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摘要: 以中温煤焦油沥青的四氢呋喃萃取物(THFS) 对石油基质沥青进行改性, 考察了掺混量、掺混温度和不同种类交联剂对改性沥青性能的影响, 确定了THFS最佳掺混量为8%, 最佳掺混温度为135 ℃, 甲醛交联剂的最佳掺混量为0.8%, 三聚甲醛的最佳掺混量为0.2%。考察了两两和单族组分对基质沥青的改性性能, 发现重油(HS) 使得改性沥青的针入度、延度增大, 沥青烯(A) 和甲苯不溶四氢呋喃可溶物(PA) 提高感温性, 软化点升高。随着醛类交联剂的添加, 提高了改性沥青的抗老化性能; 甲基(CH3)、亚甲基(CH2) 透射峰强度逐渐变强, 770-730 cm-1、710-690 cm-1和770-810 cm-1苯环取代透射峰强度逐渐增强, 1 010-1 270 cm-1处C-O-C伸缩振动峰逐渐增强; 热解峰温向高温移动, 残炭率增加2%;改性粒子呈现一种连续的流线分布, 添加三聚甲醛的改性沥青的流线分布更加集中。Abstract: Adopting tetrahydrofuran solubles of coal tar pitch (THFS) for petroleum asphalt modification, effects of different amounts of mixing, blending temperatures and cross-linking agent on the modified asphalt performance were examined. The optimum blending conditions were determined as amount of THFS, formaldehyde and trioxymethylene cross-linking agents being 8%, 0.8% and 0.2%, respectively at 135 ℃. Hexane soluble (HS) leads to the penetration and ductility of modified asphalt increase, but asphaltene (A) and preasphaltene (PA) improve the temperature sensitivity and raise the softening point. The addition of cross-linking agent improves the aging performance of modified asphalt; the methyl (CH3) and methylene (CH2) transmission peak intensity of modified asphalt gradually become stronger; the substituted benzene ring transmission peak intensity at 770-730 cm-1, 710-690 cm-1 and 770-810 cm-1 gradually increases, and C-O-C vibration transmission peak intensity of 1 010-1 270 cm-1 increases. The pyrolysis peak temperature moved to higher temperature, and the increase of char yield is about 2%. The modified particles exhibit a continuous distribution of flow lines, the streamline distribution of modified asphalt with adding trioxymethylene is more concentrated.
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Key words:
- petroleum asphalt /
- coal tar pitch /
- modification /
- pyrolysis /
- cross-linking agent
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表 1 中温煤焦油沥青性能
Table 1 Properties of CTP
Property Penetration,25 ℃, 100 g,5 s (0.1 mm) Softening point ring/ball t/ ℃ Ductility,25 ℃, 5 cm/min (cm) CTP 6.4 72.6 0.0 表 2 改性沥青针入度指数老化前后性质对比
Table 2 Comparison of properties of modified asphalt before and after aging
Property BSI BS-3690-350pen Content of THFS w/% 0 5 8 10 15 20 Penetration index PI - -0.96 -0.20 -0.34 0.05 0.22 0.53 retained properties after RTFOT (163 ℃, 85 min) Penetration index PI - 0.71 2.05 2.55 2.88 2.61 3.16 表 3 掺混温度对改性沥青性能的影响
Table 3 Effect of the mixing temperature on properties for the modified asphalt
