally friendly softening oil. Among them:

[0044] The FCC slurry has a freezing point of 18°C, a density of 1.037 g / cm 3 , a saturated fraction content of 28.12%, and an aromatic fraction content of 54.59%;

[0045] The thread-cutting oil is thread-cutting oil No. 3, has a freezing point of -8°C, a density of 0.842 g / cm 3 , a saturated fraction content of 56.82%, and an aromatic fraction content of 33.58%;

[0046] The nano zero-valent iron-loaded coffee grounds biochar is prepared by the following method:

[0047] 1) 10 g of dry coffee grounds with a particle size of 200 mesh are wrapped in filter paper and placed in a Soxhlet extractor, and a 200 mL ethanol solution with a volume fraction of 70% is prepared as an extractant to extract the coffee grounds by Soxhlet extraction, the extraction temperature is 95°C, and the extraction time is 4 h, thereby obtaining an extract and an extraction residue;

[0048] 2) The entire extraction residue obtained in step 1) is placed in a vacuum drying oven at 80°C for 12 h to fully dry, and then it is placed in a tube furnace and carbonized under sealed anaerobic conditions, the heating rate is 10°C / min, the carbonization temperature is 500°C, and the carbonization time is 4 h, thereby obtaining coffee grounds biochar with a particle size of 200 mesh;

[0049] 3) 0.05 mol of FeSO4·7H2O is dissolved in 100 mL of deionized water, and then a 0.1 mol / L sodium hydroxide solution is used to adjust the pH to 5.5, and after adjustment, ultrasonic treatment is performed for 15 min, then the entire coffee grounds biochar obtained in step 2) and the entire extract obtained in step 1) are mixed uniformly, 1 g of polyethylene glycol (4000) is then added, and the temperature is raised to 70°C for stirring reaction for 4 h, after the reaction is completed, solid-liquid separation is performed, and the solid is dried in an oven at 100°C for 4 h, thereby obtaining nano zero-valent iron-loaded coffee grounds biochar with a particle size of 200 mesh.

[0050] Figure 1 The scanning electron microscope image of the coffee grounds biochar prepared in Example 1 can be seen that it is a porous structure and the surface is smooth without load. Figure 2 The scanning electron microscope image of the pure nano zero-valent iron can be seen that it shows the characteristics of easy agglomeration. Figure 3 The scanning electron microscope image of the coffee grounds biochar loaded with nano zero-valent iron prepared in Example 1 can be seen that there are uniformly dispersed nano zero-valent iron on the surface of the coffee grounds biochar.

[0051] It is detected that the specific surface area of the coffee grounds biochar loaded with nano zero-valent iron is 742 m 2 / g, the total pore volume is 0.388 cm 3 / g, the porous structure of the biochar is retained, it has a large specific surface area and reactivity, and the nano zero-valent iron is successfully loaded on the coffee grounds biochar, solving the problem of easy agglomeration of nano zero-valent metal.

[0052] Comparative Example 1-1

[0053] The difference between Comparative Example 1-1 and Example 1 is only that in the low-volatile environmentally friendly softening oil, the coffee grounds biochar loaded with nano zero-valent iron is not added.

[0054] Comparative Example 1-2

[0055] The difference between Comparative Example 1-2 and Example 1 is only that in the low-volatile environmentally friendly softening oil, the coffee grounds biochar loaded with nano zero-valent iron is replaced by the same mass of coffee grounds biochar prepared in step 2).

[0056] The physical properties and harmful substance concentrations in volatile substances of the low-volatile environmentally friendly softening oil prepared in Example 1 and Comparative Examples 1-1 and 1-2 are tested.

[0057] (1) Physical property test: The freezing point, 60℃ viscosity and 163℃ evaporation loss of the softening oil were tested according to “GB / T 510-2018 Petroleum Products Determination of Freezing Point”, “JTG E20-T0625-2011 Bitumen Rotational Viscosity Test (Brookfield Viscosimeter Method)”, “GB / T11964-2008 Petroleum Bitumen Evaporation Loss Determination Method”, respectively, and the test results are shown in Table 1.

