阅读说明：本技术 一种改质沥青及其制备方法 (Modified asphalt and preparation method thereof ) 是由 田晓学 张鑫贺 马丛宇 于 2020-06-03 设计创作，主要内容包括：本发明公开了一种改质沥青的制备方法,所述制备方法包括以下步骤：S01将石油系沥青添加剂和软化点为70～90℃的中温沥青混合,混合时间为10～120min,保持气压为20～80kPa,保持温度为360～380℃,形成第一混合物；S02将所述第一混合物在-60～-40kpa真空条件下进行闪蒸,闪蒸时间为20～100min,蒸发的轻组分进行冷却和分离,闪蒸后的剩余物即为改质沥青。本发明还公开了一种改质沥青。本发明的制备的改质沥青与其他相同的软化点范围改质沥青相比,结焦值和β树脂含量都有提高；采用闪蒸工艺,不需要加入即可以完成蒸馏,节能降耗,符合低碳经济的发展趋势,减少了环境污染。(The invention discloses a preparation method of modified asphalt, which comprises the following steps: s01, mixing the petroleum asphalt additive and medium-temperature asphalt with a softening point of 70-90 ℃ for 10-120 min, keeping the air pressure at 20-80 kPa and the temperature at 360-380 ℃ to form a first mixture; s02, carrying out flash evaporation on the first mixture under the vacuum condition of-60 to-40 kpa for 20-100 min, cooling and separating evaporated light components, and obtaining the residue after flash evaporation, namely the modified asphalt. The invention also discloses modified asphalt. Compared with other modified asphalt with the same softening point range, the coking value and the beta resin content of the modified asphalt prepared by the invention are improved; the distillation can be completed without adding a flash evaporation process, so that the energy is saved, the consumption is reduced, the development trend of low-carbon economy is met, and the environmental pollution is reduced.)

1. The preparation method of the modified asphalt is characterized by comprising the following steps:

s01, mixing the petroleum asphalt additive and medium temperature asphalt with the softening point of 70-90 ℃ for 10-120 min, keeping the air pressure at 20-80 kPa and the temperature at 360-380 ℃ to form a first mixture;

and S02, carrying out flash evaporation on the first mixture under the vacuum condition of-60 to-40 kpa for 20-100 min, cooling and separating evaporated light components, and obtaining the residue after flash evaporation, namely the modified asphalt.

2. The method of claim 1, wherein the petroleum-based asphalt additive is one or more of ethylene tar and catalytic cracking clarified slurry oil.

3. The method for producing modified asphalt according to claim 1, wherein the mass ratio of the petroleum asphalt additive to the medium-temperature asphalt is (1:9) - (4: 6).

4. The method of claim 1, wherein carbon black is added to the petroleum-based asphalt additive and the mixture is stirred at a constant temperature (S00) before the step of S01.

5. The method of claim 4, wherein the amount of carbon black added is 25% to 50% by mass of the petroleum asphalt additive.

6. An upgraded asphalt prepared by the method according to any one of claims 1 to 5.

7. The modified asphalt of claim 6, wherein the modified asphalt has a softening point of 105 to 110 ℃, a coking value of 60% or more, and a beta resin of 22% or more.

8. The process for producing an upgraded asphalt according to claim 1, wherein the medium-temperature asphalt is refined medium-temperature asphalt having a low quinoline insoluble content.

9. The method of claim 8, wherein the petroleum-based asphalt additive is one or more of ethylene tar and catalytic cracking clarified slurry oil.

10. The method for producing modified asphalt according to claim 8, wherein the mass ratio of the petroleum asphalt additive to the refined medium-temperature asphalt having a low quinoline insoluble content is (1:9) - (4: 6).

11. The process of claim 8, wherein carbon black is added to the petroleum asphalt additive and the mixture is stirred at a constant temperature before the step S01.

12. The method of claim 11, wherein the amount of carbon black added is 25% to 50% by mass of the petroleum asphalt additive.

13. An upgraded asphalt prepared by the method according to any one of claims 8 to 12.

14. The modified asphalt of claim 13, wherein the modified asphalt has a softening point of 100 to 110 ℃, a coking value of 57 to 65%, and a β resin of 18 to 25%.

