Water-in-oil type super-high solid content emulsified asphalt and method for preparing the same

Abstract

The application discloses an oil-in-water type super-high solid content emulsified asphalt and a preparation method thereof, and belongs to the field of road engineering materials. The oil-in-water type super-high solid content emulsified asphalt is prepared from petroleum asphalt, polymeric condensed polycyclic aromatic amide, polyglycerol acid ester, acrylic acid (ester) / behenyl alcohol polyether-25 methacrylate copolymer and hydrochloric acid solution in a specific proportion. Compared with the prior art, the oil-in-water type emulsified asphalt has super-high asphalt content, stability and high and low temperature performance, and when used as a cementing material, can solve problems such as slow opening traffic, low early strength and insufficient road performance caused by excessive water content, and can be used as a mixing type and a spraying type emulsified asphalt.

Description

Technical Field

[0001] This invention relates to the field of road engineering materials, specifically providing a water-in-oil type ultra-high solids content emulsified asphalt and its preparation method. Background Technology

[0002] Emulsified asphalt is a water-in-oil emulsion formed by dispersing asphalt droplets in water. It is widely used in road construction and maintenance due to its convenient construction, energy efficiency, environmental friendliness, and wide range of applications. However, traditional emulsified asphalt is mainly prepared by high-speed shearing or grinding of asphalt under the action of emulsifiers. The asphalt content of traditional emulsified asphalt is generally between 50-70%. In this case, the viscosity of the emulsion itself is low, thus failing to effectively bind the aggregates. Furthermore, the lower the asphalt content in emulsified asphalt, the higher the water content, resulting in excessive residual water content in the mixture. This requires a long time for the water to evaporate before achieving good bonding. In addition, the water in emulsified asphalt is difficult to completely evaporate, or requires an extremely long evaporation process, inevitably leaving water residue in the asphalt or mixture, thus reducing the road performance of the mixture. Increasing the asphalt content of emulsified asphalt can effectively improve the road performance of asphalt mixtures. However, due to limitations in current production processes, there are currently no research reports on water-in-oil type ultra-high asphalt content (>80%) emulsified asphalt. Summary of the Invention

[0003] This invention addresses the shortcomings of the prior art by providing a water-in-oil type ultra-high solids content emulsified asphalt with ultra-high asphalt content, stability, and high and low temperature performance.

[0004] A further technical objective of this invention is to provide a method for preparing the above-mentioned emulsified asphalt.

[0005] The technical solution adopted by this invention to solve its technical problem is: water-in-oil type ultra-high solids content emulsified asphalt, which is prepared from the following raw materials by mass percentage:

[0006]

[0007] The polycyclic aromatic hydrocarbon amide is composed of polycyclic aromatic hydrocarbon-12 amide and polycyclic aromatic hydrocarbon-16 amide;

[0008] The polyglycerol ester is composed of polyglycerol-10 myristate and polyglycerol-6 stearate.

[0009] As a preferred embodiment, the mass percentages of each raw material in the water-in-oil type ultra-high solids content emulsified asphalt of the present invention are as follows:

[0010]

[0011] Preferably, the petroleum asphalt is AH-70 asphalt and / or AH-90 asphalt. Petroleum asphalt constitutes the main component of the ultra-high solids content emulsified asphalt of this invention, accounting for over 80 wt%, allowing the performance advantages of the asphalt to be fully realized, and minimizing the impact of the emulsification process on the asphalt's performance.

[0012] Preferably, the mass ratio of polycyclic aromatic hydrocarbon-12 amide to polycyclic aromatic hydrocarbon-16 amide is (0.25-1.5):(0.25-1.5), and particularly preferably (0.5-1):(0.5-1). Polycyclic aromatic hydrocarbon-12 amide and polycyclic aromatic hydrocarbon-16 amide are dissolved in acidic water and asphalt, respectively, and work together to reduce interfacial tension. Since the polycyclic aromatic hydrocarbon carboxylic acid used to prepare the amides is obtained by oxidizing petroleum asphalt with a strong acid, these amides have a similar molecular structure to petroleum asphalt, allowing for better dissolution and dispersion in asphalt, thus enhancing their ability to reduce interfacial tension. Furthermore, the polycyclic aromatic hydrocarbon carboxylic acid obtained from the oxidation of asphalt has a molecular structure with polycyclic aromatic hydrocarbon as the core and multiple carboxylic acid groups connected around it. Therefore, the amide prepared is a multi-headed amide structure with polycyclic aromatic hydrocarbon as the core and multiple amide chains connected around it. On the one hand, it exhibits a strong ability to reduce interfacial tension. On the other hand, after protonation under acidic conditions, it carries the same positive charge and has a strong repulsive force between molecules, making it difficult for asphalt droplets to aggregate, thus enabling it to exist stably in the form of an emulsion.

[0013] Preferably, the polycyclic aromatic hydrocarbon-12 amide is generated by an amidation reaction of polycyclic aromatic hydrocarbon carboxylic acid and dodecylamine, wherein the polycyclic aromatic hydrocarbon carboxylic acid is obtained by oxidizing asphalt with a strong acid.

[0014] Preferably, the polycyclic aromatic hydrocarbon-16 amide is generated by an amidation reaction of polycyclic aromatic hydrocarbon carboxylic acid and hexadecylamine, and the polycyclic aromatic hydrocarbon carboxylic acid is obtained by oxidizing asphalt with a strong acid.

[0015] Preferably, the preparation method of polycyclic aromatic hydrocarbon-12 amide or polycyclic aromatic hydrocarbon-16 amide includes:

[0016] (1) The asphalt was chemically oxidized with a strong acid, and after separation and purification, polycyclic aromatic carboxylic acid was obtained.