[0058] (2) Harmful substance concentration test in volatile matter: test the content of VOCs and H2S in the volatile matter of the softening oil, the test method is: weigh 100 g of the softening oil into a three-necked flask, place the three-necked flask in an oil bath, set the temperature to 180℃, close the opening of the flask, set the rotation speed to 300 rpm, stop after stirring for 1 h, take a KORNO GT-1000 type gas detector, set it to a double-channel detection mode, and detect the content of VOCs and H2S respectively, the test range is VOCs: 0-2000 ppm, H2S: 0-200 ppm, the resolution is 0.1 ppm, and the test results are shown in Table 1.

[0059] Table 1 Performance and volatile matter concentration of the softening oil prepared in Example 1 and Comparative Examples 1-1 and 1-2

[0060] Performance Example 1 Comparative Example 1-1 Comparative Example 1-2 Freezing point (°C) -2 -2 -2 Viscosity at 60°C (mPa-s) 45 40 48 Evaporation loss (%) 0.45 0.58 0.48 VOCs (ppm) 436 1947 968 [H2S (ppm)] 2.8 182 55.7

[0061] Application Example 1

[0062] The low-volatile environment-friendly softening oil prepared by the application is applied to a polymer modified asphalt waterproofing membrane, and one polymer modified asphalt waterproofing membrane is listed here, the components and the weight percentage of which are: 100 parts of asphalt, 10-40 parts of low-volatile environment-friendly softening oil, 4-12 parts of SBS elastomer, 30-40 parts of rubber powder, and 40-70 parts of filler.

[0063] The low-volatile environment-friendly softening oil prepared in Example 1 and Comparative Examples 1-1 and 1-2 is respectively applied to a polymer modified asphalt waterproofing membrane, and the specific components and the mass percentage of the polymer modified asphalt waterproofing membrane in use are: 100 parts of asphalt (softening point 49.3℃, 25℃ penetration 71 dmm), 30 parts of low-volatile environment-friendly softening oil, 8 parts of SBS elastomer, 40 parts of rubber powder, and 60 parts of filler. The specific preparation process is as follows:

[0064] a) weigh the measured parts of asphalt and low-volatile environment-friendly softening oil and put them into a modified tank, control the temperature to 140±5℃, and set the rotation speed to 300 rpm for stirring for 10 min;

[0065] b) add the measured parts of SBS elastomer to a, adjust the temperature to 180±5℃, and set the rotation speed to 4000 rpm for high-speed shearing for 60 min;

[0066] c) add the measured parts of rubber powder to b, adjust the temperature to 180±5℃, and set the rotation speed to 4000 rpm for high-speed shearing for 90 min;

[0067] d) add the measured parts of filler to c, adjust the temperature to 190±5℃, and set the rotation speed to 3000 rpm for high-speed shearing for 90 min;

[0068] e) The d is coated on both sides of the polyester base, the thickness of one side is controlled to be 1.5 mm, and polyethylene release film is covered on the upper and lower surfaces to obtain a polymer modified asphalt waterproof roll.

[0069] The physical properties and aging resistance of the polymer modified asphalt waterproof roll prepared by using the low-volatile environmentally friendly softening oil prepared in Example 1 and Comparative Examples 1-1 and 1-2 are tested.

[0070] (1) Physical property test: The high and low temperature properties of the polymer modified asphalt waterproof roll are tested according to the “Bitumen Softening Point Test - Ring and Ball Method” (GB / T 4507-2014) and “Test Methods for Building Waterproofing Membranes - Part 14: Low Temperature Flexibility of Asphalt Waterproofing Membranes” (GB / T 328.14-2007), respectively; the seam peel strength is tested according to “Test Methods for Building Waterproofing Membranes - Part 20: Seam Peel Strength of Asphalt Waterproofing Membranes” (GB / T 328.20-2007), and the test results are shown in Table 2.