Technical Field

The invention relates to the technical field of asphalt deep processing, in particular to modified asphalt and a preparation method thereof.

Background

The current industrial production methods of modified asphalt mainly include 2 thermal polycondensation methods and a vacuum flash evaporation method, wherein the vacuum flash evaporation method is that medium-temperature asphalt is vaporized under the vacuum condition, so that the softening point and the coke yield of the asphalt are increased, and toluene insoluble substances and quinoline insoluble substances are changed less. The thermal polycondensation method can be divided into a kettle type heating method and a tube furnace heating method according to the heating mode, and can be divided into 3 methods of negative pressure, normal pressure and pressurization according to the operation pressure; the process for producing modified asphalt by using a normal-pressure and pressurized tube furnace is less applied in China, and the application of the process for producing modified asphalt by using a heating negative pressure of the domestic tube furnace belongs to the just-rising stage at present.

The literature is searched, and the quality improvement of the modified or impregnated asphalt is mainly carried out from the aspects of process, parameters and equipment, and the literature for preparing the modified asphalt by changing the raw material components and improving the reaction system is less. Chinese patent CN104946288A discloses that coal liquefied asphalt is used as raw material, coke powder or coal powder is used as modifier, and after mixing and melting with heavy oil and cross-linking agent, the mixture is fully mixed with catalyst, and then cross-linking polymerization reaction is carried out under pressurized condition to obtain modified asphalt; chinese patent CN103740395B discloses that high-temperature asphalt is used as a raw material, heavy oil and a crosslinking agent are added firstly to slowly raise the temperature to obtain molten asphalt, and then the high-temperature asphalt is subjected to a crosslinking polymerization reaction under the action of a catalyst to obtain modified asphalt with a low softening point and a high beta resin content; the softening points of the raw materials are both high, the softening point of the coal liquefied asphalt is 130-150 ℃, and the softening point of the high-temperature asphalt is 115-160 ℃. Therefore, the energy consumption in the production process is high, and the development trend of low-carbon economy is not met.

Therefore, there is still a need for improvement of the prior art and a more reasonable technical solution to solve the above technical problems.

Disclosure of Invention

In order to solve the problems, the invention aims to provide a method for preparing modified asphalt with low energy consumption, low loss and low raw material softening point and high beta resin content through modification.

The invention is realized by the following technical scheme:

a process for producing an upgraded asphalt, the process comprising the steps of:

s01, mixing the petroleum asphalt additive and medium temperature asphalt with the softening point of 70-90 ℃ for 10-120 min, keeping the air pressure at 20-80 kPa and the temperature at 360-380 ℃ to form a first mixture;

and S02, carrying out flash evaporation on the first mixture under the vacuum condition of-60 to-40 kpa for 20-100 min, cooling and separating evaporated light components, and obtaining the residue after flash evaporation, namely the modified asphalt.

Preferably, the petroleum asphalt additive is one or more of ethylene tar, catalytic clarified slurry oil and cracking clarified slurry oil.

Preferably, the mass ratio of the petroleum asphalt additive to the medium-temperature asphalt is (1:9) - (4: 6).

Preferably, before the S01 step, carbon black is added to the petroleum-based asphalt additive and constant-temperature stirring is performed (step S00).

Preferably, the addition amount of the carbon black accounts for 25-50% of the mass of the petroleum asphalt additive.

It is another object of the present invention to provide an upgraded asphalt.

The modified asphalt is prepared by adopting the preparation method of any one technical scheme.

Preferably, the modified asphalt has a softening point of 105-110 ℃, a coking value of not less than 60% and a beta resin of not less than 22%.

In another embodiment of the modified asphalt preparation method, preferably, the medium-temperature asphalt is refined medium-temperature asphalt with low quinoline insoluble content.

Preferably, the petroleum asphalt additive is one or more of ethylene tar, catalytic clarified slurry oil and cracking clarified slurry oil.

Preferably, the mass ratio of the petroleum asphalt additive to the refined medium-temperature asphalt with low quinoline insoluble content is (1:9) - (4: 6).

Preferably, before the S01 step, carbon black is added to the petroleum-based asphalt additive and constant-temperature stirring is performed (step S00).