[0017] (2) After adding polycyclic aromatic hydrocarbon carboxylic acid, dodecylamine or hexadecylamine, catalyst and solvent to the reaction vessel, seal the reaction vessel and replace the gas inside the vessel with N2;

[0018] (3) When the temperature inside the reactor reaches 160-180℃, turn on the stirring device and continue heating to 210-230℃. Maintain this temperature and pressure for 1-2 hours, then release the steam for 2-3 hours, and continue the reaction under vacuum for 3-5 hours. After the reaction is completed, lower the temperature to room temperature to obtain the crude product.

[0019] (4) The crude product was washed and filtered with acetone and then dried under vacuum to obtain polycyclic aromatic hydrocarbon-12 amide or polycyclic aromatic hydrocarbon-16 amide final product.

[0020] Preferably, the strong acid in step (1) is concentrated nitric acid.

[0021] Preferably, the asphalt is hard asphalt. Compared with ordinary base asphalt, hard asphalt has a higher content of resins and asphaltenes, and a higher content of polycyclic aromatic hydrocarbons (PAHs). Using it as a raw material for strong acid oxidation can yield more PAH carboxylic acids.

[0022] During the oxidation reaction, asphalt and concentrated nitric acid are mixed at a mass ratio of 1:(5-15), heated to 80-95℃ under stirring, and refluxed for 3-5 hours. After the reaction is completed, the mixture is cooled to room temperature and diluted with distilled water. Then, it is filtered through a 0.2-micron microporous membrane, and the remaining nitric acid in the filtrate is removed by vacuum distillation to obtain polycyclic aromatic carboxylic acid.

[0023] The preferred mass ratio of asphalt to concentrated nitric acid is 1:(8-12); the preferred oxidation reaction temperature is 85-95℃.

[0024] Preferably, the catalyst in step (2) is sodium hypophosphite and the solvent is sulfolane.

[0025] The mass ratio of polycyclic aromatic carboxylic acid to dodecylamine (or hexadecylamine) is 1:(2-5); the amount of catalyst added is 0.5-2% of the total mass of polycyclic aromatic carboxylic acid and dodecylamine (or hexadecylamine).

[0026] Preferably, the stirring speed in step (3) is 50-70 r / min, and more preferably 55-65 r / min.

[0027] Preferably, the vacuum drying temperature in step (4) is 60-80℃, and more preferably 65-75℃.

[0028] Preferably, the mass ratio of polyglycerol-10 myristate to polyglycerol-6 stearate is (0.25-1.5):(0.25-1.5), and particularly preferably (0.5-1):(0.5-1). Polyglycerol-10 myristate is dissolved in acidic water and is used as a nonionic surfactant in combination with the cationic emulsifier polycyclic aromatic hydrocarbon-12 amide. Under acidic conditions, the two components exhibit additive and synergistic effects in reducing interfacial tension and forming mixed micelles.

[0029] Preferably, the hydrochloric acid solution has a pH value of 1-4, and more preferably 1-2.

[0030] The present invention discloses a method for preparing water-in-oil type ultra-high solids content emulsified asphalt, comprising the following steps:

[0031] S1. Add polycyclic aromatic hydrocarbon-12 amide, polyglycerol-10 myristate and acrylate / behenol polyether-25 methacrylate copolymer to hot hydrochloric acid solution, stir evenly, and cool to obtain soap solution for later use;

[0032] S2. Polycyclic aromatic hydrocarbon-16 amide and polyglycerol-6 stearate are added to hot asphalt and stirred at high speed until homogeneous to obtain activated asphalt mixture for later use.

[0033] S3. Quickly add the soap solution obtained in step S1 to the activated asphalt mixture obtained in step S2 in one go, and continue stirring for a certain period of time to obtain high solids content emulsified asphalt.

[0034] The mass percentages of each component in the oil-in-water ultra-high solids emulsified asphalt are as follows:

[0035]

[0036] Preferably, in step S1, the temperature of the hot hydrochloric acid solution is 70-80℃, the temperature of the soap solution is 50-60℃, and the stirring rate is preferably 300-500 r / min. The specific method is as follows:

[0037] Heat water to 70-80℃, add hydrochloric acid to adjust the pH of the water to about 1-4, then add polycyclic aromatic hydrocarbon-12 amide, polyglycerol-10 myristate and acrylate / behenol polyether-25 methacrylate copolymer, stir evenly, and then cool to 50-60℃ under natural conditions to obtain soap solution.

[0038] Preferably, in step S2, the temperature of the hot asphalt is 110-140℃, and the stirring rate is 1000-2000 r / min. The specific method is as follows:

[0039] The asphalt is heated to 110-140℃, then polycyclic aromatic hydrocarbon-16 amide and polyglycerol-6 stearate are added, and the mixture is stirred at 1000-2000 r / min for 5-10 min to obtain an activated asphalt mixture, which is then maintained at this temperature. The stirring rate is particularly preferably 1000-1500 r / min.

[0040] Preferably, in step S3, the soap solution and activated asphalt mixture are stirred for 10-20 minutes at 110-140°C and a stirring rate of 800-1500 r / min to obtain high-solids-content emulsified asphalt. The stirring rate is particularly preferably 800-1200 r / min.

[0041] Compared with existing technologies, the water-in-oil type ultra-high solids content emulsified asphalt and its preparation method of the present invention have the following outstanding advantages:

[0042] (i) Polycyclic aromatic hydrocarbon amides are prepared by amidation reaction of hard asphalt with long-chain aliphatic amines after strong acid oxidation. They have a similar structure to asphalt components and can be better dispersed in asphalt. They also contain multiple amide groups, which can better reduce interfacial tension. In addition, the hydrophilic segments are protonated and carry the same positive charge, which prevents the aggregation of asphalt particles and maintains the stability of the emulsion.