Mixing temperature t/℃ Penetration,25 ℃, 100 g,5 s (0.1 mm) Penetration ratio,25 ℃(%) Softening point ring/ball t/ ℃ Ductility,15 ℃, 5 cm/min (cm) 125 before aging 53.4 55.2 52.8 > 150 after aging 29.5 76.6 6.7 135 before aging 52.4 56.5 53.1 > 150 after aging 29.6 76.5 6.5 145 before aging 50.2 55.3 54.4 > 150 after aging 27.8 77.6 6.4 155 before aging 47.8 53.1 55.6 124 after aging 25.4 79.0 6.1 表 4 煤沥青两两族组分对改性沥青性能的影响
Table 4 Effect of coal tar pitch between two ethnic components on modified asphalt
Property THFS HS+A HS+PA A+PA Penetration 25 ℃, 100 g, 5 s (0.1 mm) 52.4 68.1 64.4 47.9 Softening point ring/ball t/ ℃ 53.1 54.8 55.9 58.5 Ductility, 5 ℃, 5 cm/min (cm) > 150 131.8 114.0 62.5 Penetration index PI -0.34 0.07 0.61 0.60 表 5 煤沥青单族组分对改性沥青性能的影响
Table 5 Effect of coal tar pitch single-family component on modified asphalt
Property HS A PA Penetration 25 ℃, 100 g, 5 s (0.1 mm) 79.6 38.3 37.9 Softening point ring/ball t/ ℃ 49.7 64.2 65.1 Ductility 15 ℃, 5 cm/min (cm) 127.9 52.6 41.3 Penetration index PI 0.10 1.19 1.32 表 6 甲醛含量对改性沥青性能的影响
Table 6 Effects of formaldehyde content for the modified asphalt
Property BSI BS-3690 50pen Content of formaldehyde in 8T/70 /% 0 0.6 0.8 1.0 1.2 Penetration 25 ℃, 100 g, 5 s (0.1 mm) 40-60 52.4 54.9 57.8 56.4 55.9 Softening point ring/ball t/℃ 47-58 53.1 53.0 52.7 53.8 54.5 Ductility, 15 ℃, 5 cm/min (cm) - > 150 > 150 > 150 > 150 > 150 Ductility, 5 ℃, 5 cm/min (cm) - 60.4 61.7 75.5 64.5 62.9 Penetration index PI - -0.34 -0.25 -0.20 0 0.14 retained property after RTFOT*(163 ℃, 85 min) Penetration 25 ℃, 100 g, 5 s (0.1 mm) - 29.6 31.5 35.3 32.4 31.7 Penetration drop, 25 ℃, 100 g, 5 s (0.1 mm) 30 22.8 21.4 22.5 24 24.2 Penetration ratio, 25 ℃ (%) - 56.5 59.5 61.1 57.4 56.7 Softening point ring/ball, t/℃ - 76.5 76.3 76.0 76.6 77.5 Ductility, 15 ℃, 5 cm/min (cm) - 6.4 6.5 7.6 7.1 6.7 Weight loss w /% < 1.0 0.85 0.78 0.68 0.74 0.77 表 7 三聚甲醛含量对改性沥青性能的影响
Table 7 Effects of trioxymethylene content for the modified asphalt
Property BSI BS-369050pen Content of trioxymethylene in 8T/70 / % 0 0.2 0.4 Penetration 25 ℃, 100 g, 5 s (0.1 mm) 40-60 52.4 56.5 60.1 Softening point ring/ball t/℃ 47-58 53.1 53.0 52.3 Ductility, 15 ℃, 5 cm/min (cm) - > 150 > 150 > 150 Ductility, 5 ℃, 5 cm/min (cm) - 60.4 77.8 85.4 Penetration index PI - -0.34 -0.18 -0.21 表 8 TG与DTG分析结果
Table 8 TG and DTG analysis of different samples
Sample THFS 70 8T/70 15T/70 0.6%F-8T/70 0.4%TOX-8T/70 Stages 1 1 2 1 2 1 2 1 2 1 2 Initial temp. t/ ℃ 186 201 392 195 388 192 383 196 390 199 401 Peak temp. t/℃ 310 370 457 360 456 362 456 362 457 369 458 Final temp. t/ ℃ 526 392 532 388 527 383 525 390 529 401 532 Peak mass loss rate (%·℃-1) -0.49 -0.67 -0.60 -0.57 -0.61 -0.59 Mass loss w/% 81.79 79.84 79.27 78.27 77.27 77.14 Residue at 800 ℃/% 18.21 20.16 20.73 21.73 22.73 22.86 -
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