Process for the production of modified emulsified bitumen
By using a combination of SBS modifier and specific surfactants to control the emulsification process and particle size, the problems of high and low temperature performance and stability of emulsified asphalt were solved, enabling large-scale production of modified emulsified asphalt.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SHANDONG EXPRESSWAY MATERIAL STORAGE & TRANSPORTATION CO LTD
- Filing Date
- 2023-08-22
- Publication Date
- 2026-07-24
AI Technical Summary
Existing emulsified asphalt modifiers cannot simultaneously achieve high-temperature and low-temperature performance, and SBS-modified emulsified asphalt has poor stability, making it difficult to achieve large-scale production.
By using SBS modifier and combining it with specific proportions of cationic, nonionic, and anionic surfactants, and through soap preparation, asphalt modification, and emulsification processes, particle size and emulsification conditions are controlled to improve the high and low temperature performance and storage stability of asphalt.
It achieves a balance between high and low temperature performance of modified emulsified asphalt, improves storage stability, and is suitable for large-scale production.
Smart Images
Figure BDA0004407614110000061 
Figure BDA0004407614110000071
Abstract
Description
Technical Field
[0001] This invention belongs to the field of road engineering technology, specifically relating to a production process for modified emulsified asphalt. Background Technology
[0002] Emulsified asphalt is widely used in road construction due to its excellent properties such as easy transportation and storage, superior performance, low construction difficulty, low energy consumption, and low pollution. However, unmodified emulsified asphalt has the defects of low-temperature clumping and high-temperature flowing, which greatly limits its application in terms of season and region. Therefore, it is necessary to modify emulsified asphalt to broaden its application range.
[0003] Currently, most emulsified asphalt modifications on the market involve adding modifiers such as SBR, chloroprene latex, and EVA emulsion. However, after being modified by these modifiers, the emulsified asphalt cannot maintain both high-temperature and low-temperature performance, nor can it comprehensively improve the performance of the modified emulsified asphalt, thus failing to meet the contemporary requirements for road surface performance.
[0004] SBS-modified asphalt can effectively improve the high and low temperature performance of asphalt and its elasticity, but it also increases the viscosity of the asphalt system and makes emulsification more difficult. At the same time, the compatibility between SBS and asphalt affects the storage stability of emulsified asphalt. SBS-modified asphalt is extremely difficult to emulsify, and even after emulsification under very special conditions, the stability of SBS-modified emulsified asphalt is extremely poor. Moreover, most SBS-modified asphalt emulsification is only at the laboratory stage and it is difficult to achieve large-scale production. At present, there is no mature production process for SBS-modified emulsified asphalt in the industry. Summary of the Invention
[0005] In view of the shortcomings of the existing technology, the purpose of this invention is to provide a production process for modified emulsified asphalt, which uses SBS as a modifier to modify the asphalt, thus taking into account the high and low temperature performance of emulsified asphalt and having good storage and placement stability.
[0006] The production process of the modified emulsified asphalt described in this invention includes the following steps:
[0007] (1) Preparation of soap solution
[0008] Add water to the reaction vessel, heat to 55-95℃, add emulsifier and emulsification aid, stir for 30 minutes, add acid-base adjuster to adjust pH to 1-4, and the soap solution is obtained.
[0009] (2) Modification of asphalt
[0010] Add base asphalt to a shear mill, shear at 3000-3500 rpm, heat to 165-220℃, add SBS modifier, compatibilizer and stabilizer, and maintain the temperature for 2-3 hours to obtain modified asphalt.
[0011] (3) Emulsification of modified asphalt
[0012] The soap solution obtained in step (1) and the modified asphalt obtained in step (2) are put into the American DALWORTH colloid mill for emulsification. After emulsification, the modified emulsified asphalt product is obtained by cooling.
[0013] The emulsifier in step (1) is a mixture of octadecyltrimethylammonium chloride, acidified oleylamine polyoxyethylene ether 12EO, and sodium dodecyl diphenyl ether disulfonate in a mass ratio of 3:(1.2-1.5):(0.2-0.5);
[0014] The solid material is ground and then passed through a 50-mesh sieve.