[0043] (II) Both polycyclic aromatic hydrocarbon amides and polyglycerol esters are composed of oil-soluble and water-soluble materials. When water-soluble polycyclic aromatic hydrocarbon amides and polyglycerol esters are added to water, they dissolve and protonate under acidic conditions, reducing the surface tension of water. Oil-soluble polycyclic aromatic hydrocarbon amides and polyglycerol esters dissolve in asphalt, and together they reduce the surface tension of the asphalt, thus activating it. Under the synergistic effect of oil-soluble and water-soluble polycyclic aromatic hydrocarbon amides and polyglycerol esters, the interfacial tension between asphalt and water can be significantly reduced, thus allowing asphalt to disperse in water under relatively "low-energy" conditions.

[0044] (III) The applicant discovered that acrylate / behenol polyether-25 methacrylate copolymer exhibits excellent dispersibility in high-solids-content emulsified asphalt, demonstrating enhanced thickening ability and providing the emulsion with a certain degree of elastic recovery. It works synergistically with emulsifiers to stabilize high-solids-content emulsified asphalt. Simultaneously, this substance can form a thin film on the surface of the high-internal-phase emulsion, providing protection and sealing, helping to "lock in" moisture and prevent moisture loss. This avoids demulsification and phase inversion caused by the loss of small amounts of moisture in the high-solids-content emulsified asphalt due to evaporation.

[0045] (iv) The high-solids-content emulsified asphalt is prepared using a stirring method. Traditional emulsified asphalt preparation processes involve dispersing asphalt into a soap solution using high-speed shearing and grinding. However, the asphalt content in this process generally does not exceed 70%. Exceeding this limit may cause the emulsified asphalt to reverse, resulting in a sharp increase in viscosity that the emulsification equipment cannot withstand, forcing it to stop operating. This method, with the synergistic effect of selected polycyclic aromatic hydrocarbon amides and polyglycerol ester emulsifiers, adds the soap solution to the asphalt in one step under stirring. The water instantly vaporizes, breaking the oil-water interfacial tension, causing the asphalt to foam. This reduces the viscosity of the system, and the asphalt disperses into the water under stirring, forming an oil-in-water emulsion. Attached Figure Description

[0046] Appendix Figure 1 This is a diagram showing the dispersion effect of emulsified asphalt in water in Example 6;

[0047] Appendix Figure 2 This is a diagram illustrating the dispersion effect of emulsified asphalt in water, as shown in Comparative Example 2.

[0048] Appendix Figure 3 The graph shows the variation of the average particle size of ultra-high solids content emulsified asphalt with stirring time in Examples 6, 11, 12, 13, and 14. Detailed Implementation

[0049] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but this is not intended to limit the present invention.

[0050] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of this application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.

[0051] Material descriptions for various embodiments of the present invention:

[0052] Petroleum asphalt: AH-90 petroleum asphalt, penetration 83 (0.1 mm), emulsification point 46.5℃;

[0053] Hydrochloric acid, chemically pure, concentration 38%;

[0054]

Example 1

[0055] 1. Weigh a certain amount of hard asphalt and add it to a 250ml flask. Add 65% concentrated nitric acid at a ratio of 1:10, then heat to 90℃ with stirring and reflux for 4 hours. After cooling to room temperature, dilute with distilled water, then filter through a 0.2-micron microporous membrane. Remove the remaining nitric acid from the filtrate by vacuum distillation to obtain polycyclic aromatic carboxylic acids.

[0056] 2. First, polycyclic aromatic hydrocarbon carboxylic acid and dodecylamine are added to the reactor at a mass ratio of 1:3. Then, 1% sodium hypophosphite is added as a catalyst, and finally, 10 times the mass of the reactants is added as a solvent. The reactor is sealed, and the gas inside is replaced three times with N2.

[0057] 3. Turn on the heating device and turn on the stirring device when the internal temperature rises to 160℃. Set the stirring speed to 60r / min. Continue to raise the temperature to 210℃ and maintain this temperature and pressure for 1 hour. Then release the vapor for 2 hours and evacuate the vacuum for 4 hours. After the reaction is completed, lower the temperature to room temperature to obtain the crude product.

[0058] 4. The crude product was washed and filtered three times with acetone and then dried under vacuum at 70°C to obtain the final product.

[0059] [Example 2] Preparation method of polycyclic aromatic hydrocarbon-16 amide:

[0060] 1. Weigh a certain amount of hard asphalt and add it to a 250ml flask. Add 65% concentrated nitric acid at a ratio of 1:10, then heat to 90℃ with stirring and reflux for 4 hours. After cooling to room temperature, dilute with distilled water, then filter through a 0.2-micron microporous membrane. Remove the remaining nitric acid from the filtrate by vacuum distillation to obtain polycyclic aromatic carboxylic acids.

[0061] 2. First, polycyclic aromatic hydrocarbon carboxylic acid and hexadecylamine are added to the reactor at a mass ratio of 1:3. Then, 1% sodium hypophosphite is added as a catalyst, and finally, 10 times the mass of the reactants is added as a solvent. The reactor is sealed, and the gas inside is replaced three times with N2.

[0062] 3. Turn on the heating device and turn on the stirring device when the internal temperature rises to 170℃. Set the stirring speed to 60r / min. Continue to raise the temperature to 220℃ and maintain this temperature and pressure for 1 hour. Then release the vapor for 2 hours and evacuate the vacuum for 4 hours. After the reaction is completed, lower the temperature to room temperature to obtain the crude product.

[0063] 4. The crude product was washed and filtered three times with acetone and then dried under vacuum at 70°C to obtain the final product.

