Reaction behaviors and synergistic effects for co-pyrolysis of Huadian oil shale and waste tire
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摘要: 为了提高油页岩热解制油的效率和半焦的利用价值，将桦甸油页岩和废轮胎共热解，采用热重分析仪和铝甑反应器考察共热解的失重行为、产物产率和组成性质，基于实验值和计算值的差异分析协同效应。结果表明，共热解可以促进挥发分的释放，500 ℃时实际失重量比计算值高，当废轮胎占比为80 % 时二者差值为2.86 %; 共热解过程存在“增油减水”效应，废轮胎占比为50 % 时实际油产率为32.91 %，比计算值高约1.5 %，实际水产率比计算值低1.20 % ~1.77 %，同时使热解油中大于350 ℃的重质组分含量升高; 废轮胎热解的半焦发热量达30.43 MJ/kg，热解气中C1—C4烃类含量更高，使共热解半焦和热解气的热值高于油页岩热解。Abstract: In order to improve the efficiency of oil shale pyrolysis and the utilization value of semi-coke, this paper co-pyrolyzed Huadian oil shale and waste tire.The weight loss behavior, product yield and composition properties of co-pyrolysis were investigated by thermogravimetric analyzer and aluminum retort reactor.The synergistic effect was analyzed based on the difference between experimental and calculated values.The results show that co-pyrolysis can promote the release of volatile matter, the actual weight loss is higher than the calculated value at 500 ℃, and reaches the maximum value of 2.86 % when the proportion of waste tire is 80 %.The mixed pyrolysis of oil shale and waste tire has the effect of "increasing oil and reducing water".When the waste tire accounts for 50 %, the actual oil yield is 32.91 %, which is 1.5 % higher than the calculated value, and the actual water yield is 1.20 % to 1.77 % lower than the calculated value.Meanwhile, the content of heavy components with boiling point higher than 350 ℃ in the pyrolysis oil increases.There is higher yield of C1~C4 hydrocarbons from waste tire pyrolysis, and the calorific value of semi-coke is up to 30.43 MJ/kg.Co-pyrolysis can also improve the calorific value of pyrolysis gas and semi-coke.
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Key words:
- oil shale /
- waste tire /
- co-pyrolysis characteristic /
- product distribution /
- synergistic effect
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图 1 铝甑热解实验装置示意图
1—质量流量计; 2—环式电阻炉; 3—铝甑; 4—热电偶; 5—锥形瓶; 6—冰水浴; 7—干燥管; 8—有机玻璃瓶; 9—U型管压力计; 10—水龙头
Figure 1. Aluminum retort pyrolysis apparatus
图 3 不同配比共热解的实际失重量与计算失重量
Figure 3. Actual and calculated weight losses for co-pyrolysis with different ratios
图 4 油页岩与废轮胎共热解产物产率
Figure 4. Product yields for co-pyrolysis of oil shale and waste tire
图 5 共热解产物产率的计算值与实验值
Figure 5. Calculated and experimental product yields for co-pyrolysis of oil shale and waste tyre
表 1 油页岩和废轮胎的工业分析及元素分析
Table 1. Proximate and ultimate analyses of oil shale and waste tyre
% 样品 工业分析 元素分析(daf) Mad Ad Vd FCd C H N S O* 油页岩 5.99 73.13 25.39 1.48 74.19 11.11 2.12 4.45 8.13 废轮胎 0.94 14.71 59.13 26.16 80.76 8.76 0.91 2.65 6.92 注：*为氧含量由差减法计算。 
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表 2 不同配比共热解实际失重量与计算失重量的差值
Table 2. Differences between actual and calculated weight losses for co-pyrolysis with different ratios
废轮胎质量分数/% 失重量差值/% 500 ℃ 900 ℃ 20 -0.03 0.25 40 0.48 0.72 50 1.07 0.98 60 1.74 1.45 80 2.86 2.45
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表 3 热解油的元素分析和馏分组成
Table 3. Ultimate analysis and fraction composition of pyrolysis oil
样品 元素分析/% H/C 馏分组成/% C H N S O ＜180 ℃ 180~350 ℃ >350 ℃ 页岩油 82.36 11.35 1.16 1.04 4.09 1.65 11.10 41.17 47.74 轮胎油 81.13 10.21 0.76 0.84 7.06 1.51 9.97 45.19 44.84 共热解油 81.37 10.15 0.83 0.92 6.73 1.50 9.94 39.32 50.74
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表 4 热解油中氢原子的相对含量
Table 4. Hydrogens content in the oil samples
化学位移/10-6 相对含量/% 油页岩油 废轮胎油 共热解油 6~10(芳氢) 6.30 10.07 8.68 2~4.5(α-氢) 9.20 19.49 14.17 1~2(β-氢) 69.62 52.51 57.66 0.1~1(γ-氢) 14.89 17.93 19.49
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表 5 油页岩和废轮胎热解气的组分产率
Table 5. Gas component yields for co-pyrolysis of oil shale and waste tire
气体组分 气体组分产率/(mL·g-1) 油页岩 废轮胎 共热解(实验值) 共热解(计算值) H2 8.76 4.45 8.80 6.61 CO 1.27 0.96 1.49 1.12 CO2 6.05 3.94 5.99 4.99 CH4 3.20 5.82 4.85 4.51 C2H6 1.34 2.26 1.90 1.80 C2H4 0.55 1.65 1.03 1.10 C3H8 0.56 1.22 0.95 0.89 C3H6 0.74 0.94 0.93 0.84 C4H10 0.26 0.63 0.46 0.44 1-C4H8 0.08 0.32 0.30 0.20
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表 6 共热解半焦的工业分析和发热量
Table 6. Proximate analysis and calorific value of co-pyrolysis semi-coke
废轮胎质量分数/% 工业分析/% 发热量/ (MJ·kg-1) Mad Ad Vd FCd Qad 0 0.00 86.19 10.91 2.90 4.36 20 0.10 77.38 10.34 12.28 5.19 40 0.32 67.70 8.60 23.70 9.55 50 0.00 61.49 8.47 30.04 11.81 60 0.31 54.78 7.74 37.48 15.86 80 0.19 37.40 6.08 56.52 20.94 100 0.27 11.24 3.50 85.26 30.43
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