Preferably, the addition amount of the carbon black accounts for 25-50% of the mass of the petroleum asphalt additive.

The modified asphalt is prepared by adopting the preparation method of any one technical scheme.

Preferably, the modified asphalt has a softening point of 100-110 ℃, a coking value of 57-65% and beta resin of 18-25%.

Compared with the prior art, the invention has the beneficial effects that:

1. the distillation can be completed without adding a flash evaporation process, so that the energy is saved, the consumption is reduced, the development trend of low-carbon economy is met, and the environmental pollution is reduced.

2. The medium temperature pitch is added with carbon black with a certain proportion, so that a reaction system can be improved, and the generation of large anisotropy can be inhibited in a proper proportion.

3. Compared with other modified asphalt with the same softening point range, the coking value of the prepared modified asphalt is improved by 4-15%, and the beta resin is improved by 10-25%.

Drawings

FIG. 1 is a step of a process for producing upgraded pitch in one embodiment of the present invention;

FIG. 2 is a schematic flow diagram of a process for producing upgraded pitch in an embodiment of the present invention;

FIG. 3 is a step of the process for producing upgraded pitch in another embodiment of the present invention;

FIG. 4 is a schematic flow diagram of a process for producing upgraded pitch in another embodiment of the present invention;

FIG. 5 is a schematic flow diagram of a process for producing upgraded pitch in another embodiment of the present invention;

fig. 6 is a schematic flow diagram of a process for producing upgraded pitch in another embodiment of the present invention.

Detailed Description

The invention is described in further detail below with reference to the following detailed description and accompanying drawings:

as shown in fig. 1 and 2, the method for producing the modified asphalt of the present invention comprises the steps of:

s01, mixing the petroleum asphalt additive and medium temperature asphalt with the softening point of 70-90 ℃ for 10-120 min, keeping the air pressure at 20-80 kPa and the temperature at 360-380 ℃ to form a first mixture;

and S02, carrying out flash evaporation on the first mixture under the vacuum condition of-60 to-40 kpa for 20-100 min, cooling and separating evaporated light components, and obtaining the residue after flash evaporation, namely the modified asphalt.

The modified asphalt prepared by the method not only has a reduced softening point, but also has improved beta resin content, quinoline insoluble content and coking value, and the modified asphalt with lower softening point and improved beta resin content, quinoline insoluble content and coking value meets the requirements of modified asphalt meeting national standards through detection. The modified asphalt with relatively low softening point and improved beta resin content and quinoline insoluble content has good bonding performance and high coking value, and can meet the requirement of modified asphalt required in the market.

Flash principle: after the high pressure saturated liquid enters the relatively low pressure vessel, the saturated liquid becomes a portion of the saturated vapor and saturated liquid at the vessel pressure due to the sudden drop in pressure. The boiling point of a substance increases with increasing pressure, while the lower the pressure, the lower the boiling point. Therefore, the high-pressure high-temperature fluid can enter the flash tank after being decompressed to reduce the boiling point, the temperature of the fluid is higher than the boiling point under the pressure, the fluid is boiled and vaporized in the flash tank rapidly, and two phases are separated. Flash evaporation does not require heating.

Further, the petroleum asphalt additive is one or more of ethylene tar and catalytic cracking clarified slurry oil. The petroleum asphalt additive has certain viscosity, can be used as a solvent to dissolve medium-temperature asphalt, and can form medium-temperature asphalt slurry with good fluidity and stability with the medium-temperature asphalt. The petroleum asphalt additive maintains a sufficient liquid phase during the flashing process of step S02, and the petroleum asphalt additive can sufficiently exert the heat transfer function of the solvent.

Further, the mass ratio of the petroleum asphalt additive to the medium-temperature asphalt is (1:9) - (4: 6). When the mass ratio is (1:9) - (4:6), the petroleum asphalt additive has good dissolving and impregnating effects on medium-temperature asphalt, and the medium-temperature asphalt cannot be completely dissolved and impregnated when the dosage is too small; when the amount is too much, not only the production cost is increased, but also the resource waste is caused.