[0071] (2) Aging resistance test: The polymer modified asphalt waterproof roll is placed in an oven at a temperature of 80°C for aging for 10 days, the softening point, low temperature flexibility and seam peel strength of the waterproof roll before and after aging are tested, the softening point increment, flexibility change and seam peel strength retention rate are calculated according to formula (1), formula (2) and formula (3), and the test results are shown in Table 2. The smaller the softening point increment and flexibility change before and after aging, and the higher the peel strength retention rate, the better the aging resistance of the waterproof roll.

[0072] Softening point increment = softening point after aging - softening point before aging (1)

[0073] Flexibility change = low temperature flexibility after aging - low temperature flexibility before aging (2)

[0074] Peel strength retention rate = peel strength after aging / peel strength before aging x 100% (3)

[0075] Table 2 Properties of the polymer modified asphalt waterproof roll prepared in Example 1 and Comparative Examples 1-1 and 1-2

[0076]

[0077] As can be seen from Table 1 and Table 2, the evaporation loss, VOCs concentration and H2S concentration of the softening oil prepared in Comparative Example 1-2 are much lower than those of Comparative Example 1-1, which is because the adsorption of the coffee grounds biochar significantly reduces the volatilization amount of VOCs and H2S after the softening oil is heated, and the polymer modified asphalt waterproof roll prepared by using the same has higher softening point and seam peeling strength and lower low-temperature flexibility, and has lower softening point increment and low-temperature flexibility change amount and higher seam peeling strength retention rate after heat aging, which indicates that the addition of the coffee grounds biochar makes the polymer modified asphalt have better high and low temperature performance and aging resistance; compared with Comparative Example 1-2, the evaporation loss, VOCs concentration and H2S concentration of the softening oil prepared in Example 1 are lower, which indicates that the coffee grounds biochar loaded with nano zero-valent metal more significantly reduces the volatilization amount of VOCs and H2S after the softening oil is heated, and the polymer modified asphalt waterproof roll prepared by using the same has higher softening point and seam peeling strength, lower low-temperature flexibility, smaller softening point increment and low-temperature flexibility change amount and higher seam peeling strength retention rate after heat aging, which indicates that the addition of the coffee grounds biochar loaded with nano zero-valent metal can make the polymer modified asphalt have more superior physical properties and aging resistance.

[0078] Example 2

[0079] A low-volatility environment-friendly softening oil, comprising the following raw materials in mass fraction: 100 parts of FCC oil slurry, 100 parts of thread-cutting oil, and 4 parts of coffee grounds biochar loaded with nano zero-valent copper. The FCC oil slurry, thread-cuting oil and coffee grounds biochar loaded with nano zero-valent metal are placed in a stirrer for blending, the blending temperature is 80°C, and the blending time is 30 min, thereby obtaining the low-volatility environment-friendly softening oil. Among them:

[0080] The FCC oil slurry has a freezing point of 20°C, a density of 1.041 g / cm 3 , a saturated fraction content of 22.57%, and an aromatic fraction content of 62.32%;

[0081] The thread-cutting oil is a thread-cutting oil No. 2, has a freezing point of -13°C, a density of 0.911 g / cm 3 , a saturated fraction content of 61.25%, and an aromatic fraction content of 25.17%;

[0082] The coffee grounds biochar loaded with nano zero-valent copper is prepared by the following method:

[0083] 1) 5 g of dry coffee grounds with a mesh size of 300 are wrapped in filter paper and placed in a Soxhlet extractor, 200 mL of ethanol solution with a volume fraction of 60% is prepared as an extractant, and the coffee grounds are subjected to Soxhlet extraction, the extraction temperature is 105°C, and the extraction time is 2 h, thereby obtaining an extract and an extraction residue;

[0084] 2) Put all the extraction residues obtained in step 1) into a vacuum drying oven at 90℃ for 8h to dry them sufficiently, and then put them into a tube furnace to be carbonized under sealed anaerobic conditions, with a heating rate of 15℃ / min, a carbonization temperature of 550℃, and a carbonization time of 3h, to obtain coffee residue biochar with a particle size of 300 mesh;