[0015] The mass ratio of the modified asphalt to the soap solution is (40-50):(50-60).
[0016] The preparation method of the acidified oleylamine polyoxyethylene ether 12EO is as follows: acetic acid is added to a container, then oleylamine polyoxyethylene ether 12EO is added, and the mixture is stirred evenly. The mass ratio of acetic acid to oleylamine polyoxyethylene ether 12EO is (0.2-0.3):5. The concentration of acetic acid is preferably 40 wt.%.
[0017] The emulsifying agent in step (1) is a mixture of calcium chloride and hydroxyethyl cellulose in a mass ratio of 1:(0.4-0.6).
[0018] The acid-base regulator in step (1) is a 30 wt.% aqueous solution of hydrochloric acid and citric acid in a mass ratio of 1:(3.5-4).
[0019] The SBS modifier mentioned in step (2) is a mixture of SBS modifier YH-4303 and SBS modifier YH-791 in a mass ratio of 1:(0.5-2).
[0020] The compatibilizer in step (2) is a naphthenic rubber oil. Preferably, it is naphthenic rubber oil of model 4010 from Jinan Runchang Chemical Co., Ltd.
[0021] The stabilizer mentioned in step (2) is HMD-2 type modified asphalt stabilizer.
[0022] The emulsification time in step (3) is 1-3 min, the temperature of the colloid mill is 55-95℃, and the pressure is 0.15-0.25 MPa.
[0023] The mixing mass ratio of water, emulsifier, and emulsifying aid in step (1) is 100:(7-10):(0.8-1.6).
[0024] In step (2), 7-11 wt.% SBS modifier, 1-2 wt.% compatibilizer, and 0.2-0.5 wt.% stabilizer are added to each ton of base asphalt.
[0025] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0026] (1) The present invention uses an emulsifier composed mainly of cationic surfactants, with the addition of nonionic surfactants and a small amount of anionic surfactants. Octadecyltrimethylammonium chloride is used in SBS modified asphalt to play a fusion role, which improves the physical properties of modified asphalt while maintaining its microstructure. At the same time, nonionic surfactants play a steric hindrance protection role. The introduction of a small amount of anionic surfactants prevents them from reacting with cationic surfactants to produce flocculents. The introduction of anionic surfactants can enhance the emulsification performance of the system, improve the storage stability of emulsified asphalt, and effectively improve its high and low temperature performance.
[0027] (2) In this invention, acetic acid is used to acidify oleamine polyoxyethylene ether. Originally a nonionic surfactant, oleamine polyoxyethylene ether will become weakly positive after acidification. Weakly positive surfactants are more suitable for emulsifying SBS modified asphalt and can improve the high and low temperature performance of emulsified asphalt.
[0028] (3) In this invention, all solid materials are ground to a finer mesh size of 50 mesh or more. The fine particle size makes the emulsified asphalt more stable and less prone to demulsification. Detailed Implementation
[0029] The present invention will be further described below with reference to the embodiments, but the scope of protection of the present invention is not limited thereto.
[0030] Unless otherwise specified, all raw materials used in the examples were commercially available.
[0031] Example 1
[0032] The production process of the modified emulsified asphalt includes the following steps:
[0033] (1) Preparation of soap solution
[0034] Water was added to the reaction vessel and the temperature was raised to 55°C. Then, a mixture of emulsifiers (octadecyltrimethylammonium chloride, acidified oleylamine polyoxyethylene ether 12EO, and sodium dodecyl diphenyl ether disulfonate in a mass ratio of 3:1.2:0.2) and emulsifying aids (calcium chloride and hydroxyethyl cellulose in a mass ratio of 1:0.4) were added and stirred for 30 minutes. Finally, a 30 wt.% aqueous solution of hydrochloric acid and citric acid in a mass ratio of 1:3.5 was added to adjust the pH to 1, thus obtaining the soap solution.