Further, referring to fig. 3 and 4, before the step S01, carbon black is added to the petroleum-based asphalt additive and stirred at a constant temperature (step S00). The carbon black acts to increase the quinoline insoluble content of the pitch. In the preferred embodiment, the diameter of the coke powder is not particularly limited as long as it can be uniformly mixed with the medium temperature pitch. The addition of carbon black in certain proportion can improve the reaction system and inhibit the formation of great anisotropy. In a preferred embodiment of the present invention, the carbon black has a diameter of 180um or less. Carbon black having a diameter within this range can be uniformly mixed with the asphalt.

Furthermore, the addition amount of the carbon black accounts for 25-50% of the mass of the petroleum asphalt additive. When the using amount of the carbon black accounts for 25-50% of the mass of the petroleum asphalt additive, the quinoline insoluble content and the coking value can be effectively improved, and the modified asphalt standard is reached; when the content is less than 25wt%, the content standard of quinoline insoluble substances in the modified asphalt cannot be met, so that the coking value is low; when the content is more than 50wt%, the content exceeds the modified asphalt quinoline insoluble content standard, and the asphalt adhesiveness is liable to be adversely affected.

It is another object of the present invention to provide an upgraded asphalt.

The modified asphalt is prepared by adopting the preparation method of any one technical scheme.

Furthermore, the modified asphalt has a softening point of 105-110 ℃, a coking value of not less than 60% and a beta resin of not less than 22%.

In another embodiment of the modified asphalt preparation method, the medium-temperature asphalt is refined medium-temperature asphalt with low quinoline insoluble content (QI). The flow chart is schematically shown in FIG. 5.

Further, the petroleum asphalt additive is one or more of ethylene tar and catalytic cracking clarified slurry oil.

Further, the mass ratio of the petroleum asphalt additive to the refined medium-temperature asphalt with low quinoline insoluble content is (1:9) - (4: 6).

Further, before step S01, carbon black is added to the petroleum-based asphalt additive, and constant-temperature stirring is performed (step S00). The carbon black acts to increase the quinoline insoluble content of the pitch. In the preferred embodiment, the diameter of the coke powder is not particularly limited, as long as it can be uniformly mixed with the refined medium-temperature pitch having a low quinoline insoluble content. The addition of carbon black in certain proportion can improve the reaction system and inhibit the formation of great anisotropy. In a preferred embodiment of the present invention, the carbon black has a diameter of 180um or less. Carbon black having a diameter within this range can be uniformly mixed with the asphalt. The flow chart is as shown in FIG. 6.

Furthermore, the addition amount of the carbon black accounts for 25-50% of the mass of the petroleum asphalt additive. When the using amount of the carbon black accounts for 25-50% of the mass of the petroleum asphalt additive, the quinoline insoluble content and the coking value can be effectively improved, and the modified asphalt standard is reached; when the content is less than 25wt%, the content standard of quinoline insoluble substances in the modified asphalt cannot be met, so that the coking value is low; when the content is more than 50wt%, the content exceeds the modified asphalt quinoline insoluble content standard, and the asphalt adhesiveness is liable to be adversely affected.

The modified asphalt is prepared by adopting the preparation method of any one technical scheme.

Furthermore, the modified asphalt has a softening point of 100-110 ℃, a coking value of 57-65% and beta resin of 18-25%.

The advantageous effects of the present invention will be further described with reference to specific examples.

The medium temperature asphalts selected in the examples 1 to 5 are all medium temperature asphalts purchased from other manufacturers, and the refined medium temperature asphalts with low quinoline insoluble substance content selected in the examples 6 to 10 are all refined medium temperature asphalts purchased from other manufacturers.

Example 1

Mixing 10 parts by mass of ethylene tar and 90 parts by mass of medium-temperature asphalt with a softening point of 80 ℃ for 10min, keeping the air pressure at 20kPa and the temperature at 380 ℃ to form a first mixture;

and (3) carrying out flash evaporation on the first mixture under the vacuum condition of-40 kpa, wherein the flash evaporation time is 20min, cooling and separating evaporated light components, and obtaining the residue after flash evaporation, namely the modified asphalt.