[0064] [Example 3] The raw materials used in an oil-in-water type ultra-high solids content emulsified asphalt are as follows:

[0065] 75wt% AH-90 asphalt, 1wt% polycyclic aromatic hydrocarbon-12 amide, 1wt% polycyclic aromatic hydrocarbon-16 amide, 1wt% polyglycerol-10 myristate, 1wt% polyglycerol-6 stearate, 0.5wt% acrylic (ester) / behenol polyether-25 methacrylate copolymer, 0.2wt% hydrochloric acid, and 20.3wt% water.

[0066] The preparation method of water-in-oil type ultra-high solids content emulsified asphalt is as follows:

[0067] 1. Heat water to 70℃, add hydrochloric acid to adjust the pH of the water to about 2, then add polycyclic aromatic hydrocarbon-12 amide, polyglycerol-10 myristate and acrylate / behenol polyether-25 methacrylate copolymer, stir at 400r / min for 20 minutes until uniform, then cool to 60℃ under natural conditions to obtain soap solution for later use.

[0068] 2. Heat the asphalt to 110℃, then add polycyclic aromatic hydrocarbon-16 amide and polyglycerol-6 stearate, and stir at 1000r / min for 10min to obtain an activated asphalt mixture. Maintain this temperature for later use.

[0069] 3. At the temperature and stirring rate described in step 2, the soap solution obtained in step 1 is quickly added to the activated asphalt mixture described in step 2 in one go, and stirring is continued for 10 minutes at a speed of 1000 r / min to obtain high solids content emulsified asphalt.

[0070] [Example 4] The raw materials used in a water-in-oil type ultra-high solids content emulsified asphalt are as follows:

[0071] AH-90 asphalt 82wt%, polycyclic aromatic hydrocarbon-12 amide 1wt%, polycyclic aromatic hydrocarbon-16 amide 1wt%, polyglycerol-10 myristate ester 1wt%, polyglycerol-6 stearate ester 1wt%, acrylate / behenyl alcohol polyether-25 methacrylate copolymer 0.5wt%, hydrochloric acid 0.2wt%, water 13.3wt%.

[0072] The preparation method of the water-in-oil type ultra-high solids content emulsified asphalt in this embodiment is the same as that in Embodiment 3.

[0073] [Example 5] The raw materials used in a water-in-oil type ultra-high solids content emulsified asphalt are as follows:

[0074] AH-90 asphalt 86wt%, polycyclic aromatic hydrocarbon-12 amide 1wt%, polycyclic aromatic hydrocarbon-16 amide 1wt%, polyglycerol-10 myristate ester 1wt%, polyglycerol-6 stearate ester 1wt%, acrylate / behenyl alcohol polyether-25 methacrylate copolymer 0.5wt%, hydrochloric acid 0.2wt%, water 9.3wt%.

[0075] The preparation method of the water-in-oil type ultra-high solids content emulsified asphalt in this embodiment is the same as that in Embodiment 3.

[0076] [Example 6] The raw materials used in a water-in-oil type ultra-high solids content emulsified asphalt are as follows:

[0077] AH-90 asphalt 88wt%, polycyclic aromatic hydrocarbon-12 amide 0.5wt%, polycyclic aromatic hydrocarbon-16 amide 0.5wt%, polyglycerol-10 myristate ester 0.5wt%, polyglycerol-6 stearate ester 0.5wt%, acrylate / behenol polyether-25 methacrylate copolymer 0.5wt%, hydrochloric acid 0.1wt%, water 9.4wt%.

[0078] The preparation method of the water-in-oil type ultra-high solids content emulsified asphalt in this embodiment is the same as that in Embodiment 3.

[0079] [Example 7] The raw materials used in an oil-in-water type ultra-high solids content emulsified asphalt are as follows:

[0080] AH-90 asphalt 88wt%, polycyclic aromatic hydrocarbon-12 amide 0.5wt%, polycyclic aromatic hydrocarbon-16 amide 1wt%, polyglycerol-10 myristate ester 0.5wt%, polyglycerol-6 stearate ester 1wt%, acrylate / behenyl alcohol polyether-25 methacrylate copolymer 0.5wt%, hydrochloric acid 0.2wt%, water 8.3wt%.

[0081] The preparation method of the water-in-oil type ultra-high solids content emulsified asphalt in this embodiment is the same as that in Embodiment 3.

[0082] [Example 8] The raw materials used in an oil-in-water type ultra-high solids content emulsified asphalt are as follows:

[0083] AH-90 asphalt 88wt%, polycyclic aromatic hydrocarbon-12 amide 1.5wt%, polycyclic aromatic hydrocarbon-16 amide 1.5wt%, polyglycerol-10 myristate ester 1wt%, polyglycerol-6 stearate ester 1wt%, acrylate / behenol polyether-25 methacrylate copolymer 0.5wt%, hydrochloric acid 0.3wt%, water 6.2wt%.

[0084] The preparation method of the water-in-oil type ultra-high solids content emulsified asphalt in this embodiment is the same as that in Embodiment 3.

[0085] [Example 9] The raw materials used in an oil-in-water type ultra-high solids content emulsified asphalt are as follows:

[0086] AH-90 asphalt 88wt%, polycyclic aromatic hydrocarbon-12 amide 1wt%, polycyclic aromatic hydrocarbon-16 amide 1wt%, polyglycerol-10 myristate ester 1wt%, polyglycerol-6 stearate ester 1wt%, acrylate / behenyl alcohol polyether-25 methacrylate copolymer 0.5wt%, hydrochloric acid 0.2wt%, water 7.3wt%.