[0035] (2) Modification of asphalt
[0036] Add SK 70# base asphalt to a shear mill, shear speed at 3000 rpm, heat to 165℃, add SBS modifier: a mixture of YH-4303 type SBS modifier and YH-791 type SBS modifier in a mass ratio of 1:0.5, compatibilizer: naphthenic rubber oil 4010, and HMD-2 type modified asphalt stabilizer, and maintain the temperature for 2 hours to obtain modified asphalt;
[0037] (3) Emulsification of modified asphalt
[0038] The soap solution obtained in step (1) and the modified asphalt obtained in step (2) are put into a DALWORTH colloid mill in the United States for emulsification. The mass ratio of the modified asphalt and the soap solution is 50:50. The emulsification time is 3 minutes. The temperature of the colloid mill is 55°C and the pressure is 0.15 MPa. After emulsification, the modified emulsified asphalt product is obtained by cooling.
[0039] The solid material is ground and then passed through a 50-mesh sieve.
[0040] The preparation method of the acidified oleamine polyoxyethylene ether 12EO is as follows: add 40 wt.% acetic acid to a container, then add oleamine polyoxyethylene ether 12EO, and stir evenly. The mass ratio of acetic acid to oleamine polyoxyethylene ether 12EO is 0.2:5.
[0041] The mass ratio of water, emulsifier and emulsifying aid in step (1) is 100:7:0.8.
[0042] In step (2), 7 wt.% SBS modifier, 1 wt.% compatibilizer, and 0.2 wt.% stabilizer are added to each ton of base asphalt.
[0043] Example 2
[0044] The production process of the modified emulsified asphalt includes the following steps:
[0045] (1) Preparation of soap solution
[0046] Water was added to the reaction vessel and the temperature was raised to 75°C. Then, a mixture of emulsifiers (octadecyltrimethylammonium chloride, acidified oleylamine polyoxyethylene ether 12EO, and sodium dodecyl diphenyl ether disulfonate in a mass ratio of 3:1.3:0.4) and emulsifying aids (calcium chloride and hydroxyethyl cellulose in a mass ratio of 1:0.5) were added and stirred for 30 minutes. Finally, a 30 wt.% aqueous solution of hydrochloric acid and citric acid in a mass ratio of 1:3.7 was added to adjust the pH to 2.5, thus obtaining the soap solution.
[0047] (2) Modification of asphalt
[0048] Add SK 70# base asphalt to a shear mill, shear speed at 3300 rpm, heat to 180℃, add SBS modifier: a mixture of YH-4303 type SBS modifier and YH-791 type SBS modifier in a 1:1 mass ratio, compatibilizer: naphthenic rubber oil 4010, and HMD-2 type modified asphalt stabilizer, and maintain the temperature for 2.5 hours to obtain modified asphalt;
[0049] (3) Emulsification of modified asphalt
[0050] The soap solution obtained in step (1) and the modified asphalt obtained in step (2) were put into a DALWORTH colloid mill in the United States for emulsification. The mixing ratio of the modified asphalt and the soap solution was 48:52. The emulsification time was 2 minutes. The temperature of the colloid mill was 75°C and the pressure was 0.2 MPa. After emulsification, the modified emulsified asphalt product was obtained by cooling.
[0051] The solid material is ground and then passed through a 50-mesh sieve.
[0052] The preparation method of the acidified oleamine polyoxyethylene ether 12EO is as follows: 40 wt.% acetic acid is added to a container, then oleamine polyoxyethylene ether 12EO is added, and the mixture is stirred evenly. The mass ratio of acetic acid to oleamine polyoxyethylene ether 12EO is 0.25:5.
[0053] The mass ratio of water, emulsifier and emulsifying aid in step (1) is 100:8:1.2.
[0054] In step (2), 9 wt.% SBS modifier, 1.5 wt.% compatibilizer, and 0.3 wt.% stabilizer are added to each ton of base asphalt.