[0085] 3) After 0.03mol of CuSO4·6H2O is dissolved in 100mL of deionized water, adjust the pH to 5.5 with a sodium hydroxide solution with a concentration of 0.15mol / L, and then ultrasonic treat for 5min after adjustment, then mix all the coffee residue biochar obtained in step 2) and all the extraction liquid obtained in step 1) uniformly, and then add 1.5g of polyethylene glycol (4000), and then heat to 80℃ and stir for 2h, and then separate the solid and liquid after the reaction is completed, and dry the solid in an oven at 105℃ for 2.5h, to obtain nano zero-valent copper loaded coffee residue biochar with a particle size of 300 mesh.

[0086] It is detected that the specific surface area of the nano zero-valent copper loaded coffee residue biochar is 519m 2 / g, and the total pore volume is 0.344cm 3 / g.

[0087] Comparative Example 2-1

[0088] Comparative Example 2-1 differs from Example 2 only in that no nano zero-valent copper loaded coffee residue biochar is added to the low-volatility environmentally friendly softening oil.

[0089] Comparative Example 2-2

[0090] Comparative Example 2-2 differs from Example 2 only in that the nano zero-valent copper loaded coffee residue biochar is replaced with the same mass of coffee residue biochar prepared in step 2) in the low-volatility environmentally friendly softening oil.

[0091] The physical properties and harmful substance concentrations in volatiles of the low-volatility environmentally friendly softening oil prepared in Example 1 and Comparative Examples 1-1 and 1-2 are tested. The test results are shown in Table 3.

[0092] Table 3 Performance and volatile concentration of softening oil prepared in Example 2 and Comparative Examples 2-1 and 2-2

[0093] Performance Example 2 Comparative Example 2-1 Comparative Example 2-2 Freezing point (°C) -6 -6 -6 Viscosity at 60°C (mPa-s) 35 30 38 Evaporation loss (%) 0.50 0.61 0.55 VOCs (ppm) 372 1742 750 [H2S (ppm)] 1.6 192 43.6

[0094] Application Example 2

[0095] The low-volatility environment-friendly softening oil prepared in Example 2 and Comparative Examples 2-1 and 2-2 was applied to a polymer modified asphalt waterproofing membrane, and the specific composition and mass fraction of the polymer modified asphalt waterproofing membrane during application were as follows: asphalt (softening point 48.3℃, 25℃ penetration 73dmm) 100 parts, low-volatility environment-friendly softening oil 20 parts, SBS elastomer 6 parts, rubber powder 45 parts, and filler 57 parts.

[0096] The physical properties and aging resistance of the polymer modified asphalt waterproofing membrane after application of the low-volatility environment-friendly softening oil prepared in Example 2 and Comparative Examples 2-1 and 2-2 were tested. The test results are shown in Table 4.

[0097] Table 4 Performance of polymer modified asphalt waterproofing membranes prepared in Example 2 and Comparative Examples 2-1 and 2-2

[0098]

[0099] As can be seen from Tables 3 and 4, compared with Comparative Examples 2-1 and 2-2, the softening oil prepared in Example 2 has the lowest evaporation loss, VOCs concentration and H2S concentration, the highest softening point and seam peeling strength, the lowest low-temperature flexibility, the smallest softening point increment and low-temperature flexibility change after heat aging, and the highest seam peeling strength retention rate, which indicates that the addition of nano zero-valent metal loaded coffee grounds biochar significantly reduces the VOCs and H2S concentrations in the volatiles after heating of the softening oil, and effectively improves the physical properties and aging resistance of the polymer modified asphalt.