[0087] The preparation method of water-in-oil type ultra-high solids content emulsified asphalt is as follows:

[0088] 1. Heat water to 70℃, add hydrochloric acid to adjust the pH of the water to about 2, then add polycyclic aromatic hydrocarbon-12 amide, polyglycerol-10 myristate and acrylate / behenol polyether-25 methacrylate copolymer, stir at 400r / min for 20 minutes until uniform, then cool to 60℃ under natural conditions to obtain soap solution for later use.

[0089] 2. Heat the asphalt to 110℃, then add polycyclic aromatic hydrocarbon-16 amide and polyglycerol-6 stearate, and stir at 1000r / min for 10min to obtain an activated asphalt mixture. Maintain this temperature for later use.

[0090] 3. At the temperature and stirring rate described in step 3, the soap solution obtained in step (2) is quickly added to the activated asphalt mixture described in step 2 in one go, and stirring is continued for 10 minutes at a speed of 1200 r / min to obtain high solids content emulsified asphalt.

[0091]

Example 10

[0092] The preparation method of water-in-oil type ultra-high solids content emulsified asphalt is as follows:

[0093] 1. Heat water to 70℃, add hydrochloric acid to adjust the pH of the water to about 2, then add polycyclic aromatic hydrocarbon-12 amide, polyglycerol-10 myristate and acrylate / behenol polyether-25 methacrylate copolymer, stir at 400r / min for 20 minutes until uniform, then cool to 60℃ under natural conditions to obtain soap solution for later use.

[0094] 2. Heat the asphalt to 110℃, then add polycyclic aromatic hydrocarbon-16 amide and polyglycerol-6 stearate, and stir at 1000r / min for 10min to obtain an activated asphalt mixture. Maintain this temperature for later use.

[0095] 3. At the temperature and stirring rate described in step 3, the soap solution obtained in step (2) is quickly added to the activated asphalt mixture described in step 2 in one go, and stirring is continued for 10 minutes at a speed of 800 r / min to obtain high solids content emulsified asphalt.

[0096]

Example 11

[0097] The preparation method of water-in-oil type ultra-high solids content emulsified asphalt is as follows:

[0098] 1. Heat water to 70℃, add hydrochloric acid to adjust the pH of the water to about 2, then add polycyclic aromatic hydrocarbon-12 amide, polyglycerol-10 myristate and acrylate / behenol polyether-25 methacrylate copolymer, stir at 400r / min for 20 minutes until uniform, then cool to 60℃ under natural conditions to obtain soap solution for later use.

[0099] 2. Heat the asphalt to 110℃, then add polycyclic aromatic hydrocarbon-16 amide and polyglycerol-6 stearate, and stir at 1000r / min for 10min to obtain an activated asphalt mixture. Maintain this temperature for later use.

[0100] 3. At the temperature and stirring rate described in step 3, the soap solution obtained in step (2) is quickly added to the activated asphalt mixture described in step 2 in one go, and stirring is continued for 1 minute at a speed of 1000 r / min to obtain high solids content emulsified asphalt.

[0101]

Example 12

[0102] The preparation method of water-in-oil type ultra-high solids content emulsified asphalt is as follows:

[0103] 1. Heat water to 70℃, add hydrochloric acid to adjust the pH of the water to about 2, then add polycyclic aromatic hydrocarbon-12 amide, polyglycerol-10 myristate and acrylate / behenol polyether-25 methacrylate copolymer, stir at 400r / min for 20 minutes until uniform, then cool to 60℃ under natural conditions to obtain soap solution for later use.

[0104] 2. Heat the asphalt to 110℃, then add polycyclic aromatic hydrocarbon-16 amide and polyglycerol-6 stearate, and stir at 1000r / min for 10min to obtain an activated asphalt mixture. Maintain this temperature for later use.

[0105] 3. At the temperature and stirring rate described in step 3, the soap solution obtained in step (2) is quickly added to the activated asphalt mixture described in step 2 in one go, and stirring is continued for 3 minutes at a speed of 1000 r / min to obtain high solids content emulsified asphalt.

[0106]

Example 13

[0107] 1. Heat water to 70℃, add hydrochloric acid to adjust the pH of the water to about 2, then add polycyclic aromatic hydrocarbon-12 amide, polyglycerol-10 myristate and acrylate / behenol polyether-25 methacrylate copolymer, stir at 400r / min for 20 minutes until uniform, then cool to 60℃ under natural conditions to obtain soap solution for later use.

[0108] 2. Heat the asphalt to 110℃, then add polycyclic aromatic hydrocarbon-16 amide and polyglycerol-6 stearate, and stir at 1000r / min for 10min to obtain an activated asphalt mixture. Maintain this temperature for later use.

[0109] 3. At the temperature and stirring rate described in step 3, the soap solution obtained in step (2) is quickly added to the activated asphalt mixture described in step 2 in one go, and stirring is continued for 5 minutes at a speed of 1000 r / min to obtain high solids content emulsified asphalt.

[0110]

Example 14

[0111] The preparation method of water-in-oil type ultra-high solids content emulsified asphalt is as follows:

[0112] 1. Heat water to 70℃, add hydrochloric acid to adjust the pH of the water to about 2, then add polycyclic aromatic hydrocarbon-12 amide, polyglycerol-10 myristate and acrylate / behenol polyether-25 methacrylate copolymer, stir at 400r / min for 20 minutes until uniform, then cool to 60℃ under natural conditions to obtain soap solution for later use.

[0113] 2. Heat the asphalt to 110℃, then add polycyclic aromatic hydrocarbon-16 amide and polyglycerol-6 stearate, and stir at 1000r / min for 10min to obtain an activated asphalt mixture. Maintain this temperature for later use.

[0114] 3. At the temperature and stirring rate described in step 3, the soap solution obtained in step (2) is quickly added to the activated asphalt mixture described in step 2 in one go, and stirring is continued for 20 minutes at a speed of 1000 r / min to obtain high solids content emulsified asphalt.