Example 2

Adding 5 parts by mass of carbon black into 10 parts by mass of ethylene tar, stirring at a constant temperature, and mixing with 85 parts by mass of medium-temperature asphalt with a softening point of 70 ℃, wherein the mixing time is 40min, the air pressure is kept at 40kPa, and the temperature is kept at 360 ℃ to form a first mixture;

and (3) carrying out flash evaporation on the first mixture under the vacuum condition of-50 kpa for 30min, cooling and separating evaporated light components, and obtaining the residue after flash evaporation, namely the modified asphalt.

Example 3

Adding 4 parts by mass of carbon black into 10 parts by mass of ethylene tar, stirring at a constant temperature, and mixing with 86 parts by mass of medium-temperature asphalt with a softening point of 80 ℃, wherein the mixing time is 60min, the air pressure is kept at 60kPa, and the temperature is kept at 380 ℃ to form a first mixture;

and (3) carrying out flash evaporation on the first mixture under the vacuum condition of-55 kpa, wherein the flash evaporation time is 50min, cooling and separating evaporated light components, and obtaining the residue after flash evaporation, namely the modified asphalt.

Example 4

Adding 10 parts by mass of carbon black into 40 parts by mass of ethylene tar, stirring at a constant temperature, and mixing with 50 parts by mass of medium-temperature asphalt with a softening point of 90 ℃, wherein the mixing time is 120min, the air pressure is kept at 80kPa, and the temperature is kept at 380 ℃ to form a first mixture;

and (3) carrying out flash evaporation on the first mixture under the vacuum condition of-60 kpa, wherein the flash evaporation time is 100min, cooling and separating evaporated light components, and obtaining the residue after flash evaporation, namely the modified asphalt.

Example 5

Adding 4 parts by mass of carbon black into 10 parts by mass of a mixture of ethylene tar and catalytic cracking clarified slurry oil, stirring at a constant temperature, mixing with 86 parts by mass of medium-temperature asphalt with a softening point of 80 ℃, mixing for 120min, keeping the air pressure at 40kPa and the temperature at 380 ℃ to form a first mixture;

and (3) carrying out flash evaporation on the first mixture under the vacuum condition of-55 kpa, wherein the flash evaporation time is 60min, cooling and separating evaporated light components, and obtaining the residue after flash evaporation, namely the modified asphalt.

Example 6

Mixing 10 parts by mass of ethylene tar and 90 parts by mass of refined medium-temperature pitch with a low quinoline insoluble content and a softening point of 80 ℃ for 10min, keeping the air pressure at 20kPa and the temperature at 380 ℃ to form a first mixture;

and (3) carrying out flash evaporation on the first mixture under the vacuum condition of-40 kpa, wherein the flash evaporation time is 20min, cooling and separating evaporated light components, and obtaining the residue after flash evaporation, namely the modified asphalt.

Example 7

Adding 5 parts by mass of carbon black into 10 parts by mass of ethylene tar, stirring at a constant temperature, and mixing with 85 parts by mass of refined medium-temperature pitch with a softening point of 70 ℃ and a low quinoline insoluble content for 40min, keeping the air pressure at 40kPa and the temperature at 380 ℃ to form a first mixture;

and (3) carrying out flash evaporation on the first mixture under the vacuum condition of-50 kpa for 30min, cooling and separating evaporated light components, and obtaining the residue after flash evaporation, namely the modified asphalt.

Example 8

Adding 4 parts by mass of carbon black into 10 parts by mass of ethylene tar, stirring at a constant temperature, and mixing with 86 parts by mass of refined medium-temperature pitch with a low quinoline insoluble content and a softening point of 80 ℃, wherein the mixing time is 60min, the air pressure is kept at 60kPa, and the temperature is kept at 380 ℃ to form a first mixture;

and (3) carrying out flash evaporation on the first mixture under the vacuum condition of-55 kpa, wherein the flash evaporation time is 50min, cooling and separating evaporated light components, and obtaining the residue after flash evaporation, namely the modified asphalt.