[0055] Example 3
[0056] The production process of the modified emulsified asphalt includes the following steps:
[0057] (1) Preparation of soap solution
[0058] Water was added to the reaction vessel and the temperature was raised to 95°C. Then, a mixture of emulsifiers (octadecyltrimethylammonium chloride, acidified oleylamine polyoxyethylene ether 12EO, and sodium dodecyl diphenyl ether disulfonate in a mass ratio of 3:1.5:0.5) and emulsifying aids (calcium chloride and hydroxyethyl cellulose in a mass ratio of 1:0.6) were added and stirred for 30 minutes. Finally, a 30 wt.% aqueous solution of hydrochloric acid and citric acid in a mass ratio of 1:4 was added to adjust the pH to 4, thus obtaining the soap solution.
[0059] (2) Modification of asphalt
[0060] Add SK 70# base asphalt to a shear mill, shear speed at 3500 rpm, heat to 220℃, add SBS modifier: a mixture of YH-4303 type SBS modifier and YH-791 type SBS modifier in a mass ratio of 1:2, compatibilizer: naphthenic rubber oil 4010, and HMD-2 type modified asphalt stabilizer, and maintain the temperature for 3 hours to obtain modified asphalt;
[0061] (3) Emulsification of modified asphalt
[0062] The soap solution obtained in step (1) and the modified asphalt obtained in step (2) are put into a DALWORTH colloid mill in the United States for emulsification. The mixing ratio of the modified asphalt and the soap solution is 45:55, the emulsification time is 1 min, the temperature of the colloid mill is 95℃, and the pressure is 0.25 MPa. After emulsification, the modified emulsified asphalt product is obtained by cooling.
[0063] The solid material is ground and then passed through a 50-mesh sieve.
[0064] The preparation method of the acidified oleamine polyoxyethylene ether 12EO is as follows: 40 wt.% acetic acid is added to a container, then oleamine polyoxyethylene ether 12EO is added and stirred evenly. The mass ratio of acetic acid to oleamine polyoxyethylene ether 12EO is 0.3:5.
[0065] The mass ratio of water, emulsifier, and emulsifying aid in step (1) is 100:10:1.6.
[0066] In step (2), 11 wt.% SBS modifier, 2 wt.% compatibilizer, and 0.5 wt.% stabilizer are added to each ton of base asphalt.
[0067] Comparative Example 1
[0068] The production process of the modified emulsified asphalt includes the following steps:
[0069] (1) Preparation of soap solution
[0070] Add water to the reaction vessel, heat to 55°C, add an emulsifier: a mixture of octadecyltrimethylammonium chloride, oleylamine polyoxyethylene ether 12EO, and sodium dodecyl diphenyl ether disulfonate in a mass ratio of 3:1.2:0.2, and an emulsifying aid: a mixture of calcium chloride and hydroxyethyl cellulose in a mass ratio of 1:0.4. Stir for 30 minutes, then add a 30 wt.% aqueous solution of hydrochloric acid and citric acid in a mass ratio of 1:3.5 to adjust the pH to 1 to obtain the soap solution.
[0071] (2) Modification of asphalt
[0072] Add SK 70# base asphalt to a shear mill, shear speed at 3000 rpm, heat to 165℃, add SBS modifier: a mixture of YH-4303 type SBS modifier and YH-791 type SBS modifier in a mass ratio of 1:0.5, compatibilizer: naphthenic rubber oil 4010, and HMD-2 type modified asphalt stabilizer, and maintain the temperature for 2 hours to obtain modified asphalt;
[0073] (3) Emulsification of modified asphalt
[0074] The soap solution obtained in step (1) and the modified asphalt obtained in step (2) were put into a DALWORTH colloid mill in the United States for emulsification. The mixing ratio of the soap solution and the modified asphalt was 40:60, the emulsification time was 3 minutes, the temperature of the colloid mill was 55°C, and the pressure was 0.15 MPa. After emulsification, the modified emulsified asphalt product was obtained by cooling.
[0075] The solid material is ground and then passed through a 50-mesh sieve.
[0076] The mass ratio of water, emulsifier and emulsifying aid in step (1) is 100:7:0.8.