[0115] [Comparative Example 1] The raw materials used in a water-in-oil type ultra-high solids content emulsified asphalt are as follows:

[0116] AH-90 asphalt 88wt%, polycyclic aromatic hydrocarbon-12 amide 2wt%, polycyclic aromatic hydrocarbon-16 amide 2wt%, polyglycerol-10 myristate ester 0wt%, polyglycerol-6 stearate ester 0wt%, acrylate / behenyl alcohol polyether-25 methacrylate copolymer 0.5wt%, hydrochloric acid 0.4wt%, water 7.3wt%.

[0117] The preparation method of this comparative example of water-in-oil type ultra-high solids content emulsified asphalt is basically the same as that of Example 3, except that polyglycerol-10 myristate and polyglycerol-6 stearate (0 wt) are not added.

[0118] [Comparative Example 2] The raw materials used in a water-in-oil type ultra-high solids content emulsified asphalt are as follows:

[0119] AH-90 asphalt 88wt%, polycyclic aromatic hydrocarbon-12 amide 0wt%, polycyclic aromatic hydrocarbon-16 amide 0wt%, polyglycerol-10 myristate ester 2wt%, polyglycerol-6 stearate ester 2wt%, acrylate / behenyl alcohol polyether-25 methacrylate copolymer 0.5wt%, hydrochloric acid 0wt%, water 7.5wt%.

[0120] The preparation method of this comparative example of water-in-oil type ultra-high solids content emulsified asphalt is basically the same as that of Example 3, except that polycyclic aromatic hydrocarbon-12 amide, polycyclic aromatic hydrocarbon-16 amide, and hydrochloric acid are not added.

[0121] [Comparative Example 3] The raw materials used in a water-in-oil type ultra-high solids content emulsified asphalt are as follows:

[0122] AH-90 asphalt 88wt%, polycyclic aromatic hydrocarbon-12 amide 1wt%, polycyclic aromatic hydrocarbon-16 amide 1wt%, polyglycerol-10 myristate ester 1wt%, polyglycerol-6 stearate ester 1wt%, acrylate / behenyl alcohol polyether-25 methacrylate copolymer 0wt%, hydrochloric acid 0.2wt%, water 7.8wt%.

[0123] The preparation method of the comparative example of water-in-oil type ultra-high solids content emulsified asphalt is basically the same as that of Example 3, except that no acrylic (ester) / behenol polyether-25 methacrylate copolymer is added.

[0124] [Comparative Example 4] The raw materials used in a water-in-oil type ultra-high solids content emulsified asphalt are as follows:

[0125] AH-90 asphalt 88wt%, polycyclic aromatic hydrocarbon-12 amide 2wt%, polycyclic aromatic hydrocarbon-16 amide 0wt%, polyglycerol-10 myristate ester 2wt%, polyglycerol-6 stearate 0wt%, acrylate / behenyl alcohol polyether-25 methacrylate copolymer 0.5wt%, hydrochloric acid 0.2wt%, water 7.3wt%.

[0126] The preparation method of water-in-oil type ultra-high solids content emulsified asphalt is as follows:

[0127] 1. Heat water to 70℃, add hydrochloric acid to adjust the pH of the water to about 2, then add polycyclic aromatic hydrocarbon-12 amide, polyglycerol-10 myristate and acrylate / behenol polyether-25 methacrylate copolymer, stir at 400r / min for 20 minutes until uniform, then cool to 60℃ under natural conditions to obtain soap solution for later use.

[0128] 2. Heat the asphalt to 110℃ and maintain this temperature for later use.

[0129] 3. At the temperature and stirring rate described in step 3, the soap solution obtained in step (2) is quickly added to the asphalt in step 2 in one go, and stirring is continued for 10 minutes at a speed of 1000 r / min to obtain high solids content emulsified asphalt.

[0130] [Comparative Example 5] The raw materials used in a water-in-oil type ultra-high solids content emulsified asphalt are as follows:

[0131] AH-90 asphalt 88wt%, polycyclic aromatic hydrocarbon-12 amide 0wt%, polycyclic aromatic hydrocarbon-16 amide 2wt%, polyglycerol-10 myristate ester 0wt%, polyglycerol-6 stearate ester 2wt%, acrylate / behenyl alcohol polyether-25 methacrylate copolymer 0.5wt%, hydrochloric acid 0.2wt%, water 7.3wt%.

[0132] The preparation method of this comparative example of water-in-oil type ultra-high solids content emulsified asphalt is basically the same as that of Example 3, except that polycyclic aromatic hydrocarbon-12 amide and polyglycerol-10 myristate are not added.

[0133] [Comparative Example 6] The raw materials used in a water-in-oil type ultra-high solids content emulsified asphalt are as follows:

[0134] AH-90 asphalt 88wt%, polycyclic aromatic hydrocarbon-12 amide 4wt%, polycyclic aromatic hydrocarbon-16 amide 0wt%, polyglycerol-10 myristate ester 0wt%, polyglycerol-6 stearate ester 0wt%, acrylate / behenyl alcohol polyether-25 methacrylate copolymer 0.5wt%, hydrochloric acid 0.2wt%, water 7.3wt%.

[0135] The preparation method of this comparative example of water-in-oil type ultra-high solids content emulsified asphalt is basically the same as that of Example 3, except that polycyclic aromatic hydrocarbon-16 amide, polyglycerol-10 myristate and polyglycerol-6 stearate are not added.

[0136] [Comparative Example 7] The raw materials used in a water-in-oil type ultra-high solids content emulsified asphalt are as follows:

[0137] AH-90 asphalt 88wt%, polycyclic aromatic hydrocarbon-12 amide 0wt%, polycyclic aromatic hydrocarbon-16 amide 4wt%, polyglycerol-10 myristate ester 0wt%, polyglycerol-6 stearate ester 0wt%, acrylate / behenyl alcohol polyether-25 methacrylate copolymer 0.5wt%, hydrochloric acid 0.2wt%, water 7.3wt%.