Example 9

Adding 10 parts by mass of carbon black into 40 parts by mass of ethylene tar, stirring at a constant temperature, and mixing with 50 parts by mass of refined medium-temperature pitch with a low quinoline insoluble content and a softening point of 90 ℃, wherein the mixing time is 120min, the air pressure is kept at 80kPa, and the temperature is kept at 380 ℃ to form a first mixture;

and (3) carrying out flash evaporation on the first mixture under the vacuum condition of-60 kpa, wherein the flash evaporation time is 100min, cooling and separating evaporated light components, and obtaining the residue after flash evaporation, namely the modified asphalt.

Example 10

Adding 4 parts by mass of carbon black into a mixture of 10 parts by mass of ethylene tar and catalytic cracking clarified slurry oil, stirring at a constant temperature, and mixing with 86 parts by mass of refined medium-temperature pitch with a low quinoline insoluble content and a softening point of 80 ℃, wherein the mixing time is 120min, the air pressure is kept at 40kPa, and the temperature is kept at 380 ℃ to form a first mixture;

and (3) carrying out flash evaporation on the first mixture under the vacuum condition of-55 kpa, wherein the flash evaporation time is 60min, cooling and separating evaporated light components, and obtaining the residue after flash evaporation, namely the modified asphalt.

Comparative example 1

Modified asphalt produced by a certain manufacturer with a commercial softening point of 103 ℃ is selected.

Comparative example 2

Modified bitumen produced by a certain commercial producer with a softening point of 106 ℃ is selected.

Comparative example 3

Modified asphalt produced by a certain manufacturer with a commercially available softening point of 109 ℃ is selected.

Comparative example 4

Modified bitumen produced by a certain commercial producer with a softening point of 112 ℃ is selected.

Comparative example 5

Modified asphalt produced by a certain manufacturer with a softening point of 118 ℃ is selected and sold.

And (3) detection:

the modified asphalts obtained in comparative examples 1 to 5 and examples 1 to 10 were tested for their properties, and the results are shown in Table 1.

Wherein the softening point is determined by adopting a standard GB/T2292-2019, the content of Toluene Insoluble (TI) is determined by adopting a standard GB/T2292-2018, the content of Quinoline Insoluble (QI) is determined by adopting a standard GB/T2293-2019, the difference value obtained by subtracting the content of the quinoline insoluble from the content of the toluene insoluble is the content of beta resin, and the coking value is determined by adopting a GB/T8727-2008 method.

	Softening point/. degree.C	TI/wt%	QI/wt%	Beta resin content/wt%	Coking value/wt%
						Example 1	105	34	9	25	61
Example 2	105	36	12	24	62
						Example 3	107	35	9	26	65
Example 4	120	39	10	29	69
						Example 5	108	32	7	25	64
Example 6	103	22	0.23	22	58
						Example 7	105	23	0.34	23	59
Example 8	110	25	0.33	25	60
						Example 9	118	28	0.40	28	67
Example 10	112	26	0.32	26	62
						Comparative example 1	103	20	3	18	54
Comparative example 2	106	23	3	20	56
						Comparative example 3	109	26	3	23	52
Comparative example 4	112	27	6	21	55
						Comparative example 5	118	26	6	20	52

Table 1:

the components and the structure of the medium-temperature asphalt can be changed by adding the petroleum asphalt additive with a certain proportion into the medium-temperature asphalt, the quality of the product is difficult to improve by adjusting the process parameters due to the factors of the components of the raw materials in the actual production process, and the purposes can be achieved by changing the components and the structure of the raw materials; the medium temperature pitch is added with carbon black with a certain proportion, so that a reaction system can be improved, and the generation of large anisotropy can be inhibited in a proper proportion; the distillation can be completed without adding a flash evaporation process, so that energy is saved; compared with other modified asphalt with the same softening point range, the coking value of the modified asphalt prepared in the examples 1-5 is improved by 9-15%, and the beta resin is improved by 10%; compared with other modified asphalt with the same softening point range, the coking value of the modified asphalt prepared in the embodiments 6-10 is improved by 4-15%, and the beta resin is improved by 10-25%.

The modified asphalt prepared by the invention has low softening point, improved beta resin content, quinoline insoluble content and coking value and better bonding property, and can obtain better application effect when being applied to high-temperature binder asphalt, such as being used as a binder for carbon industry, a waterproof coiled material and the like.

The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.