[0077] In step (2), 7 wt.% SBS modifier, 1 wt.% compatibilizer, and 0.2 wt.% stabilizer are added to each ton of base asphalt.
[0078] Comparative Example 2
[0079] The production process of the modified emulsified asphalt includes the following steps:
[0080] (1) Preparation of soap solution
[0081] Add water to the reaction vessel, heat to 55°C, add emulsifier: a mixture of octadecyltrimethylammonium chloride and acidified oleylamine polyoxyethylene ether 12EO in a mass ratio of 3:1.2, and emulsifying aid: a mixture of calcium chloride and hydroxyethyl cellulose in a mass ratio of 1:0.4. Stir for 30 min, then add a 30 wt.% aqueous solution of hydrochloric acid and citric acid in a mass ratio of 1:3.5 to adjust the pH to 1 to obtain the soap solution.
[0082] (2) Modification of asphalt
[0083] Add SK 70# base asphalt to a shear mill, shear speed at 3000 rpm, heat to 165℃, add SBS modifier: a mixture of YH-4303 type SBS modifier and YH-791 type SBS modifier in a mass ratio of 1:0.5, compatibilizer: naphthenic rubber oil 4010, and HMD-2 type modified asphalt stabilizer, and maintain the temperature for 2 hours to obtain modified asphalt;
[0084] (3) Emulsification of modified asphalt
[0085] The soap solution obtained in step (1) and the modified asphalt obtained in step (2) were put into a DALWORTH colloid mill in the United States for emulsification. The mixing ratio of the soap solution and the modified asphalt was 40:60, the emulsification time was 3 minutes, the temperature of the colloid mill was 55°C, and the pressure was 0.15 MPa. After emulsification, the modified emulsified asphalt product was obtained by cooling.
[0086] The solid material is ground and then passed through a 50-mesh sieve.
[0087] The preparation method of the acidified oleamine polyoxyethylene ether 12EO is as follows: add 40 wt.% acetic acid to a container, then add oleamine polyoxyethylene ether 12EO, and stir evenly. The mass ratio of acetic acid to oleamine polyoxyethylene ether 12EO is 0.2:5.
[0088] The mass ratio of water, emulsifier and emulsifying aid in step (1) is 100:7:0.8.
[0089] In step (2), 7 wt.% SBS modifier, 1 wt.% compatibilizer, and 0.2 wt.% stabilizer are added to each ton of base asphalt.
[0090] Comparative Example 3
[0091] The production process of the modified emulsified asphalt includes the following steps:
[0092] (1) Preparation of soap solution
[0093] Water was added to the reaction vessel and the temperature was raised to 55°C. Then, a mixture of emulsifiers (octadecyltrimethylammonium chloride, acidified oleylamine polyoxyethylene ether 12EO, and sodium dodecyl diphenyl ether disulfonate in a mass ratio of 3:1.2:0.2) and emulsifying aids (calcium chloride and hydroxyethyl cellulose in a mass ratio of 1:0.4) were added and stirred for 30 minutes. Finally, a 30 wt.% aqueous solution of hydrochloric acid and citric acid in a mass ratio of 1:3.5 was added to adjust the pH to 1, thus obtaining the soap solution.
[0094] (2) Modification of asphalt
[0095] Add SK 70# base asphalt to a shear mill, shear speed at 3000 rpm, heat to 165℃, add SBS modifier: a mixture of YH-4303 type SBS modifier and YH-791 type SBS modifier in a mass ratio of 1:0.5, compatibilizer: naphthenic rubber oil 4010, and HMD-2 type modified asphalt stabilizer, and maintain the temperature for 2 hours to obtain modified asphalt;
[0096] (3) Emulsification of modified asphalt
[0097] The soap solution obtained in step (1) and the modified asphalt obtained in step (2) were put into a DALWORTH colloid mill in the United States for emulsification. The mixing ratio of the soap solution and the modified asphalt was 40:60, the emulsification time was 3 minutes, the temperature of the colloid mill was 55°C, and the pressure was 0.15 MPa. After emulsification, the modified emulsified asphalt product was obtained by cooling.