[0138] The preparation method of this comparative example of water-in-oil type ultra-high solids content emulsified asphalt is basically the same as that of Example 3, except that polycyclic aromatic hydrocarbon-12 amide, polyglycerol-10 myristate and polyglycerol-6 stearate are not added.

[0139] [Comparative Example 8] The raw materials used in a water-in-oil type ultra-high solids content emulsified asphalt are as follows:

[0140] AH-90 asphalt 88wt%, polycyclic aromatic hydrocarbon-12 amide 0wt%, polycyclic aromatic hydrocarbon-16 amide 0wt%, polyglycerol-10 myristate ester 4wt%, polyglycerol-6 stearate ester 0wt%, acrylate / behenyl alcohol polyether-25 methacrylate copolymer 0.5wt%, hydrochloric acid 0.2wt%, water 7.3wt%.

[0141] The preparation method of this comparative example of water-in-oil type ultra-high solids content emulsified asphalt is basically the same as that of Example 3, except that polycyclic aromatic hydrocarbon-12 amide, polycyclic aromatic hydrocarbon-16 amide and polyglycerol-6 stearate are not added.

[0142] [Comparative Example 9] The raw materials used in a water-in-oil type ultra-high solids content emulsified asphalt are as follows:

[0143] AH-90 asphalt 88wt%, polycyclic aromatic hydrocarbon-12 amide 0wt%, polycyclic aromatic hydrocarbon-16 amide 0wt%, polyglycerol-10 myristate ester 0wt%, polyglycerol-6 stearate 4wt%, acrylate / behenyl alcohol polyether-25 methacrylate copolymer 0.5wt%, hydrochloric acid 0.2wt%, water 7.3wt%.

[0144] The preparation method of this comparative example of water-in-oil type ultra-high solids content emulsified asphalt is basically the same as that of Example 3, except that polycyclic aromatic hydrocarbon-12 amide, polycyclic aromatic hydrocarbon-16 amide and polyglycerol-10 myristate are not added.

[0145] Examples 3-15, Comparative Examples 1, 3, and 4: Due to the high asphalt content, ultra-high solids content emulsified asphalt has almost no fluidity at room temperature, making it impossible to use the T 0655 test method specified in the "Test Procedures for Asphalt and Asphalt Mixtures in Highway Engineering" (JTG E20-2011) to test the long-term storage stability of high-content emulsified asphalt. Therefore, the conductivity method was used to determine the dispersion state of the prepared emulsified asphalt in water to determine whether an oil-in-water emulsion was formed. For example, the emulsified asphalt in Example 6 could be dispersed in water to form an oil-in-water emulsion (e.g., ...). Figure 1 As shown in the figure), while the emulsified asphalt in Comparative Example 2 could not be dispersed in water (as shown in the figure). Figure 2 (As shown).

[0146] During the test, 1g of ultra-high solids content emulsified asphalt was dispersed in 100ml of water. First, the dispersion state of the ultra-high solids content emulsified asphalt in water was determined. If it could disperse in water, it indicated that water was the continuous phase, forming an oil-in-water emulsion. Then, the conductivity of the aqueous solution was tested using a conductivity meter. Since the conductivity of pure water and asphalt is close to zero, while the conductivity of soap solution is approximately 1600 μS / cm, if ultra-high solids content emulsified asphalt could disperse in asphalt, the conductivity value should be much greater than zero.

[0147] The initial particle size (1d) was used to determine the emulsification effect of ultra-high solids content emulsified asphalt; the smaller the particle size, the better the emulsification effect. Since the demulsification process of emulsified asphalt is a process in which the particle size gradually increases, the 30d particle size was further used to determine the storage stability of the emulsified asphalt.

[0148] Comparative Examples 2 and 5-9 were not dispersed, and their conductivity and particle size were not measured.

[0149] The test results are shown in the table below:

[0150]

[0151] As the data results above show, all ultra-high solids content emulsified asphalts in the embodiments exhibit good dispersion effects. After dispersion in water, they show high electrical conductivity, indicating the formation of an oil-in-water emulsion. Furthermore, the average particle size of the emulsions at 1 day and 30 days is low, indicating that this type of emulsified asphalt has good storage stability.

[0152] Examples 3, 4, 5, and 6 show that the average particle size of the emulsion tends to decrease with increasing asphalt content; Examples 6, 7, and 8 show that increasing the emulsifier content leads to a decrease in the average particle size of the emulsion, but the change is not significant; Examples 6, 9, and 10 show that increasing the rotation speed leads to a decrease in the average particle size of the emulsion, and the change is relatively significant; Examples 6, 11, 12, 13, and 14 show that increasing the stirring time leads to a decrease in the average particle size of the emulsion (e.g., ...). Figure 3 (As shown).

[0153] Comparative Example 1 uses only polycyclic aromatic hydrocarbon-12 amide and polycyclic aromatic hydrocarbon-16 amide. Although it can produce emulsified asphalt with high solids content, the emulsion will break down quickly if it is not used in combination with other substances. The synergistic effect of the substances is obvious.

[0154] Comparative Example 2 shows that using only two types of nonionic emulsifiers, polyglycerol-10 myristate and polyglycerol-6 stearate, combined with acrylic (ester) / behenol polyether-25 methacrylate copolymer, it is impossible to obtain emulsified asphalt with ultra-high solids content.

[0155] In Comparative Example 3, no acrylic (ester) / behend polyether-25 methacrylate copolymer was added during the asphalt activation process. Although high solids content emulsified asphalt could be obtained, the emulsion would break down quickly and become unusable.