[0100] Example 3

[0101] A low-volatility environment-friendly softening oil, comprising the following mass fractions of raw materials: FCC oil slurry 100 parts, thread-cutting oil 80 parts, and nano zero-valent zinc loaded coffee grounds biochar 2 parts. The FCC oil slurry, thread-cutting oil and nano zero-valent metal loaded coffee grounds biochar were placed in a stirrer for blending, the blending temperature was 70℃, and the blending time was 40 min, thereby obtaining the low-volatility environment-friendly softening oil. Among them:

[0102] The FCC oil slurry has a freezing point of 17℃, a density of 1.055g / cm 3 , a saturated fraction content of 23.54%, and an aromatic fraction content of 58.14%;

[0103] The thread-cutting oil is a second thread-cutting oil, has a freezing point of -20℃, a density of 0.842g / cm 3 , a saturated fraction content of 56.82%, and an aromatic fraction content of 33.58%;

[0104] The nano zero-valent zinc loaded coffee grounds biochar was prepared by the following method:

[0105] 1) Take 8 g of dry coffee residue of 400 mesh, wrap it in filter paper, and place it in a Soxhlet extractor. Prepare 200 mL of 50% ethanol solution as the extracting agent. Perform Soxhlet extraction on the coffee residue at 100°C for 3 h to obtain an extract and an extraction residue;

[0106] 2) Dry the entire extraction residue obtained in step 1) in a vacuum drying oven at 85°C for 8 h, then place it in a tube furnace and heat it to carbonize under sealed anaerobic conditions. The heating rate is 15°C / min, the carbonization temperature is 600°C, and the carbonization time is 2 h. The coffee residue biochar obtained has a particle size of 400 mesh;

[0107] 3) Dissolve 0.03 mol of ZnSO4·7H2O in 100 mL of deionized water, adjust the pH to 6 with a 0.2 mol / L sodium hydroxide solution, and then ultrasonically treat for 10 min. Then, add all the coffee residue biochar obtained in step 2) and all the extract obtained in step 1) and mix well. Add 0.5 g of polyethylene glycol (4000), heat to 60°C, and stir for 4 h. After the reaction is completed, separate the solid and liquid, and dry the solid in an oven at 115°C for 2 h to obtain nano zero-valent zinc loaded coffee residue biochar with a particle size of 400 mesh.

[0108] The specific surface area of the nano zero-valent zinc loaded coffee residue biochar is 764 m 2 / g, and the total pore volume is 0.488 cm 3 / g.

[0109] Comparative Example 3

[0110] Comparative Example 3 differs from Example 3 only in that no nano zero-valent iron loaded coffee residue biochar is added to the low-volatile environmentally friendly softening oil.

[0111] The physical properties and harmful substance concentrations of the volatile substances of the low-volatile environmentally friendly softening oil prepared in Example 3 and Comparative Example 3 were tested. The test results are shown in Table 5.

[0112] Table 5 Properties and volatile substance concentrations of the softening oil prepared in Example 3 and Comparative Example 3

[0113]

[0114]

[0115] Application Example 3

[0116] The low-volatile environment-friendly softening oil prepared in Example 3 and Comparative Example 3 was applied to a polymer modified asphalt waterproofing membrane respectively. The specific composition and mass fraction of the polymer modified asphalt waterproofing membrane when applied were as follows: asphalt (softening point 49.5℃, 25℃ penetration 86dmm) 100 parts, low-volatile environment-friendly softening oil 25 parts, SBS elastomer 12 parts, rubber powder 40 parts, and filler 60 parts.

[0117] The physical properties and aging resistance of the polymer modified asphalt waterproofing membrane after application of the low-volatile environment-friendly softening oil prepared in Example 3 and Comparative Example 3 were tested. The test results are shown in Table 6.

[0118] Table 6 Performance of polymer modified asphalt waterproofing membrane prepared in Example 3 and Comparative Example 3

[0119]

[0120] From Tables 5 and 6, compared with Comparative Example 3, the VOCs and H2S values of the softening oil prepared in Example 3 were significantly reduced, the softening point and joint peeling strength and low-temperature flexibility of the polymer modified asphalt waterproofing membrane prepared therefrom were higher than those of Comparative Example 3, the softening point increment and low-temperature flexibility change after heat aging were lower than those of Comparative Example 3, and the joint peeling strength retention rate was higher than that of Comparative Example 3, indicating that the nano zero-valent metal loaded coffee grounds biochar effectively reduced the organic volatile matter generated by heating of the softening oil, and the polymer modified asphalt waterproofing membrane prepared therefrom had better physical properties and aging resistance.