[0098] The solid material is ground and then passed through a 20-mesh sieve.
[0099] The preparation method of the acidified oleamine polyoxyethylene ether 12EO is as follows: add 40 wt.% acetic acid to a container, then add oleamine polyoxyethylene ether 12EO, and stir evenly. The mass ratio of acetic acid to oleamine polyoxyethylene ether 12EO is 0.2:5.
[0100] The mass ratio of water, emulsifier and emulsifying aid in step (1) is 100:7:0.8.
[0101] In step (2), 7 wt.% SBS modifier, 1 wt.% compatibilizer, and 0.2 wt.% stabilizer are added to each ton of base asphalt.
[0102] The above embodiments and comparative examples were tested, and the test results are shown in the table below:
[0103] Table 1 Test Results
[0104]
[0105]
[0106] In summary, the production process of the modified emulsified asphalt described in this invention can improve the low-temperature and high-temperature properties of asphalt, while effectively enhancing its storage stability.
Claims
1. A production process for modified emulsified asphalt, characterized in that, Includes the following steps: (1) Preparation of soap solution Add water to the reaction vessel, heat to 55-95℃, add emulsifier and emulsification aid, stir, add acid-base adjuster to adjust pH to 1-4, and the soap solution is obtained. (2) Modification of asphalt Add base asphalt to a shear mill, heat to 165-220℃, add SBS modifier, compatibilizer and stabilizer, and maintain the temperature for 2-3 hours to obtain modified asphalt. (3) Emulsification of modified asphalt The soap solution obtained in step (1) and the modified asphalt obtained in step (2) are put into a colloid mill for emulsification. After emulsification, the modified emulsified asphalt product is obtained by cooling. The emulsifier in step (1) is a mixture of octadecyltrimethylammonium chloride, acidified oleylamine polyoxyethylene ether 12EO, and sodium dodecyl diphenyl ether disulfonate in a mass ratio of 3:(1.2-1.5):(0.2-0.5); Solid materials are ground and then passed through a 50-mesh sieve. The mass ratio of the modified asphalt to the soap solution is (40-50):(50-60); The preparation method of the acidified oleamine polyoxyethylene ether 12EO is as follows: add acetic acid to a container, then add oleamine polyoxyethylene ether 12EO, and stir evenly. The mass ratio of acetic acid to oleamine polyoxyethylene ether 12EO is (0.2-0.3):
5. The emulsifying agent in step (1) is a mixture of calcium chloride and hydroxyethyl cellulose in a mass ratio of 1:(0.4-0.6).
2. The production process of modified emulsified asphalt according to claim 1, characterized in that, The acid-base regulator mentioned in step (1) is an aqueous solution of hydrochloric acid and citric acid in a mass ratio of 1:(3.5-4).
3. The production process of modified emulsified asphalt according to claim 1, characterized in that, The SBS modifier mentioned in step (2) is a mixture of SBS modifier YH-4303 and SBS modifier YH-791 in a mass ratio of 1:(0.5-2).
4. The production process of modified emulsified asphalt according to claim 1, characterized in that, The compatibilizer in step (2) is a cycloalkyl rubber oil.
5. The production process of modified emulsified asphalt according to claim 1, characterized in that, The stabilizer mentioned in step (2) is HMD-2 type modified asphalt stabilizer.
6. The production process of modified emulsified asphalt according to claim 1, characterized in that, The emulsification time in step (3) is 1-3 min, the temperature of the colloid mill is 55-95℃, and the pressure is 0.15-0.25 MPa.
7. The production process of modified emulsified asphalt according to claim 1, characterized in that, The mass ratio of water, emulsifier, and emulsifying aid in step (1) is 100:(7-10):(0.8-1.6).
8. The production process of modified emulsified asphalt according to claim 1, characterized in that, In step (2), 7-11 wt.% SBS modifier, 1-2 wt.% compatibilizer, and 0.2-0.5 wt.% stabilizer are added to the base asphalt.