[0156] Comparative Example 4, which simply uses polycyclic aromatic hydrocarbon-12 amide, polyglycerol-10 myristate, and acrylate / behenol polyether-25 methacrylate copolymer, also exhibits demulsification problems.

[0157] Comparative Example 5 shows that simply using oil-soluble polycyclic aromatic hydrocarbon-16 amide and polyglycerol-6 stearate with acrylate / behenol polyether-25 methacrylate copolymer cannot produce ultra-high solids content emulsified asphalt.

[0158] Comparative examples 6, 7, 8, and 9 also failed to produce emulsified asphalt with ultra-high solids content.

[0159] Obviously, the above embodiments are merely examples for clear illustration and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A water-in-oil type ultra-high solids content emulsified asphalt, characterized in that, It is produced from the following raw materials by weight percentage: Petroleum asphalt 80wt%-92wt%, Polycyclic aromatic hydrocarbon amides 0.5wt%-3wt%, Polyglycerol esters 0.5wt%-3wt%, Acrylic (ester) / behenol polyether-25 methacrylate copolymer 0.2wt%-1wt%, Remaining hydrochloric acid solution. The polycyclic aromatic hydrocarbon amide is composed of polycyclic aromatic hydrocarbon-12 amide and polycyclic aromatic hydrocarbon-16 amide, with a mass ratio of polycyclic aromatic hydrocarbon-12 amide to polycyclic aromatic hydrocarbon-16 amide of (0.25-1.5):(0.25-1.5). The polycyclic aromatic hydrocarbon-12 amide is generated by an amidation reaction of a polycyclic aromatic hydrocarbon carboxylic acid and dodecylamine, wherein the polycyclic aromatic hydrocarbon carboxylic acid is obtained by oxidation of asphalt with a strong acid. The polycyclic aromatic hydrocarbon-16 amide is generated by an amidation reaction of polycyclic aromatic hydrocarbon carboxylic acid and hexadecylamine, and the polycyclic aromatic hydrocarbon carboxylic acid is obtained by oxidizing asphalt with a strong acid. The polyglycerol ester is composed of polyglycerol-10 myristate and polyglycerol-6 stearate, with a mass ratio of polyglycerol-10 myristate to polyglycerol-6 stearate of (0.25-1.5):(0.25-1.5).

2. The water-in-oil type ultra-high solids content emulsified asphalt according to claim 1, characterized in that: The mass ratio of polycyclic aromatic hydrocarbon-12 amide to polycyclic aromatic hydrocarbon-16 amide is (0.5-1):(0.5-1).

3. The water-in-oil type ultra-high solids content emulsified asphalt according to claim 1, characterized in that: The mass ratio of polyglycerol-10 myristate to polyglycerol-6 stearate is (0.5-1):(0.5-1).

4. The water-in-oil type ultra-high solids content emulsified asphalt according to claim 1, 2 or 3, characterized in that: The pH value of the hydrochloric acid solution is 1-4.

5. A method for preparing water-in-oil type ultra-high solids content emulsified asphalt, characterized in that... Includes the following steps: S1. Add polycyclic aromatic hydrocarbon-12 amide, polyglycerol-10 myristate and acrylate / behenol polyether-25 methacrylate copolymer to hot hydrochloric acid solution, stir evenly, and cool to obtain soap solution for later use; S2. Polycyclic aromatic hydrocarbon-16 amide and polyglycerol-6 stearate are added to hot asphalt and stirred at high speed until homogeneous to obtain activated asphalt mixture for later use; S3. Quickly add the soap solution obtained in step S1 to the activated asphalt mixture obtained in step S2 in one go, and continue stirring for a certain period of time to obtain high solids content emulsified asphalt. The mass percentages of each component in the oil-in-water ultra-high solids emulsified asphalt are as follows: Petroleum asphalt 80wt%-92wt%, Polycyclic aromatic hydrocarbon-12 amide 0.25wt%-1.5wt%, Polycyclic aromatic hydrocarbon-16 amide 0.25wt%-1.5wt%, Polyglycerol-10 myristate ester 0.25wt%-1.5wt%, Polyglycerol-6 stearate 0.25wt%-1.5wt% Acrylic (ester) / behenol polyether-25 methacrylate copolymer 0.2wt%-1wt%, Remaining hydrochloric acid solution. The polycyclic aromatic hydrocarbon-12 amide is generated by an amidation reaction of a polycyclic aromatic hydrocarbon carboxylic acid and dodecylamine, wherein the polycyclic aromatic hydrocarbon carboxylic acid is obtained by oxidation of asphalt with a strong acid. The polycyclic aromatic hydrocarbon-16 amide is generated by an amidation reaction of polycyclic aromatic hydrocarbon carboxylic acid and hexadecylamine, and the polycyclic aromatic hydrocarbon carboxylic acid is obtained by oxidizing asphalt with a strong acid.

6. The method for preparing water-in-oil type ultra-high solids content emulsified asphalt according to claim 5, characterized in that: In step S1: the temperature of the hot hydrochloric acid solution is 70-80℃, and the temperature of the soap solution is 50-60℃.

7. The method for preparing water-in-oil type ultra-high solids content emulsified asphalt according to claim 5, characterized in that: In step S2: the temperature of the hot asphalt is 110-140℃, and it is stirred at a rate of 1500-2000 r / min for 5-10 min to obtain an activated asphalt mixture.

8. The method for preparing water-in-oil type ultra-high solids content emulsified asphalt according to claim 5, characterized in that: In step S3: The mixture of soap solution and activated asphalt is stirred for 10-20 minutes at 110-140℃ and 1500-2000 r / min to obtain high solids content emulsified asphalt.

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