[0121] The above examples are merely illustrative for the sake of clarity and are in no way limiting on the scope of the application. Other variations to those disclosed herein can be apparent to those having ordinary skill in the art and can be made without departing from the scope of the application. Accordingly, the disclosure is intended to embrace all such alternatives, modifications and variations as fall within the scope of the present application.

Claims

1. A low-volatility, environmentally friendly softening oil, characterized in that, The raw materials include the following parts by weight: 100 parts FCC oil slurry, 50-150 parts line-reducing oil, and 1-5 parts nano-zero-valent metal-supported coffee grounds biochar; The preparation method of the nano-zero-valent metal-supported coffee grounds biochar includes the following steps: 1) Using an ethanol solution with a volume fraction of 60-80% as the extractant, the coffee grounds were subjected to Soxhlet extraction. The mass ratio of coffee grounds to the volume of ethanol solution was (5-10) g: 200 mL. The extraction temperature was 95-105℃ and the extraction time was 2-4 h to obtain the extract and the extract residue. 2) After drying the extraction residue, carbonize it at 400-600℃ for 2-4 hours under sealed and oxygen-free conditions with a heating rate of 10-15℃ / min to obtain coffee ground biochar. 3) After dissolving the metal salt in water, adjust the pH to 5-6 with sodium hydroxide solution, then add coffee grounds biochar and extract and mix evenly. The metal salt is one of iron, copper, or zinc salts. The mass ratio of the metal salt to the coffee grounds used to prepare the coffee grounds biochar is controlled to be (0.02-0.06) mol: 10g. Then add polyethylene glycol, heat to 60-80℃ and stir for 2-4 hours. After the reaction is completed, separate the solid and liquid, dry the solid, and obtain nano-zero-valent metal-supported coffee grounds biochar. The nano-zero-valent metal in the coffee grounds biochar supported by the nano-zero-valent metal has a core-shell structure, with the shell being a metal oxide and the core being a zero-valent metal.

2. The low-volatility, environmentally friendly softening oil according to claim 1, characterized in that, The extraction residue was vacuum dried at a temperature of 70-90℃ for 6-12 hours.

3. The low-volatility, environmentally friendly softening oil according to claim 1, characterized in that, The molar ratio of the metal salt to the volume of water is (0.01~0.05) mol:100mL; the mass ratio of the polyethylene glycol to the volume of water is (0.1~2g):100mL; the concentration of the sodium hydroxide solution is 0.1~0.2mol / L, and the solution is ultrasonically treated for 5~15min after pH adjustment.

4. The low-volatility, environmentally friendly softening oil according to claim 1, characterized in that, The nano-sized zero-valent metal-supported coffee grounds biochar has a particle size of 100-500 mesh and a specific surface area of ​​300-800 m². 2 / g, total pore volume is 0.1~0.5 cm³ 3 / g.

5. The low-volatility, environmentally friendly softening oil according to claim 1, characterized in that, The FCC slurry has a pour point of 15~25℃ and a density of 1.03~1.07 g / cm³. 3 The saturated content is 20-30%, and the aromatic content is 50-65%; the reduced-line oil is a second- or third-line reduced-line oil, with a pour point of -5 to -20℃ and a density of 0.8-1.0 g / cm³. 3 The saturated content is 50-65%, and the aromatic content is 20-40%.

6. A method for preparing a low-volatility, environmentally friendly softening oil as described in any one of claims 1 to 5, characterized in that, Includes the following steps: FCC oil slurry, reduced-line oil, and nano-zero-valent metal-loaded coffee grounds biochar were placed in a mixer and blended at a temperature of 60-90°C for 20-60 minutes to obtain a low-volatility, environmentally friendly softened oil.

7. The application of a low-volatility, environmentally friendly softening oil as described in any one of claims 1 to 5 in polymer-modified bitumen waterproof membranes.

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